CN108659457B - Boron nitride coated sulfonated graphene-epoxy resin composite material and preparation method thereof - Google Patents
Boron nitride coated sulfonated graphene-epoxy resin composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a boron nitride coated sulfonated graphene-epoxy resin composite material and a preparation method thereof. According to the preparation method, boron nitride particles are coated on the surface of sulfonated graphene by adopting an electrostatic self-assembly method, and then the BN @ SGO composite heat-conducting filler is added into an epoxy resin matrix by using a mechanical spraying method, so that the boron nitride coated sulfonated graphene composite filler is uniformly distributed in the resin matrix. According to the invention, by utilizing the low dielectric property of boron nitride and combining the high heat conduction characteristics of boron nitride and sulfonated graphene, the heat conductivity of the epoxy resin is effectively improved, the low dielectric property of the epoxy resin is maintained, and the problem of uneven heat conduction brought by the traditional addition scheme is obviously improved. The boron nitride coated sulfonated graphene-epoxy resin composite material disclosed by the invention is excellent in heat conductivity, good in dielectric property and excellent in thermal stability, and has a great application prospect in the field of electronic packaging materials.
Description
Technical Field
The invention belongs to the technical field of preparation of heat-conducting composite materials, and particularly relates to a boron nitride coated sulfonated graphene-epoxy resin composite material and a preparation method thereof.
Background
With the acceleration of the integration and miniaturization of electronic products, the requirements for electronic packaging materials are becoming more stringent and diversified. The high load of the electronic product, which is operated for a long time, causes a large amount of heat to be generated by the electronic product, which poses a great challenge to the heat dissipation capability of the substrate. The electronic material matrix which is mainstream in the market at present is mainly an epoxy resin (EP) composite material which has the advantages of good bonding performance, small curing shrinkage, stable process,Low price and the like. However, the thermal conductivity of the epoxy resin is too low to meet the thermal conductivity requirement of the electronic material, and therefore, the thermal conductivity of the epoxy resin needs to be improved by adding a high thermal conductive filler. The commonly used heat-conducting filler is generally copper powder, tin powder, aluminum oxide, silicon nitride, aluminum nitride and the like. Graphene becomes a hotspot of research in recent years, Shahil and the like adopt a solution method to prepare a graphene epoxy resin composite material, and research results show that: even if a very small amount of graphene is added, the thermal conductivity of the composite material can be effectively improved; when in use
When the volume of the graphene is 5% (relative to the volume of EP), the thermal conductivity of the corresponding composite material can be improved by 5-10 times (SHAPHIL. KMF, et al. thermal properties of graphene: Application of thermal interface materials [ J ]]ECST ransactions, 2011, 35 (3): 193-199.). However, due to the special large pi-bond conjugated electronic structure of graphene, great van der waals attraction exists between layers of graphene, the sheet layers of graphene are easy to reunite and stack, and graphene is insufficient in water solubility, so that the graphene is difficult to perform surface modification in an aqueous solution, and further application of graphene is limited.
Graphene Oxide (GO) is an important graphene derivative generated in the process of preparing a graphene material by an oxidation-reduction method, but is different from graphene in that the graphene oxide structure contains a large number of oxygen-containing functional groups, so that the graphene oxide is very easy to absorb water and can form a stable dispersion liquid in an aqueous solution system. However, due to strong hydrophilicity and weak lipophilicity of graphene oxide, graphene oxide cannot be stably dispersed and peeled in a plurality of common organic solvent systems, which brings certain obstacles to the application of graphene oxide in the field of composite materials. Tao Huang and the like utilize boron nitride to coat graphene oxide to prepare epoxy resin composite materials, and when the BN @ GO composite filler accounts for 40 wt%, the heat conductivity coefficient of a composite system can reach 2.23 W.m-1·K-1The thermal conductivity is obviously improved, but the introduction of the graphene also reduces the thermal stability and dielectric property of the material (Tao Huang, ethylene, boron nitride @ graphene oxide hybrids for epoxy composites with enhanced thermal properties con)ductivity[J].RSC Advances.2016,6,35847-35854.)。
Sulfonated Graphene (SGO) is a modified graphene oxide obtained by introducing a sulfonic acid group to a terminal group of graphene oxide and partially reducing the obtained product, thereby reducing an oxidizing group and retaining the sulfonic acid group. The modified SGO can well improve the water solubility of graphene, so that the graphene is more favorable for showing excellent physicochemical properties in an aqueous solution or an organic solution system. However, SGO itself has good electrical conductivity, and cannot meet the low dielectric requirement of the composite material, and no relevant report is found at present for preparing a high thermal conductivity composite material by filling epoxy resin with sulfonated graphene as a thermal conductive filler.
Boron Nitride (BN) has excellent thermal conductivity, and it is added to a polymer matrix to obtain a composite material having excellent thermal conductivity, and in recent years, BN has been widely used as a filler material for improving thermal conductivity of various polymers. Li and the like are added into the nanometer BN and the micron BN with different particle sizes to prepare the composite material, when the BN content of the mixed particle size is 30 wt%, the thermal conductivity of the composite material is increased to 1.2 W.m-1·K-1About 10 times of the thermal conductivity of the Polyimide matrix, it can be seen that BN has a significant effect on improving the thermal conductivity of the matrix (Li Tunglin, Hsu Steve Lienchung. enhanced thermal conductivity of Polyimide Films via Hybrid of micro-and Nano-Sized BoronNitride [ J].The Journal of Physiacal Chemistry B,2010,114(20):6825-6829.)。
The traditional heat-conducting filler adding method mainly comprises heating, stirring, mixing, curing and forming, and the method is simple, efficient and easy to implement, but the composite material prepared by the method is easy to have the problems of poor filler dispersibility, uneven heat conduction, waste of raw materials and the like. Filling BN powder into an epoxy resin matrix by adopting a traditional addition method, wherein the heat conductivity coefficient of the composite material reaches 0.44 W.m when the BN content is 25wt percent-1·K-1Poor heat conductivity (preparation of Duyan-aromatic epoxy resin-based composite material and research on heat conductivity and insulation properties thereof [ D]Tai university of principals, 2012).
Disclosure of Invention
Aiming at the defects of low heat conductivity coefficient, poor dielectric property and unfavorable later-stage application of the existing epoxy resin composite material, the invention provides the boron nitride coated sulfonated graphene-epoxy resin composite material and the preparation method thereof.
The technical scheme of the invention is as follows:
the boron nitride coated sulfonated graphene-epoxy resin composite material comprises the following components in parts by weight:
65-85 parts of epoxy resin powder,
10-30 parts of boron nitride powder,
1-5 parts of sulfonated graphene powder,
0.5 to 2.5 parts of a silane coupling agent,
1-10 parts of low-molecular polyamide curing agent.
Preferably, the epoxy resin powder accounts for 75-78 parts, and the boron nitride powder accounts for 22-25 parts.
Preferably, the silane coupling agent is a silane coupling agent KH-550 or KH-792.
Preferably, the low molecular polyamide curing agent is 650 low molecular polyamide curing agent.
The invention further provides a preparation method of the boron nitride coated sulfonated graphene-epoxy resin composite material, which comprises the following specific steps:
step 1, preparing high-thermal conductivity BN surface modified powder: dissolving a silane coupling agent in a 95% ethanol solution, stirring and hydrolyzing, and adding a mixture of the silane coupling agent and the silane coupling agent in a mass ratio of 100: 1.2-1.8 of BN powder, stirring and reacting in a water bath at the temperature of 80 ℃, and then cooling, filtering, washing and drying to obtain modified BN powder;
step 2, preparing BN @ SGO composite powder: ultrasonically dispersing modified BN powder and SGO powder into water respectively according to the mass ratio of 10: 1-3, then adding and mixing the two dispersions drop by drop, coating BN particles on the surface of SGO through electrostatic self-assembly, stirring and mixing uniformly at normal temperature, and drying to obtain BN @ SGO composite powder;
step 3, preparing the BN @ SGO filled epoxy resin composite material: heating epoxy resin at 40-60 ℃ to improve the flow property of the epoxy resin, adding a low-molecular polyamide curing agent, spraying the resin on the surface of a substrate in a vacuum environment to form a single-layer resin layer with the thickness of 1-3 mu m, uniformly spraying BN @ SGO powder on the surface of the resin layer to form a single-layer heat-conducting filler layer, and repeatedly spraying the resin and the BN @ SGO powder in sequence to obtain the boron nitride coated sulfonated graphene-epoxy resin composite material.
Preferably, in the step 1, the stirring reaction time is 3-5 h.
Preferably, in step 1, the mass ratio of the BN powder to the silane coupling agent is 100: 1.5.
preferably, in the step 2, the stirring and mixing time is 20-30 min.
According to the invention, the SGO powder is coated by BN, and then the mixed powder is added into the EP resin matrix by a mechanical spraying method, so that the prepared composite material has excellent heat conduction and dielectric properties. The BN coats the SGO, so that the high heat-conducting property of the SGO is utilized, and the electric conductivity of the SGO is reduced. By adopting a mechanical spraying method, an effective heat conduction network can be formed between every two layers of heat conduction fillers, meanwhile, the heat transfer between the layers has better directionality, and the heat conduction efficiency is obviously improved. Tests show that when the content of the BN @ SGO composite filler in a resin matrix is 24 to 27 weight percent, the thermal conductivity coefficient of the composite material can reach 1.21 W.m-1·K-1The dielectric loss tangent value is about 0.03, and the thermal weight loss temperature Td 0.5% is 361 ℃. The boron nitride coated sulfonated graphene-epoxy resin composite material disclosed by the invention is excellent in heat conductivity, good in dielectric property and excellent in thermal stability, and has a great application prospect in the field of electronic packaging materials.
Drawings
FIG. 1 is a schematic diagram of the BN surface modification and the preparation principle of BN @ SGO composite powder.
Detailed Description
The present invention will be described in more detail with reference to the following examples and the accompanying drawings.
FIG. 1 is a schematic diagram of the BN surface modification and the preparation principle of BN @ SGO composite powder in the invention. In the modification stage of BN, silane coupling agent is firstly hydrolyzed in 95 percent absolute ethyl alcohol, then BN powder is added, BN surface is activated through-OH bonds, and then-NH is carried out2A bond, grafting the coupling agent to the BN surface. Due to-NH2The BN modified powder is positively charged in aqueous solution, while the SGO powder is negatively charged in aqueous solution due to the existence of sulfonic acid group, carboxyl group and other groups, and the BN is coated on the surface of the SGO by the mutual attraction of positive and negative charges.
The preparation of the high-thermal-conductivity BN surface modified powder in the embodiment of the invention can be referred to in the literature (Liangxinlin, the preparation and performance research of the nano Al2O 3/epoxy resin composite thermal-conductivity insulation adhesive [ D ]. Shanghai university, 2007 ].
Example 1
The boron nitride coated sulfonated graphene-epoxy resin composite material comprises the following components in parts by weight:
EP powder 85, BN powder 10, SGO powder 1, silane coupling agent KH-5500.5 and 650 low-molecular-weight polyamide curing agent 3.5.
The preparation method of the boron nitride coated sulfonated graphene-epoxy resin composite material comprises the following specific steps:
step 1, preparing high-thermal conductivity BN surface modified powder: dissolving a silane coupling agent KH-550 in a 95% ethanol solution, stirring and hydrolyzing, adding BN powder with the mass ratio of (100: 1.5) to the silane coupling agent, stirring for 3 hours in a water bath at 80 ℃, and after the reaction is finished, cooling, filtering, washing and drying to obtain modified BN powder;
step 2, preparing BN @ SGO composite powder: respectively ultrasonically dispersing the modified BN powder obtained in the step 1 and untreated SGO powder in deionized water according to the mass ratio of 10:1, dropwise adding and mixing two kinds of dispersion liquid, coating BN particles on the surface of SGO through electrostatic self-assembly, stirring and mixing uniformly at normal temperature, and drying to obtain coated powder, namely BN @ SGO composite powder;
step 3, preparing the BN @ SGO filled epoxy resin composite material: heating the epoxy resin at 40 ℃ to improve the flow property of the epoxy resin, adding a curing agent, spraying the resin on the surface of a substrate in a vacuum environment to form a single-layer resin layer with the thickness of about 1-3 mu m, uniformly spraying BN @ SGO powder on the surface of the resin layer to form a single-layer heat-conducting filler layer, and repeatedly spraying the resin and the BN @ SGO powder in sequence to obtain the boron nitride coated sulfonated graphene-epoxy resin composite material.
Example 2
The boron nitride coated sulfonated graphene-epoxy resin composite material comprises the following components in parts by weight:
EP powder 85, BN powder 12, SGO powder 1.2, silane coupling agent KH-5500.8 and 650 low-molecular-weight polyamide curing agent 1.
The preparation method of the boron nitride coated sulfonated graphene-epoxy resin composite material comprises the following specific steps:
step 1, preparing high-thermal conductivity BN surface modified powder: dissolving a silane coupling agent KH-550 in a 95% ethanol solution, stirring and hydrolyzing, adding BN powder with the mass ratio of (100: 1.5) to the silane coupling agent, stirring for 3 hours in a water bath at 80 ℃, and after the reaction is finished, cooling, filtering, washing and drying to obtain modified BN powder;
step 2, preparing BN @ SGO composite powder: respectively ultrasonically dispersing the modified BN powder obtained in the step 1 and untreated SGO powder in deionized water according to the mass ratio of 10:1, dropwise adding and mixing two kinds of dispersion liquid, coating BN particles on the surface of SGO through electrostatic self-assembly, stirring and mixing uniformly at normal temperature, and drying to obtain coated powder, namely BN @ SGO composite powder;
step 3, preparing the BN @ SGO filled epoxy resin composite material: heating the epoxy resin at 40 ℃ to improve the flow property of the epoxy resin, adding a curing agent, spraying the resin on the surface of a substrate in a vacuum environment to form a single-layer resin layer with the thickness of about 1-3 mu m, uniformly spraying BN @ SGO powder on the surface of the resin layer to form a single-layer heat-conducting filler layer, and repeatedly spraying the resin and the BN @ SGO powder in sequence to obtain the boron nitride coated sulfonated graphene-epoxy resin composite material.
Example 3
The boron nitride coated sulfonated graphene-epoxy resin composite material comprises the following components in parts by weight:
EP powder 78, BN powder 10, SGO powder 1, silane coupling agent KH-5501 and 650 low-molecular-weight polyamide curing agent 10.
The preparation method of the boron nitride coated sulfonated graphene-epoxy resin composite material comprises the following specific steps:
step 1, preparing high-thermal conductivity BN surface modified powder: dissolving a silane coupling agent KH-550 in a 95% ethanol solution, stirring and hydrolyzing, adding BN powder with the mass ratio of (100: 1.5) to the silane coupling agent, stirring for 3 hours in a water bath at 80 ℃, and after the reaction is finished, cooling, filtering, washing and drying to obtain modified BN powder;
step 2, preparing BN @ SGO composite powder: respectively ultrasonically dispersing the modified BN powder obtained in the step 1 and untreated SGO powder in deionized water according to the mass ratio of 10:1, dropwise adding and mixing two kinds of dispersion liquid, coating BN particles on the surface of SGO through electrostatic self-assembly, stirring and mixing uniformly at normal temperature, and drying to obtain coated powder, namely BN @ SGO composite powder;
step 3, preparing the BN @ SGO filled epoxy resin composite material: heating the epoxy resin at 40 ℃ to improve the flow property of the epoxy resin, adding a curing agent, spraying the resin on the surface of a substrate in a vacuum environment to form a single-layer resin layer with the thickness of about 1-3 mu m, uniformly spraying BN @ SGO powder on the surface of the resin layer to form a single-layer heat-conducting filler layer, and repeatedly spraying the resin and the BN @ SGO powder in sequence to obtain the boron nitride coated sulfonated graphene-epoxy resin composite material.
Example 4
The boron nitride coated sulfonated graphene-epoxy resin composite material comprises the following components in parts by weight:
EP powder 75, BN powder 16.7, SGO powder 5, silane coupling agent KH-5500.8 and 650 low-molecular-weight polyamide curing agent 2.5.
The preparation method of the boron nitride coated sulfonated graphene-epoxy resin composite material comprises the following specific steps:
step 1, preparing high-thermal conductivity BN surface modified powder: dissolving a silane coupling agent KH-550 in a 95% ethanol solution, stirring and hydrolyzing, adding BN powder with the mass ratio of (100: 1.5) to the silane coupling agent, stirring for 3 hours in a water bath at 80 ℃, and after the reaction is finished, cooling, filtering, washing and drying to obtain modified BN powder;
step 2, preparing BN @ SGO composite powder: respectively ultrasonically dispersing the modified BN powder obtained in the step 1 and untreated SGO powder in deionized water according to the mass ratio of 10:3, dropwise adding and mixing two kinds of dispersion liquid, coating BN particles on the surface of SGO through electrostatic self-assembly, stirring and mixing uniformly at normal temperature, and drying to obtain coated powder, namely BN @ SGO composite powder;
step 3, preparing the BN @ SGO filled epoxy resin composite material: heating the epoxy resin at 40 ℃ to improve the flow property of the epoxy resin, adding a curing agent, spraying the resin on the surface of a substrate in a vacuum environment to form a single-layer resin layer with the thickness of about 1-3 mu m, uniformly spraying BN @ SGO powder on the surface of the resin layer to form a single-layer heat-conducting filler layer, and repeatedly spraying the resin and the BN @ SGO powder in sequence to obtain the boron nitride coated sulfonated graphene-epoxy resin composite material.
Example 5
The boron nitride coated sulfonated graphene-epoxy resin composite material comprises the following components in parts by weight:
EP powder 72, BN powder 20, SGO powder 2, silane coupling agent KH-5501 and 650 low-molecular-weight polyamide curing agent 5.
The preparation method of the boron nitride coated sulfonated graphene-epoxy resin composite material comprises the following specific steps:
step 1, preparing high-thermal conductivity BN surface modified powder: dissolving a silane coupling agent KH-550 in a 95% ethanol solution, stirring and hydrolyzing, adding BN powder with the mass ratio of (100: 1.5) to the silane coupling agent, stirring for 3 hours in a water bath at 80 ℃, and after the reaction is finished, cooling, filtering, washing and drying to obtain modified BN powder;
step 2, preparing BN @ SGO composite powder: respectively ultrasonically dispersing the modified BN powder obtained in the step 1 and untreated SGO powder in deionized water according to the mass ratio of 10:1, dropwise adding and mixing two kinds of dispersion liquid, coating BN particles on the surface of SGO through electrostatic self-assembly, stirring and mixing uniformly at normal temperature, and drying to obtain coated powder, namely BN @ SGO composite powder;
step 3, preparing the BN @ SGO filled epoxy resin composite material: heating epoxy resin at 40 ℃ to improve the flow property of the epoxy resin, adding a curing agent, spraying the resin on the surface of a substrate in a vacuum environment to form a single-layer resin layer with the thickness of about 1-3 mu m, and uniformly spraying BN @ SGO powder on the surface of the resin layer to form a single-layer heat-conducting filler layer. And (3) sequentially and repeatedly spraying the resin and the BN @ SGO powder to obtain the boron nitride coated sulfonated graphene-epoxy resin composite material.
Example 6
The boron nitride coated sulfonated graphene-epoxy resin composite material comprises the following components in parts by weight:
EP powder 69, BN powder 22, SGO powder 2.2, silane coupling agent KH-5501.5 and 650 low-molecular-weight polyamide curing agent 5.3.
The preparation method of the boron nitride coated sulfonated graphene-epoxy resin composite material comprises the following specific steps:
step 1, preparing high-thermal conductivity BN surface modified powder: dissolving a silane coupling agent KH-550 in a 95% ethanol solution, stirring and hydrolyzing, adding BN powder with the mass ratio of (100: 1.5) to the silane coupling agent, stirring for 3 hours in a water bath at 80 ℃, and after the reaction is finished, cooling, filtering, washing and drying to obtain modified BN powder;
step 2, preparing BN @ SGO composite powder: respectively ultrasonically dispersing the modified BN powder obtained in the step 1 and untreated SGO powder in deionized water according to the mass ratio of 10:1, dropwise adding and mixing two kinds of dispersion liquid, coating BN particles on the surface of SGO through electrostatic self-assembly, stirring and mixing uniformly at normal temperature, and drying to obtain coated powder, namely BN @ SGO composite powder;
step 3, preparing the BN @ SGO filled epoxy resin composite material: heating epoxy resin at 40 ℃ to improve the flow property of the epoxy resin, adding a curing agent, spraying the resin on the surface of a substrate in a vacuum environment to form a single-layer resin layer with the thickness of 1-3 mu m, and uniformly spraying BN @ SGO powder on the surface of the resin layer to form a single-layer heat-conducting filler layer. And (3) sequentially and repeatedly spraying the resin and the BN @ SGO powder to obtain the boron nitride coated sulfonated graphene-epoxy resin composite material.
Example 7
The boron nitride coated sulfonated graphene-epoxy resin composite material comprises the following components in parts by weight:
EP powder 65, BN powder 25, SGO powder 2.5, silane coupling agent KH-5501.5 and 650 low-molecular-weight polyamide curing agent 6.
The preparation method of the boron nitride coated sulfonated graphene-epoxy resin composite material comprises the following specific steps:
step 1, preparing high-thermal conductivity BN surface modified powder: dissolving a silane coupling agent KH-550 in a 95% ethanol solution, stirring and hydrolyzing, adding BN powder with the mass ratio of (100: 1.5) to the silane coupling agent, stirring for 3 hours in a water bath at 80 ℃, and after the reaction is finished, cooling, filtering, washing and drying to obtain modified BN powder;
step 2, preparing BN @ SGO composite powder: respectively ultrasonically dispersing the modified BN powder obtained in the step 1 and untreated SGO powder in deionized water according to the mass ratio of 10:1, dropwise adding and mixing two kinds of dispersion liquid, coating BN particles on the surface of SGO through electrostatic self-assembly, stirring and mixing uniformly at normal temperature, and drying to obtain coated powder, namely BN @ SGO composite powder;
step 3, preparing the BN @ SGO filled epoxy resin composite material: heating epoxy resin at 40 ℃ to improve the flow property of the epoxy resin, adding a curing agent, spraying the resin on the surface of a substrate in a vacuum environment to form a single-layer resin layer with the thickness of 1-3 mu m, and uniformly spraying BN @ SGO powder on the surface of the resin layer to form a single-layer heat-conducting filler layer. And (3) sequentially and repeatedly spraying the resin and the BN @ SGO powder to obtain the boron nitride coated sulfonated graphene-epoxy resin composite material.
Example 8
The boron nitride coated sulfonated graphene-epoxy resin composite material comprises the following components in parts by weight:
EP powder 65, BN powder 30, SGO powder 3, silane coupling agent KH-5501 and 650 low-molecular-weight polyamide curing agent 1.
The preparation method of the boron nitride coated sulfonated graphene-epoxy resin composite material comprises the following specific steps:
step 1, preparing high-thermal conductivity BN surface modified powder: dissolving a silane coupling agent KH-550 in a 95% ethanol solution, stirring and hydrolyzing, adding BN powder with the mass ratio of (100: 1.5) to the silane coupling agent, stirring for 3 hours in a water bath at 80 ℃, and after the reaction is finished, cooling, filtering, washing and drying to obtain modified BN powder;
step 2, preparing BN @ SGO composite powder: respectively ultrasonically dispersing the modified BN powder obtained in the step 1 and untreated SGO powder in deionized water according to the mass ratio of 10:1, dropwise adding and mixing two kinds of dispersion liquid, coating BN particles on the surface of SGO through electrostatic self-assembly, stirring and mixing uniformly at normal temperature, and drying to obtain coated powder, namely BN @ SGO composite powder;
step 3, preparing the BN @ SGO filled epoxy resin composite material: heating the epoxy resin at 40 ℃ to improve the flow property of the epoxy resin, adding a curing agent, spraying the resin on the surface of a substrate in a vacuum environment to form a single-layer resin layer with the thickness of about 1-3 mu m, uniformly spraying BN @ SGO powder on the surface of the resin layer to form a single-layer heat-conducting filler layer, and repeatedly spraying the resin and the BN @ SGO powder in sequence to obtain the boron nitride coated sulfonated graphene-epoxy resin composite material.
Example 9
The boron nitride coated sulfonated graphene-epoxy resin composite material comprises the following components in parts by weight:
EP powder 85, BN powder 10, SGO powder 1, silane coupling agent KH-5502.5 and 650 low-molecular-weight polyamide curing agent 1.5.
The preparation method of the boron nitride coated sulfonated graphene-epoxy resin composite material comprises the following specific steps:
step 1, preparing high-thermal conductivity BN surface modified powder: dissolving a silane coupling agent KH-550 in a 95% ethanol solution, stirring and hydrolyzing, adding BN powder with the mass ratio of (100: 1.5) to the silane coupling agent, stirring for 3 hours in a water bath at 80 ℃, and after the reaction is finished, cooling, filtering, washing and drying to obtain modified BN powder;
step 2, preparing BN @ SGO composite powder: respectively ultrasonically dispersing the modified BN powder obtained in the step 1 and untreated SGO powder in deionized water according to the mass ratio of 10:1, dropwise adding and mixing two kinds of dispersion liquid, coating BN particles on the surface of SGO through electrostatic self-assembly, stirring and mixing uniformly at normal temperature, and drying to obtain coated powder, namely BN @ SGO composite powder;
step 3, preparing the BN @ SGO filled epoxy resin composite material: heating the epoxy resin at 40 ℃ to improve the flow property of the epoxy resin, adding a curing agent, spraying the resin on the surface of a substrate in a vacuum environment to form a single-layer resin layer with the thickness of about 1-3 mu m, uniformly spraying BN @ SGO powder on the surface of the resin layer to form a single-layer heat-conducting filler layer, and repeatedly spraying the resin and the BN @ SGO powder in sequence to obtain the boron nitride coated sulfonated graphene-epoxy resin composite material.
Comparative example 1
The comparative example adopts single BN powder, and the composite material comprises the following components in parts by weight: EP powder 65, BN powder 25, silane coupling agent KH-5501.5 and 650 low molecular weight polyamide curing agent 8.5.
The preparation method of the boron nitride filled epoxy resin composite material comprises the following specific steps:
step 1, preparing high-thermal conductivity BN surface modified powder: dissolving a silane coupling agent KH-550 in a 95% ethanol solution, stirring and hydrolyzing, adding BN powder with the mass ratio of (100: 1.5) to the silane coupling agent, stirring for 3 hours in a water bath at 80 ℃, and after the reaction is finished, cooling, filtering, washing and drying to obtain modified BN powder;
step 2, preparing the BN filled epoxy resin composite material: heating epoxy resin at 40 ℃ to improve the flowability of the epoxy resin, adding a curing agent, spraying the epoxy resin on the surface of a substrate in a vacuum environment to form a single-layer resin layer with the thickness of 1-3 mu m, and uniformly spraying BN powder on the surface of the resin layer to form a single-layer heat-conducting filler layer. And (4) sequentially and repeatedly spraying the resin and the BN powder to obtain the boron nitride filled epoxy resin composite material.
Comparative example 2
The comparative example adopts a BN SGO mixing method, and the composite material comprises the following components in parts by weight: EP powder 65, BN powder 25, SGO powder 2.5, silane coupling agent KH-5501.5 and 650 low-molecular-weight polyamide curing agent 6.
The composite material is prepared by the following steps:
step 1, preparing high-thermal conductivity BN surface modified powder: dissolving a silane coupling agent KH-550 in a 95% ethanol solution, stirring and hydrolyzing, adding BN powder with the mass ratio of (100: 1.5) to the silane coupling agent, stirring for 3 hours in a water bath at 80 ℃, and after the reaction is finished, cooling, filtering, washing and drying to obtain modified BN powder;
step 2, preparing the BN/SGO mixed filling epoxy resin composite material: heating epoxy resin at 40 ℃ to improve the flow property of the epoxy resin, adding a curing agent, spraying the resin on the surface of a substrate in a vacuum environment to form a single-layer resin layer with the thickness of 1-3 mu m, and uniformly spraying BN/SGO mixed powder on the surface of the resin layer to form a single-layer heat-conducting filler layer. And (4) sequentially and repeatedly spraying the resin and the BN/SGO mixed powder to finally obtain the boron nitride mixed sulfonated graphene-epoxy resin composite material.
Comparative example 3
The comparative example adopts a traditional addition method, and the composite material comprises the following components in parts by weight: EP powder 65, BN powder 25, SGO powder 2.5, silane coupling agent KH-5501.5 and 650 low-molecular-weight polyamide curing agent 6.
The composite material is prepared by the following steps:
step 1, preparing high-thermal conductivity BN surface modified powder: dissolving a silane coupling agent KH-550 in a 95% ethanol solution, stirring and hydrolyzing, adding BN powder with the mass ratio of (100: 1.5) to the silane coupling agent, stirring for 3 hours in a water bath at 80 ℃, and after the reaction is finished, cooling, filtering, washing and drying to obtain modified BN powder;
step 2, preparing BN @ SGO composite powder: respectively ultrasonically dispersing the modified BN powder obtained in the step 1 and untreated SGO powder in deionized water according to the mass ratio of 10:1, dropwise adding and mixing two kinds of dispersion liquid, coating BN particles on the surface of SGO through electrostatic self-assembly, stirring and mixing uniformly at normal temperature, and drying to obtain coated powder;
step 3, preparing the BN @ SGO filled epoxy resin composite material: heating the epoxy resin at 40 ℃ to improve the flow property of the epoxy resin, adding a curing agent and BN @ SGO composite filler, uniformly stirring, and curing to obtain the boron nitride coated sulfonated graphene-epoxy resin composite material.
The results of the performance tests on the composites prepared in the examples and comparative examples are shown in table 1.
TABLE 1
As can be seen from Table 1, the thermal conductivity of the composite material gradually increases with the increase of BN and SGO contents, the dielectric property is kept in a lower range, the low dielectric requirement is met, and meanwhile, the thermal stability of the material is improved. It can be seen from the comparison of the examples with comparative example 1 that the thermal conductivity is not significantly improved with a single BN loading. Through comparative analysis of the example and the comparative example 2, it can be seen that although the thermal conductivity of the composite material is obviously improved without adopting a mode of coating SGO with BN, the dielectric property of the composite material is higher, and meanwhile, the thermal stability of the material is poorer. Comparative example 3 adopts the composite material of traditional addition method preparation, and test result shows, heat conductivility is in general level, but dielectric properties is also higher, and thermal stability is worse simultaneously.
In conclusion, the epoxy resin composite material prepared by the method has excellent heat-conducting property, good dielectric property and excellent thermal stability, and has great application prospect in the field of electronic packaging materials.
Claims (7)
1. The boron nitride coated sulfonated graphene-epoxy resin composite material is characterized by comprising the following components in parts by weight:
65-85 parts of epoxy resin powder,
10-30 parts of boron nitride powder,
1-5 parts of sulfonated graphene powder,
0.5 to 2.5 parts of a silane coupling agent,
1-10 parts of a low-molecular polyamide curing agent, which comprises the following steps:
step 1, preparing high-thermal-conductivity boron nitride surface modified powder: dissolving a silane coupling agent in a 95% ethanol solution, stirring and hydrolyzing, and adding a mixture of the silane coupling agent and the silane coupling agent in a mass ratio of 100: 1.2-1.8, stirring and reacting the boron nitride powder in a water bath at the temperature of 80 ℃, and then cooling, filtering, washing and drying to obtain modified boron nitride powder;
step 2, preparing BN @ SGO composite powder: ultrasonically dispersing modified boron nitride powder and sulfonated graphene powder in water respectively according to a mass ratio of 10: 1-3, then dropwise adding and mixing the two dispersions, coating boron nitride particles on the surface of sulfonated graphene through electrostatic self-assembly, stirring and mixing uniformly at normal temperature, and drying to obtain BN @ SGO composite powder;
step 3, preparing the BN @ SGO filled epoxy resin composite material: heating epoxy resin at 40-60 ℃ to improve the flow property of the epoxy resin, adding a low-molecular polyamide curing agent, spraying the resin on the surface of a substrate in a vacuum environment to form a single-layer resin layer with the thickness of 1-3 mu m, uniformly spraying BN @ SGO powder on the surface of the resin layer to form a single-layer heat-conducting filler layer, and repeatedly spraying the resin and the BN @ SGO powder in sequence to obtain the boron nitride coated sulfonated graphene-epoxy resin composite material.
2. The boron nitride coated sulfonated graphene-epoxy resin composite material according to claim 1, wherein the epoxy resin powder is 75-78 parts, and the boron nitride powder is 22-25 parts.
3. The boron nitride-coated sulfonated graphene-epoxy resin composite material according to claim 1, wherein the silane coupling agent is a silane coupling agent KH-550 or KH-792.
4. The boron nitride coated sulfonated graphene-epoxy resin composite material according to claim 1, wherein the low molecular polyamide curing agent is 650 low molecular polyamide curing agent.
5. The boron nitride coated sulfonated graphene-epoxy resin composite material according to claim 1, wherein in the step 1, the stirring reaction time is 3-5 hours.
6. The boron nitride-coated sulfonated graphene-epoxy resin composite material according to claim 1, wherein in the step 1, the mass ratio of the boron nitride powder to the silane coupling agent is 100: 1.5.
7. the boron nitride coated sulfonated graphene-epoxy resin composite material according to claim 1, wherein in the step 2, the stirring and mixing time is 20-30 min.
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