Preparation method and application of heterogeneous structure polymer-based heat-conducting composite material with heat transfer-potential dual synergistic heat dissipation mode

Abstract

The present application relates to the field of polymer-based high-thermal-conductivity composite materials, and particularly relates to a preparation method and application of a heterogeneous structure polymer-based thermal-conductivity composite material with heat transfer-potential dual synergistic heat dissipation mode; the present application solves the problems of single heat dissipation mode and low heat dissipation efficiency of the existing polymer-based thermal-conductivity composite material. The heterogeneous structure polymer-based thermal-conductivity composite material is divided into two layers, the lower layer structure is a boron nitride / natural rubber composite material (BN / NR) with boron nitride (BN) as the thermal-conductivity filler, and the heat transfer performance is rapidly improved through the construction of a thermal-conductivity network; the upper layer structure is a phase change heat absorption structure layer mainly composed of a porous structure water absorption material, and the latent heat absorption energy is used to achieve the effect of heat dissipation and cooling. The heat transfer-potential dual synergistic effect involved in the present application can significantly improve the heat dissipation mode of the polymer-based composite material, and is expected to be used as a new generation of packaging materials for electronic devices. In addition, the preparation method of the present application is simple, pollution-free, and the required instruments are easy to operate, so that the industrial production is easy.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of polymer-based high-thermal-conductivity composite materials, and in particular to a preparation method and application of a heterogeneous structure polymer-based thermal-conductivity composite material with heat transfer-potential dual synergistic heat dissipation. BACKGROUND

[0002] With the rapid development of the fifth generation communication technology, electronic devices and equipment have developed towards miniaturization, multifunctionalization and high integration, and are widely used in various fields of national life. At present, high-integration electronic devices will continuously generate heat accumulation during operation, which will cause the temperature of the electronic devices to rise sharply if not eliminated in time, thereby causing a serious decline in the efficiency and service life of the equipment. Therefore, the heat dissipation problem of electronic devices has gradually become a bottleneck restricting the development of technology in the field of electronic devices. In order to improve the functional stability and service life of electronic devices, polymer-based thermal-conductivity composite materials have become key materials for heat dissipation of electronic devices. Therefore, the preparation of polymer-based thermal-conductivity composite materials with strong heat dissipation capacity plays an important role in the field of modern electronic packaging. SUMMARY

[0003] The present application provides a preparation method of a heterogeneous structure polymer-based thermal-conductivity composite material with heat transfer-potential dual synergistic heat dissipation to solve the technical problems of low heat dissipation efficiency and complex preparation process of existing polymer-based thermal-conductivity composite materials. The heat dissipation capacity of the polymer-based thermal-conductivity composite material is enhanced by combining the synergistic mode of heat transfer and latent heat energy absorption.

[0004] To solve the above technical problems, the technical scheme adopted by the present application is as follows: a preparation method of a heterogeneous structure polymer-based thermal-conductivity composite material with heat transfer-potential dual synergistic heat dissipation, comprising the following steps:

[0005] (1) uniformly dispersing chromium chloride hexahydrate and terephthalic acid in deionized water, stirring vigorously at room temperature, and then placing the mixed solution in a high-pressure reaction kettle, reacting at a certain temperature and time, and then centrifuging and purifying to obtain a porous water-absorbing MOF material;

[0006] (2) dispersing the hydroxyl-modified BN-OH in deionized water, adding to natural latex after ultrasonic, and mechanically stirring to obtain a uniform mixed dispersion liquid, and then slowly adding the mixed dispersion liquid to a vacuum-assisted filtration device for filtration to obtain a high-thermal-conductivity transfer layer structure mainly composed of BN / NR;

[0007] (3) adding the water-absorbing MOF material into deionized water to obtain a MOF dispersion liquid by ultrasonic treatment, adding a certain amount of cellulose to further ultrasonic treatment, and then obtaining a MOF / CNF dispersion liquid, and slowly adding the MOF / CNF dispersion liquid onto the heat transfer layer structure to continue vacuum-assisted filtration, and obtaining a heterogeneous structure polymer-based composite material combined with the heat transfer layer structure and the latent heat energy absorption layer structure after the filtration is completed;

[0008] (4) placing the heterogeneous structure polymer-based composite material prepared in step (3) in a vacuum drying oven, drying at a certain temperature for a certain time to obtain a heat transfer-latent energy dual synergistic heat dissipation mode heterogeneous structure polymer-based heat conducting composite material.

[0009] Further, in step (1), the molar mass ratio of chromium chloride hexahydrate to terephthalic acid is 1:1, the stirring time is 3-10 min, the stirring speed is 1000-6000 r / min, and the concentrations of chromium chloride and terephthalic acid are 36.9 mg / ml and 23.1 mg / ml, respectively. Further, in step (1), the reaction temperature is 180-220 ℃, the reaction time is 16-24 h, and the centrifugal speed is 5000-8000 r / min.

[0010] Further, in step (2), the ultrasonic treatment time is 10-30 min, the stirring speed is 200-600 r / min, and the stirring time is 10-30 min.

[0011] Further, in step (3), the mass ratio of the water-absorbing MOF material to cellulose is 3-9:12.5-50, the concentration of the MOF dispersion liquid is 0.3-0.7 wt%, and the ultrasonic treatment time is 10-30 min.

[0012] Further, in step (4), the drying temperature is 40-80 ℃, and the drying time is 6-12 h.

[0013] Further, the thickness of the composite material prepared in step (4) is 100-300 μm.

[0014] In addition, the application also provides the use of the heat transfer-latent energy dual synergistic heat dissipation mode heterogeneous structure polymer-based heat conducting composite material prepared by the above preparation method in the preparation of electronic packaging materials.

[0015] Compared with the prior art, the application has the following beneficial effects:

[0016] (1) The heat transfer-potential dual synergistic heat dissipation mode heterogeneous structure polymer-based heat conducting composite material prepared by the application has both heat transfer and potential heat absorption heat dissipation modes, and the heat dissipation efficiency of the polymer-based heat conducting composite material is synergistically improved, and the operation reliability of the electronic packaging material during operation is effectively increased. The application provides a new idea for the application of the heterogeneous structure polymer-based heat conducting composite material with multiple heat dissipation modes in synergy in the field of electronic packaging.

[0017] (2) The preparation method of the heterogeneous structure polymer-based heat conducting composite material provided by the application is green and environmentally friendly, and the material is low in price. In addition, the process can be continuously produced, the instrument equipment is simple to operate, and industrial production can be easily realized.

[0018] (3) The heterogeneous structure polymer-based heat conducting composite material designed by the application utilizes the porous water absorption performance of MOF (MIL-101 (Cr)) in the potential heat absorption layer. During the operation of the electronic packaging material, the water absorbed by the MOF volatilizes under heat to achieve the cooling effect. The phase change involved in the process is water in the air, which is beneficial to environmental protection. BRIEF DESCRIPTION OF DRAWINGS

[0019] Figure 1 The scanning diagram of the material prepared by the application, wherein a is the scanning diagram of the MOF material prepared and having water absorption, b is the scanning diagram of MOF / CNF, and c is the fracture scanning diagram of the heterogeneous structure polymer-based heat conducting composite material.

[0020] Figure 2 The adsorption and desorption diagram of the water absorption MOF material for water.

[0021] Figure 3 The surface temperature of the heterogeneous structure polymer-based heat conducting composite material and the pure polymer-based heat conducting composite material applied to the LED lamp after 300 s.

[0022] Figure 4 The surface temperature of the heterogeneous structure polymer-based heat conducting composite material and the pure polymer-based heat conducting composite material applied to the LED lamp after 600 s. DETAILED DESCRIPTION

[0023] The application will be further described below in combination with specific embodiments.

[0024] Some raw material models or indexes used in the embodiments are as follows:

[0025] CrCl3·6H2O: number average molecular weight 266.44, chemical reagent purity: AR, 98%;

[0026] H2BDC: number average molecular weight 166.13, chemical molecular formula: C8H6O4, chemical reagent purity: 99%;

[0027] BN: number average molecular weight 24.82, hexagonal boron nitride, 1-2 μm

[0028] Natural latex: solid content 60% Example 1

[0029] The preparation of the heterogeneous structure polymer-based thermal conductive composite material with the heat transfer-potential dual synergistic heat dissipation mode comprises the following steps:

[0030] (1) The preparation process of the porous water-absorbing material MOF (MIL-101 (Cr)) is as follows: first, 799.5 mg of chromium sulfide (CrCl3·6H2O) and 498.3 mg of terephthalic acid (H2BDC) are weighed and dispersed in 21.6 mg of water, and stirred vigorously at room temperature for 30 min. Then, the mixture is placed in a high-pressure reaction kettle and reacted at 180 ℃ for 24 h. After the reaction is completed, centrifugal purification is performed at 6500 r / min to obtain the porous water-absorbing material MOF (MIL-101 (Cr)).

[0031] (2) 0.12 g of BN-OH is dispersed in 12 g of deionized water, and ultrasonic treatment is performed for 10 min to obtain a 1 wt% BN-OH dispersion. Then, the dispersion is added to 0.35 g of natural latex with a solid content of 60 wt%, and ultrasonic treatment is performed at a power of 50 W for 5 min to obtain a mixed dispersion. The mixed dispersion is slowly added to a vacuum-assisted filtration device, and filtration is performed for 2 h to obtain a heat transfer layer structure mainly composed of BN / NR.

[0032] (3) 0.03 g of MOF is added to 10 g of water, and ultrasonic treatment is performed for 5 min to obtain a 0.3 wt% MOF dispersion. Then, 1.25 g of cellulose CNF is added, and further ultrasonic treatment is performed for 10 min to obtain a MOF / CNF dispersion. The MOF / CNF dispersion is slowly added to the top of the heat transfer layer structure, and vacuum-assisted filtration is continued for 12 h to obtain a heterogeneous structure polymer-based thermal conductive composite material with a heat transfer layer structure combined with a latent heat absorption layer structure.

[0033] (4) The heterogeneous structure polymer-based thermal conductive composite material prepared in step (3) is placed in a vacuum drying oven and dried at 60 ℃ for 24 h to obtain a heterogeneous structure polymer-based thermal conductive composite material with a heat transfer-potential dual synergistic heat dissipation mode. Example 2

[0034] The preparation of the heterogeneous structure polymer-based thermal conductive composite material with the heat transfer-potential dual synergistic heat dissipation mode comprises the following steps:

[0035] (1) The preparation process of the porous water-absorbing material MOF (MIL-101 (Cr)) is as follows: first, 799.5 mg of chromium sulfide hexahydrate (CrCl3·6H2O) and 498.3 mg of terephthalic acid (H2BDC) are weighed and dispersed in 21.6 mg of water, and then stirred vigorously at room temperature for 30 min. Then, the mixture is placed in a high-pressure reaction kettle and reacted at 180°C for 24 h. After the reaction is completed, centrifugal purification is performed at 6500 r / min to obtain the porous water-absorbing material MOF (MIL-101 (Cr)).

[0036] (2) 0.12 g of BN-OH is dispersed in 12 g of deionized water for 10 min to obtain a 1 wt% BN-OH dispersion, which is then added to 0.35 g of natural latex with a solid content of 60 wt%. After ultrasonic treatment at a power of 50 W for 5 min, a mixed dispersion solution is obtained. Then, the mixed dispersion solution is slowly added to a vacuum-assisted filtration device and filtered for 2 h to obtain a high-thermal-conductivity transfer layer structure mainly composed of BN / NR.

[0037] (3) 0.05 g of MOF is added to 10 g of water and ultrasonically treated for 5 min to obtain a 0.5 wt% MOF water dispersion. Then, 1.25 g of cellulose CNF is added and further ultrasonically treated for 10 min to obtain a MOF / CNF dispersion. The MOF / CNF dispersion is slowly added to the thermal transfer layer structure, and vacuum-assisted filtration is continued for 12 h to obtain a heterogeneous structure polymer-based thermal conductive composite material combining the thermal transfer layer structure and the latent heat absorption layer structure.

[0038] (4) The heterogeneous structure polymer-based thermal conductive composite material prepared in step (3) is placed in a vacuum drying oven and dried at 60°C for 24 h to obtain a heterogeneous structure polymer-based thermal conductive composite material with a thermal transfer-latent energy dual synergistic heat dissipation mode. Example 3

[0039] The preparation of the heterogeneous structure polymer-based thermal conductive composite material with a thermal transfer-latent energy dual synergistic heat dissipation mode includes the following steps:

[0040] (1) The preparation process of the porous water-absorbing material MOF (MIL-101 (Cr)) is as follows: first, 799.5 mg of chromium sulfide hexahydrate (CrCl3·6H2O) and 498.3 mg of terephthalic acid (H2BDC) are weighed and dispersed in 21.6 mg of water, and then stirred vigorously at room temperature for 30 min. Then, the mixture is placed in a high-pressure reaction kettle and reacted at 180°C for 24 h. After the reaction is completed, centrifugal purification is performed at 6500 r / min to obtain the porous water-absorbing material MOF (MIL-101 (Cr)).

[0041] (2) 0.12 g BN-OH was dispersed in 12 g deionized water for 10 min to obtain a 1 wt% BN-OH dispersion, which was added to 0.35 g of natural latex with a solid content of 60 wt%. After ultrasonic treatment at 50 W for 5 min, a mixed dispersion solution was obtained, which was then slowly added to a vacuum-assisted filtration device and filtered for 2 h to obtain a high thermal conduction layer structure mainly composed of BN / NR.

[0042] (3) 0.07 g MOF was added to 10 g water and ultrasonically treated for 5 min to obtain a 0.7 wt% MOF dispersion. 1.25 g of cellulose CNF was further ultrasonically treated for 10 min to obtain a MOF / CNF dispersion, which was slowly added to the thermal conduction layer structure and vacuum-assisted filtration was continued for 12 h to obtain a heterogeneous structure polymer-based thermal conductive composite material combining the thermal conduction layer structure and the latent heat absorption layer structure.

[0043] (4) The heterogeneous structure polymer-based thermal conductive composite material prepared in step (3) was placed in a vacuum drying oven and dried at 60 °C for 24 h to obtain a heterogeneous structure polymer-based thermal conductive composite material with a thermal conduction-latent energy dual synergistic heat dissipation mode. Example 4

[0044] The preparation of the heterogeneous structure polymer-based thermal conductive composite material with a thermal conduction-latent energy dual synergistic heat dissipation mode includes the following steps:

[0045] (1) The preparation process of the porous water-absorbing material MOF (MIL-101(Cr)) is as follows: first, 799.5 mg of chromium sulfide hexahydrate (CrCl3·6H2O) and 498.3 mg of terephthalic acid (H2BDC) were dispersed in 21.6 mg of water and stirred vigorously at room temperature for 30 min. Then, the mixture was placed in a high-pressure reaction kettle and reacted at 180 °C for 24 h. After the reaction was completed, the product was centrifuged at 6500 r / min to obtain the porous water-absorbing material MOF (MIL-101(Cr)).

[0046] (2) 0.24 g BN-OH was dispersed in 12 g deionized water for 10 min to obtain a 2 wt% BN-OH dispersion, which was added to 0.35 g of natural latex with a solid content of 60 wt%. After ultrasonic treatment at 50 W for 5 min, a mixed dispersion solution was obtained, which was then slowly added to a vacuum-assisted filtration device and filtered for 2 h to obtain a high thermal conduction layer structure mainly composed of BN / NR.

[0047] (3) 0.07 g MOF was added into 10 g water, and ultrasonicated for 5 min to obtain a 0.7 wt% MOF dispersion, 1.25 g of cellulose CNF was added, and further ultrasonicated for 10 min to obtain a MOF / CNF dispersion, which was slowly added onto the heat transfer layer structure, and vacuum assisted suction filtration was continued, and suction filtration was performed for 12 h to obtain a heterogeneous structure polymer-based thermal conductive composite material combining the heat transfer layer structure and the latent heat energy absorption layer structure.

[0048] (4) The heterogeneous structure polymer-based thermal conductive composite material prepared in step (3) was placed in a vacuum drying oven, and dried at 60 °C for 24 h to obtain a heterogeneous structure polymer-based thermal conductive composite material with a heat transfer-latent energy dual synergistic heat dissipation mode.

[0049] Comparative Example 1

[0050] The heat transfer form polymer-based thermal conductive composite material comprises the following steps:

[0051] (1) 0.12 g BN-OH was dispersed in 12 g deionized water, and ultrasonicated for 10 min to obtain a 1 wt% BN-OH dispersion, which was added to 0.35 g natural latex with a solid content of 60 wt%, and ultrasonicated at a power of 50 W for 5 min to obtain a mixed dispersion solution, which was then slowly added to a vacuum assisted suction filtration device, and suction filtration was performed for 2 h to obtain a high thermal conductive transfer layer structure mainly composed of BN / NR.

[0052] (2) The polymer-based thermal conductive composite material prepared in step (1) was placed in a vacuum drying oven, and dried at 60 °C for 24 h to obtain a heat transfer form polymer-based thermal conductive composite material.

[0053] Comparative Example 2

[0054] The heat transfer form polymer-based thermal conductive composite material comprises the following steps:

[0055] (1) 0.24 g BN-OH was dispersed in 12 g deionized water, and ultrasonicated for 10 min to obtain a 2 wt% BN-OH dispersion, which was added to 0.35 g natural latex with a solid content of 60 wt%, and ultrasonicated at a power of 50 W for 5 min to obtain a mixed dispersion solution, which was then slowly added to a vacuum assisted suction filtration device, and suction filtration was performed for 2 h to obtain a high thermal conductive transfer layer structure mainly composed of BN / NR.

[0056] (2) The polymer-based thermal conductive composite material prepared in step (1) was placed in a vacuum drying oven, and dried at 60 °C for 24 h to obtain a heat transfer form polymer-based thermal conductive composite material.

[0057] The results of the LED lamp temperature performance test of Examples 1-3 and Comparative Example 1 are shown in Table 1. As can be seen from Table 1, the LED lamp in Example 3 with the highest content of MOF keeps the lowest temperature when working continuously for 300 s under the same content of the heat-conducting filler BN. The results prove that the working temperature of the LED lamp is effectively reduced and the working performance stability is increased with the increase of the content of MOF.

[0058] Table 1. Results of LED lamp temperature performance test of the composite material of Examples 1-3 and Comparative Example 1

[0059]

[0060] The results of the LED lamp temperature performance test of Examples 3-4 and Comparative Example 2 are shown in Table 2. As can be seen from Table 2, the LED lamp in Example 4 keeps the lowest temperature when working for 300 s, which proves that the working temperature of the LED lamp can be effectively reduced by increasing the content of the heat-conducting filler BN.

[0061] Table 2. Results of LED lamp temperature performance test of the composite material of Examples 3-4 and Comparative Example 2

[0062]

Claims

1. A method for preparing a heterogeneous structure polymer-based thermal conductive composite material with heat transfer-potential dual synergistic heat dissipation mode, characterized in that, The method comprises the following steps: (1) uniformly dispersing chromium chloride hexahydrate and terephthalic acid in deionized water, stirring at room temperature, and then placing the mixture in a high-pressure reaction kettle, reacting at a certain temperature and time, and then centrifuging and purifying to obtain a porous water-absorbing MOF material; (2) dispersing the hydroxyl-modified BN-OH in deionized water, adding it to natural latex after ultrasonic treatment, and mechanically stirring to obtain a uniform mixed dispersion, and then slowly adding the mixed dispersion to a vacuum-assisted filtration device to obtain a high-thermal-conductivity transfer layer structure mainly composed of BN / NR; (3) adding the water-absorbing MOF material to deionized water, ultrasonic treatment to obtain an MOF dispersion, adding a certain amount of cellulose, and further ultrasonic treatment to obtain an MOF / CNF dispersion, and then slowly adding the MOF / CNF dispersion to the thermal transfer layer structure and continuing vacuum-assisted filtration to obtain a heterogeneous structure polymer-based composite material combined with the thermal transfer layer structure and the latent heat absorption layer structure; wherein the mass ratio of the water-absorbing MOF material to cellulose is 3-9:12.5-50, the concentration of the MOF dispersion is 0.3-0.7 wt%, and the ultrasonic treatment time is 10-30 min; (4) placing the heterogeneous structure polymer-based composite material prepared in step (3) in a vacuum drying oven, drying at a certain temperature for a certain time, and obtaining a heterogeneous structure polymer-based thermal conductive composite material with a thermal transfer-latent energy dual synergistic heat dissipation mode.

2. The method of claim 1, wherein the method further comprises the step of: In step (1), the molar mass ratio of chromium chloride hexahydrate to terephthalic acid is 1:1, the stirring time is 3-10 min, the stirring speed is 1000-6000 r / min, and the concentrations of chromium chloride and terephthalic acid are 36.9 mg / ml and 23.1 mg / ml, respectively. ​ 3. The method of claim 1, wherein the method further comprises the step of: 3-1) mixing the thermally conductive polymer matrix, the thermally conductive filler, the phase change material, and the porous material to form the heterogeneous structure polymer-based thermally conductive composite material. In step (1), the reaction temperature is 180-220 ℃, the reaction time is 16-24 h, and the centrifugal speed is 5000-8000 r / min.

4. The method of claim 1, wherein the method further comprises the step of: 4-1) mixing the thermally conductive polymer matrix with the thermally conductive filler, the thermally conductive filler having a thermal conductivity of 1 W / m-K or more, and the thermally conductive polymer matrix having a thermal conductivity of 0.1 W / m-K or less, to form the thermally conductive polymer matrix composite. In step (2), the ultrasonic treatment time is 10-30 min, the stirring speed is 200-600 r / min, and the stirring time is 10-30 min.

5. The method for preparing heterogeneous polymer-based thermally conductive composite materials with a dual synergistic heat transfer and potential energy dissipation mechanism according to claim 1, characterized in that, In step (4), the drying temperature is 40-80 ℃, and the drying time is 6-12 h.

6. The method for preparing heterogeneous polymer-based thermally conductive composite materials with a dual synergistic heat transfer and potential energy dissipation mechanism according to claim 1, characterized in that, The thickness of the composite material prepared in step (4) is 100-300 μm.

7. Use of a heterogeneous structure polymer-based thermal conductive composite material with a thermal transfer-latent energy dual synergistic heat dissipation mode obtained by the preparation method of any one of claims 1-6 in the preparation of an electronic packaging material.

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