CN114806081B - Polymer composite material based on aromatic compound modified heat-conducting insulating composite powder and preparation thereof - Google Patents
Polymer composite material based on aromatic compound modified heat-conducting insulating composite powder and preparation thereof Download PDFInfo
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Abstract
The invention belongs to the field of micro-nano particle modified and electronic packaging heat conducting materials, and discloses a polymer composite material based on aromatic compound modified heat conducting insulating composite powder and a preparation method thereof, wherein the polymer composite material is obtained by adding aromatic compound modified insulating composite powder into a polymer matrix material; the aromatic compound modified insulating composite powder is prepared from at least 2 heat conduction micro-nano insulating powder serving as a raw material, an aromatic compound serving as a modifier, and an aqueous solution stirring method, wherein under the action of shearing force, the modifier is adsorbed to the surface of the powder by utilizing pi-pi interaction and covalent interaction between the modifier and the micro-nano insulating powder. The invention can greatly reduce the viscosity of the polymer composite material on the basis of ensuring the heat conductivity, and can solve the problem that the low viscosity and the high heat conductivity can not be achieved when the polymer is filled with inorganic insulating powder.
Description
Technical Field
The invention belongs to the field of micro-nano particle modified and electronic packaging heat conducting materials, and particularly relates to a polymer composite material based on aromatic compound modified heat conducting and insulating composite powder and a preparation method thereof.
Background
The improvement of nano-fabrication technology and technology level has led to the development of integrated circuits towards high integration, miniaturization and light weight, and in particular, the wide application of 5G technology has led to the increasing heat flux density of integrated circuits in electronic devices. The increase in temperature of electronic devices has a great influence on the life, efficiency and energy consumption of the electronic devices, so that the improvement of the heat dissipation capacity of the electronic devices is a hot spot for research in the field of electronic packaging.
The polymer has taken up more than 90% of the market share of integrated circuits and electronic components due to its good insulation, low density, easy mass production and low cost. However, since the polymer is a poor conductor of heat (< 0.5W/m·k) and cannot rapidly and timely dissipate heat, how to obtain a polymer-based electronic packaging material having heat conductive properties has become a hot spot of research.
Inorganic fillers with high heat conductivity coefficient, such as alumina, boron nitride, aluminum nitride, silicon dioxide, diamond, beryllium oxide, magnesium oxide, zinc oxide and the like are added into a polymer matrix, so that the method is the simplest and lowest-cost method for obtaining the filled polymer at present. However, this approach generally requires a loading of greater than 40wt% to form an effective thermally conductive network in the matrix, which necessarily results in a substantial decrease in other properties of the composite, such as flow properties, mechanical properties, etc., while increasing the thermal conductivity of the composite. The high viscosity caused by the poor flow properties of polymer composite systems makes it difficult to effectively apply in the field of electronic device packaging.
Therefore, under the background, the powder material with low viscosity and heat conduction is obtained through the surface modification of the micro-nano particles, so that the powder material has great scientific and practical values.
Chinese patent CN107189348 discloses a surface-modified epoxy resin with a modified surface of polyglyceryl methacrylate, when loaded with 33.9: 33.9wtl% modified BN, a thermal conductivity of 1.21W/m.k, which is improved by 348% compared to an epoxy resin base heat conductivity of 0.27W/m.k, a viscosity of 15000mpa.s at 30 ℃ which is reduced by 33% compared to unmodified 20000 mpa.s. And the surface polyglycerol methacrylate is modified before h-BN needs to be subjected to hydroxylation treatment, so that the process is very troublesome.
Disclosure of Invention
Aiming at the defects or improvement demands of the prior art, the invention aims to provide a polymer composite material based on aromatic compound modified heat-conducting insulating composite powder and a preparation method thereof, wherein the surface of the heat-conducting micro-nano insulating powder is modified in nanometer scale by adopting an aromatic compound, the structure of the polymer composite material is improved, and the composite powder is formed by further utilizing different heat-conducting micro-nano insulating powder, so that after the composite powder is compounded with the polymer, the viscosity of the composite material can be greatly reduced on the basis of ensuring the heat conductivity, and the problem that the polymer cannot be obtained by low viscosity and high heat conductivity when the inorganic insulating powder is filled is solved. The polymer composite material obtained by the method can be used as a low-viscosity heat-conducting polymer composite material electronic packaging material.
In order to achieve the above object, according to one aspect of the present invention, there is provided a polymer composite material based on an aromatic compound modified heat conductive insulating composite powder, characterized in that the polymer composite material is obtained by adding an aromatic compound modified insulating composite powder to a polymer base material;
the aromatic compound modified insulating composite powder is prepared from at least 2 heat conduction micro-nano insulating powder serving as a raw material, an aromatic compound serving as a modifier, and an aqueous solution stirring method, wherein under the action of shearing force, the modifier is adsorbed to the surface of the powder by utilizing pi-pi interaction and covalent interaction between the modifier and the micro-nano insulating powder; wherein, for any one of the heat conduction micro-nano insulating powder, the heat conduction rate of the compound corresponding to the micro-nano insulating powder is not lower than 10W/mK.
As a further preferred aspect of the present invention, the at least 2 kinds of heat conductive micro-nano insulating powder are Al 2 O 3 At least 2 of h-BN, c-BN, alN, siC, beO and diamond particles, wherein the particle size of the powder is not more than 50um, and the purity is more than 99 percent;
the aromatic compound is one of dopamine, salicylic acid, benzoic acid, phenol, L-phenylalanine and fluorescein;
preferably, the addition amount of the aromatic compound modified insulating composite powder is 10-40 wt% of the polymer matrix material.
As a further preferred aspect of the present invention, the at least 2 kinds of heat conductive micro-nano insulating powder are h-BN and Al 2 O 3 Is a mixture of (a) and (b);
preferably, h-BN and Al 2 O 3 The mass ratio of (2) is 1:1-4:1, more preferably 2:1.
as a further preferred aspect of the present invention, the particle diameter of the thermally conductive micro-nano insulating powder before modification is not more than 50um.
As a further preferred aspect of the present invention, the polymer matrix material is a thermoplastic resin or a thermosetting resin;
preferably, the polymer matrix material is one of polyimide, acrylic resin, vinyl resin, epoxy resin, phenolic resin and polyurethane.
According to another aspect of the present invention, the present invention provides a method for preparing the above polymer composite based on an aromatic compound modified heat conductive and insulating composite powder, which is characterized by comprising the steps of:
(1) Each heat-conducting micro-nano insulating powder is taken as a raw material, an aromatic compound is taken as a modifier, an aqueous solution stirring method is adopted, and under the action of shearing force, the modifier is adsorbed to the surface of the powder by utilizing pi-pi interaction and covalent interaction between the modifier and the micro-nano insulating powder, so that the corresponding aromatic compound modified insulating powder is obtained respectively;
(2) According to preset proportioning requirements, fully drying and uniformly mixing the aromatic compound modified insulating powder corresponding to at least 2 heat conduction micro-nano insulating powder, and grinding and sieving to obtain aromatic compound modified insulating composite powder;
(3) And (3) adding the aromatic compound modified insulating composite powder obtained in the step (2) into a prepolymer corresponding to a polymer matrix material, and carrying out blending molding with a polymer to obtain the polymer composite material.
As a further preferred aspect of the present invention, in the step (1), for each of the thermally conductive micro-nano insulating powders:
the mass ratio of the modifier to the powder in the aqueous solution system corresponding to the aqueous solution stirring method is 20:1-5:1, preferably 10:1;
the reaction temperature corresponding to the aqueous solution stirring method is room temperature-90 ℃, the stirring speed is 500-1000r/min, and the reaction time is 12-48 h;
the aromatic compound modified insulating powder obtained by the reaction is separated from an aqueous solution system by adopting a centrifugal machine to carry out centrifugal treatment for 10-30min at the rotating speed of 3000-6000 r/min;
preferably, in the step (1), the aromatic compound is dopamine, tris-HCl buffer solution and ammonia water are further added into an aqueous solution system corresponding to the aqueous solution stirring method, and the pH value of the aqueous solution system is 8.5-10.
As a further preferred aspect of the present invention, the aromatic compound modified insulating powder obtained in the step (1) preferably has a thickness of the aromatic compound modified layer on the surface of the insulating powder of not more than 10nm.
As a further preferred aspect of the present invention, in the step (3), the blending and molding is specifically: firstly, dispersing an aromatic compound modified insulating composite powder and a prepolymer mixed system, uniformly dispersing the aromatic compound modified insulating composite powder in the prepolymer, removing bubbles, and curing to obtain a cured polymer composite material;
the dispersion treatment is high-speed dispersion treatment, the rotating speed is 600-2500 r/min, and the dispersion treatment time is 30-60 min.
According to a further aspect of the invention, the invention provides the application of the polymer composite material based on the aromatic compound modified heat-conducting and insulating composite powder, which is characterized in that the application is used in encapsulation of electronic packaging or used as a heat-conducting gasket.
Compared with the prior art, the heat-conducting micro-nano insulating powder surface is modified in nanometer scale by adopting the aromatic compound, and the heat-conducting particles with nanometer thickness core-shell structures are obtained by adsorbing the modifier on the powder surface through pi-pi interaction and covalent interaction between the modifier and the powder and improving the structure of the modifier; and the heat-conducting composite powder is obtained by further utilizing different heat-conducting micro-nano insulating powder to form composite powder, utilizing the integral action of the composition and the proportion of the composite powder and utilizing the synergistic action among at least 2 different heat-conducting micro-nano insulating powder; the heat-conducting composite powder can improve the heat-conducting filler structure, so that after the composite powder is compounded with the polymer, the viscosity of the composite material can be greatly reduced, and the low-viscosity heat-conducting polymer composite material can be obtained, and particularly, the technical problems that the heat-conducting performance of the traditional electronic packaging material is poor and the viscosity is greatly increased after filler particles are added can be solved. The method is simple and feasible, nontoxic and pollution-free, and environment-friendly.
The invention adopts aromatic compound to modify micro-nano insulating powder in nanometer scale to obtain core-shell structure (core structure in the interior is micro-nano insulating powder, shell structure in the exterior is aromatic compound), and the modification method is simple and easy to implement, nontoxic and pollution-free, and environment-friendly. By adjusting the composition and the proportion of the modified powder and utilizing at least 2 different micro-nano insulating powders, the obtained composite powder can more easily form a heat conduction network passage in the polymer, can be more easily dispersed in a matrix, and the viscosity of the corresponding obtained composite polymer can be obviously reduced.
Taking the following examples of the present invention as an example, 26.66wt% of h-BN and 13.33wt% of Al are modified by filling aromatic compound of nano-scale thickness 2 O 3 The thermal conductivity of the polymer composite material under low load is 1.176W/m.K, which is improved by 546% compared with 0.182W/m.K of the matrix, the viscosity is only 20443mPa.s at 30 ℃, which is reduced by 400% compared with unmodified 102281mPa.s, and the technical problems that the thermal conductivity of the current electronic packaging material is poor and the viscosity is greatly increased after filler particles are added are solved.
In addition, according to the present invention, for the aromatic compound-modified insulating powder, the thickness of the aromatic compound-modified layer on the surface may preferably be not more than 10nm (the thickness is generally determined by the concentration of the modifier, and the greater the concentration, the greater the thickness).
In conclusion, the preparation method provided by the invention has the advantages of simple preparation process, simple process flow, low cost and environment friendliness, can simultaneously realize the low viscosity and high heat conductivity of the polymer under high load, can solve the technical problems that the traditional electronic packaging material is poor in heat conduction performance and the viscosity is greatly increased after filler particles are added, and can be widely applied to the fields of encapsulation and heat conduction gaskets of electronic packaging.
Drawings
FIG. 1 shows the different loads (h-BN and Al 2 O 3 Ratio of total mass of (2) to the total mass of (3) and different mass ratios of h-BN and Al 2 O 3 Graph of thermal conductivity of epoxy composite.
FIG. 2 is a transmission electron microscope image of h-BN.
FIG. 3 is a transmission electron microscope image of the surface dopamine modified h-BN. As shown, the thickness of dopamine on the h-BN surface is about 6nm.
FIG. 4 is Al 2 O 3 Is a transmission electron microscope image of (a).
FIG. 5 is a surface dopamine modified Al 2 O 3 Is a transmission electron microscope image of (a). As shown in the figure, is located at Al 2 O 3 The thickness of the dopamine on the surface of (a) is about 2nm.
FIG. 6 is a graph showing thermal weight loss curves before and after surface dopamine modification of h-BN.
FIG. 7 is a surface dopamine modified Al 2 O 3 Front and back thermal weight loss curves.
FIG. 8 is a Fourier transform infrared spectrum before and after surface dopamine modification of h-BN.
FIG. 9 is a surface dopamine modified Al 2 O 3 Fourier transform infrared spectra before and after.
FIG. 10 is an XRD pattern of the epoxy resin after curing of examples 1-4, comparative example 5.
FIG. 11 is a sectional scanning electron microscope image of the epoxy resin composite of example 4.
FIG. 12 is a cross-sectional scanning electron microscope image of the epoxy resin composite of comparative example 4.
Fig. 13 is a gel-like plot of the epoxy resin composite of example 4 prior to curing.
Fig. 14 is a graph of a gasket of example 4 (example gasket length 4cm, width 3cm in the figure) after curing the epoxy resin composite.
Fig. 15 is a process flow diagram of a method for preparing an aromatic modified thermally conductive insulating composite powder and a low viscosity polymer composite material according to the present invention.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. In addition, the technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
In general, the preparation method of the aromatic compound modified heat-conducting and insulating composite powder and the low-viscosity polymer composite material thereof takes heat-conducting and micro-nano insulating powder as a raw material, aromatic compound as a modifier, adopts an aqueous solution stirring method, utilizes pi-pi interaction and covalent interaction between the modifier and the powder to enable the modifier to be adsorbed on the surface of the powder, carries out nano-scale modification on the heat-conducting and micro-nano insulating powder, improves the structure of the heat-conducting and micro-nano insulating powder, then adjusts the proportion and the composition of different heat-conducting and micro-nano insulating powder, utilizes the synergistic effect among different particles to form a heat-conducting channel in a matrix more easily, prepares the heat-conducting and insulating composite powder, and then adopts a high-speed dispersion method to carry out blending molding with the polymer to prepare the polymer composite material. These polymer composites combine, inter alia, high thermal conductivity with low viscosity properties.
For example, the modifier may be dopamine, and the inorganic powder may be h-BN, al 2 O 3 (the particle size of h-BN used in the examples hereinafter is about 10 μm, and the particle size is in the form of a plate at a microscopic level, and the thermal conductivity is about 33W/mK; al) 2 O 3 The grain diameter is about 0.45um, and the particles are in a particle shape under the microcosmic conditionThe thermal conductivity is about 10W/mK).
The present invention will be described in detail with reference to the following description, in which the matrix is bisphenol a epoxy resin JY257 and the curing agent is diethyl tetramethyl imidazole.
Example 1
(1) 10g of thermally conductive inorganic particles h-BN powder and Al were each mixed with 2 O 3 Dispersing the powder in 400ml deionized water, and performing ultrasonic dispersion for 2 hours to obtain dispersion liquid A and dispersion liquid B;
(2) Dispersing 1g of dopamine hydrochloride in 100ml of deionized water respectively, and performing ultrasonic dispersion for 30min to obtain dispersion liquids C and D;
(3) Mixing the dispersion liquid A and the dispersion liquid C respectively, mixing the dispersion liquid B and the dispersion liquid D, dropwise adding Tris-HCl buffer solution and ammonia water while stirring, and regulating the pH value to 8.5 to obtain dispersion liquid E and dispersion liquid F;
(4) Stirring the E and F dispersions at 600r/min for 24 hours at room temperature, respectively;
(5) Standing E and F dispersion, centrifuging at 5000r/min for 10min, cleaning the precipitate with clear water for 3-5 times, drying in oven at 80deg.C for 12 hr (of course, other drying temperatures and drying times can be adopted, such as 60deg.C for 24-48 hr), grinding, sieving, mashing, and sieving to obtain surface modified h-BN and Al 2 O 3 Inorganic filler according to h-BN and Al 2 O 3 Grinding, sieving and blending the mixture according to the mass ratio of 2:1 to obtain composite powder;
(6) Taking 2.43g (h-BN 1.61g, al) of the surface modified composite powder obtained in the step (5) 2 O 3 0.81 g), adding the mixture into a 20g of epoxy resin JY257 matrix at 600r/min under stirring by a high-speed dispersing machine, and stirring at 2500r/min for 30min to uniformly disperse the mixture;
(7) The epoxy resin comprises the following components in parts by mass: curing agent=10:1, adding 2g of diethyl tetramethylimidazole as curing agent into the solution obtained in the step (6), and stirring for 10min at the rotating speed of 2500 r/min;
(8) Placing the solution obtained in the step (7) in a vacuum oven for 20min, and setting the vacuum degree to be 2 x 10 4 pa；
(9) Pouring the solution obtained in the step (8) into a mould, and curing for 4 hours at 80 ℃ to obtain the cured composite material.
Example 2
(1) 10g of thermally conductive inorganic particles h-BN powder and Al were each mixed with 2 O 3 Dispersing the powder in 400ml deionized water, and performing ultrasonic dispersion for 2 hours to obtain dispersion liquid A and dispersion liquid B;
(2) Dispersing 1g of dopamine hydrochloride in 100ml of deionized water respectively, and performing ultrasonic dispersion for 30min to obtain dispersion liquids C and D;
(3) Mixing the dispersion liquid A and the dispersion liquid C respectively, mixing the dispersion liquid B and the dispersion liquid D, dropwise adding Tris-HCl buffer solution and ammonia water while stirring, and regulating the pH value to 8.5 to obtain dispersion liquid E and dispersion liquid F;
(4) Stirring the E and F dispersions at 600r/min for 24 hours at room temperature, respectively;
(5) Standing E and F dispersion, centrifuging at 5000r/min for 10min, cleaning the precipitate with clear water for 3-5 times, drying in oven at 80deg.C for 12 hr (of course, other drying temperatures and drying times can be adopted, such as 60deg.C for 24-48 hr), grinding, sieving, mashing, and sieving to obtain surface modified h-BN and Al 2 O 3 Inorganic filler according to h-BN and Al 2 O 3 Grinding, sieving and blending the mixture according to the mass ratio of 2:1 to obtain composite powder;
(6) Taking 5.49g (h-BN 3.66g, al) of the surface modified composite powder obtained in the step (5) 2 O 3 1.83 g), adding the mixture into a 20g epoxy resin JY257 matrix at 600r/min under stirring by a high-speed dispersing machine, and stirring for 30min at 2500r/min to uniformly disperse the mixture;
(7) The epoxy resin comprises the following components in parts by mass: curing agent=10:1, adding 2g of diethyl tetramethylimidazole as curing agent into the solution obtained in the step (6), and stirring for 10min at the rotating speed of 2500 r/min;
(8) Placing the solution obtained in the step (7) in a vacuum oven for 20min, and setting the vacuum degree to be 2 x 10 4 pa；
(9) Pouring the solution obtained in the step (8) into a mould, and curing for 4 hours at 80 ℃ to obtain the cured composite material.
Example 3
(1) 10g of thermally conductive inorganic particles h-BN powder and Al were each mixed with 2 O 3 Dispersing the powder in 400ml deionized water, and performing ultrasonic dispersion for 2 hours to obtain dispersion liquid A and dispersion liquid B;
(2) Dispersing 1g of dopamine hydrochloride in 100ml of deionized water respectively, and performing ultrasonic dispersion for 30min to obtain dispersion liquids C and D;
(3) Mixing the dispersion liquid A and the dispersion liquid C respectively, mixing the dispersion liquid B and the dispersion liquid D, dropwise adding Tris-HCl buffer solution and ammonia water while stirring, and regulating the pH value to 8.5 to obtain dispersion liquid E and dispersion liquid F;
(4) Stirring the E and F dispersions at 600r/min for 24 hours at room temperature, respectively;
(5) Standing E and F dispersion, centrifuging at 5000r/min for 10min, cleaning the precipitate with clear water for 3-5 times, drying in oven at 80deg.C for 12 hr (of course, other drying temperatures and drying times can be adopted, such as 60deg.C for 24-48 hr), grinding, sieving, mashing, and sieving to obtain surface modified h-BN and Al 2 O 3 Inorganic filler according to h-BN and Al 2 O 3 Grinding, sieving and blending the mixture according to the mass ratio of 2:1 to obtain composite powder;
(6) 9.42g (h-BN 6.28g, al) of the surface modified composite powder obtained in the step (5) is taken 2 O 3 3.14 g) and adding the mixture into a 20g of epoxy resin JY257 matrix at 600r/min under stirring by a high-speed dispersing machine, and then stirring for 30min at 2500r/min to uniformly disperse the mixture;
(7) The epoxy resin comprises the following components in parts by mass: curing agent=10:1, adding 2g of diethyl tetramethylimidazole as curing agent into the solution obtained in the step (6), and stirring for 10min at the rotating speed of 2500 r/min;
(8) Placing the solution obtained in the step (7) in a vacuum oven for 20min, and setting the vacuum degree to be 2 x 10 4 pa；
(9) Pouring the solution obtained in the step (8) into a mould, and curing for 4 hours at 80 ℃ to obtain the cured composite material.
Example 4
(1) 10g of thermally conductive inorganic particles h-BN powder and Al were each mixed with 2 O 3 Dispersing the powder in 400ml deionized water, and performing ultrasonic dispersion for 2 hours to obtain dispersion liquid A and dispersion liquid B;
(2) Dispersing 1g of dopamine hydrochloride in 100ml of deionized water respectively, and performing ultrasonic dispersion for 30min to obtain dispersion liquids C and D;
(3) Mixing the dispersion liquid A and the dispersion liquid C respectively, mixing the dispersion liquid B and the dispersion liquid D, dropwise adding Tris-HCl buffer solution and ammonia water while stirring, and regulating the pH value to 8.5 to obtain dispersion liquid E and dispersion liquid F;
(4) Stirring the E and F dispersions at 600r/min for 24 hours at room temperature, respectively;
(5) Standing E and F dispersion, centrifuging at 5000r/min for 10min, cleaning the precipitate with clear water for 3-5 times, drying in oven at 80deg.C for 12 hr (of course, other drying temperatures and drying times can be adopted, such as 60deg.C for 24-48 hr), grinding, sieving, mashing, and sieving to obtain surface modified h-BN and Al 2 O 3 Inorganic filler according to h-BN and Al 2 O 3 Grinding, sieving and blending the mixture according to the mass ratio of 2:1 to obtain composite powder;
(6) 14.67g (h-BN 9.78g, al) of the surface modified composite powder obtained in the step (5) is taken 2 O 3 4.89 g), adding the mixture into a 20g of epoxy resin JY257 matrix at 600r/min under stirring by a high-speed dispersing machine, and stirring for 30min at 2500r/min to uniformly disperse the mixture;
(7) The epoxy resin comprises the following components in parts by mass: curing agent=10:1, adding 2g of diethyl tetramethylimidazole as curing agent into the solution obtained in the step (6), and stirring for 10min at the rotating speed of 2500 r/min;
(8) Placing the solution obtained in the step (7) in a vacuum oven for 20min, and setting the vacuum degree to be 2 x 10 4 pa；
(9) Pouring the solution obtained in the step (8) into a mould, and curing for 4 hours at 80 ℃ to obtain the cured composite material.
Comparative example 1
(1) Heat conducting inorganic particles h-BN and Al 2 O 3 Drying for 2 hours in an oven at 80 ℃, grinding, sieving and blending according to the mass ratio of 2:1 to obtain composite powder;
(2) Taking 2.43g (h-BN 1.61g, al) of the composite powder obtained in the step (1) 2 O 3 0.81 g), adding the mixture into a 20g of epoxy resin JY257 matrix at 600r/min under stirring by a high-speed dispersing machine, and stirring at 2500r/min for 30min to uniformly disperse the mixture;
(3) The epoxy resin comprises the following components in parts by mass: curing agent=10:1, adding 2g of diethyl tetramethyl imidazole curing agent into the solution obtained in the step (2), and stirring for 10min at the rotating speed of 2500 r/min;
(4) Placing the solution obtained in the step (3) in a vacuum oven for 20min, and setting the vacuum degree to be 2 x 10 4 pa；
(5) Pouring the solution obtained in the step (4) into a mold, and curing for 4 hours at 80 ℃ to obtain the cured composite material.
Comparative example 2
(1) Heat conducting inorganic particles h-BN and Al 2 O 3 Drying in an oven at 80 ℃ for 2 hours, grinding, sieving and blending according to the mass ratio of 2:1 to obtain composite powder;
(2) Taking 5.49g (h-BN 3.66g, al) of the composite powder obtained in the step (1) 2 O 3 1.83 g), adding the mixture into a 20g of epoxy resin JY257 matrix at 600r/min while stirring by a high-speed dispersing machine, and stirring at 2500r/min for 30min to uniformly disperse the mixture;
(3) The epoxy resin comprises the following components in parts by mass: curing agent=10:1, adding 2g of diethyl tetramethyl imidazole curing agent into the solution obtained in the step (2), and stirring for 10min at the rotating speed of 2500 r/min;
(4) Placing the solution obtained in the step (3) in a vacuum oven for 20min, and setting the vacuum degree to be 2 x 10 4 pa；
(5) Pouring the solution obtained in the step (4) into a mold, and curing for 4 hours at 80 ℃ to obtain the cured composite material.
Comparative example 3
(1) Heat conducting inorganic particles h-BN and Al 2 O 3 Drying in an oven at 80 ℃ for 2 hours, grinding, sieving and blending according to the mass ratio of 2:1 to obtain composite powder;
(2) 9.42g (h-BN 6.28g, al) of the composite powder obtained in the step (1) is taken 2 O 3 3.14 g), adding the mixture into a 20g of epoxy resin JY257 matrix at 600r/min while stirring by a high-speed dispersing machine, and stirring at 2500r/min for 30min to uniformly disperse the mixture;
(3) The epoxy resin comprises the following components in parts by mass: curing agent=10:1, adding 2g of diethyl tetramethyl imidazole curing agent into the solution obtained in the step (2), and stirring for 10min at the rotating speed of 2500 r/min;
(4) Placing the solution obtained in the step (3) in a vacuum oven for 20min, and setting the vacuum degree to be 2 x 10 4 pa；
(5) Pouring the solution obtained in the step (4) into a mold, and curing for 4 hours at 80 ℃ to obtain the cured composite material.
Comparative example 4
(1) Heat conducting inorganic particles h-BN and Al 2 O 3 Drying in an oven at 80 ℃ for 2 hours, grinding, sieving and blending according to the mass ratio of 2:1 to obtain composite powder;
(2) 14.67g (h-BN 9.78g, al) of the composite powder obtained in the step (1) is taken 2 O 3 4.89 g), adding the mixture into a 20g of epoxy resin JY257 matrix at 600r/min while stirring by a high-speed dispersing machine, and stirring for 30min at 2500r/min to uniformly disperse the mixture;
(3) The epoxy resin comprises the following components in parts by mass: curing agent=10:1, adding 2g of diethyl tetramethyl imidazole curing agent into the solution obtained in the step (2), and stirring for 10min at the rotating speed of 2500 r/min;
(4) Placing the solution obtained in the step (3) in a vacuum oven for 20min, and setting the vacuum degree to be 2 x 10 4 pa；
(5) Pouring the solution obtained in the step (4) into a mold, and curing for 4 hours at 80 ℃ to obtain the cured composite material.
Comparative example 5
(1) The epoxy resin comprises the following components in parts by mass: curing agent=10:1, taking 20g of epoxy resin JY257 and 2g of diethyl tetramethyl imidazole curing agent, adopting a high-speed dispersing machine, and stirring for 10min at the rotating speed of 2500r/min to uniformly disperse the curing agent;
(2) Placing the solution obtained in the step (1) in a vacuum oven for 20min, and setting the vacuum degree to be 2 x 10 4 pa；
(3) Pouring the solution obtained in the step (2) into a mold, and curing for 4 hours at 80 ℃ to obtain the cured epoxy resin material.
The materials prepared in examples 1 to 4 and comparative examples 1 to 5 were subjected to performance test (specifically, the heat conductive property was tested in accordance with test standard ISO22007-2, the viscosity property was tested in accordance with test standard GB/T2794-2013, the density property was tested in accordance with test standard GB/T13354-921, the hardness property was tested in accordance with test standard GB/T531.1-2008, the moisture absorption property was tested in accordance with test standard IOS62, and the glass transition temperature property was tested in accordance with test standard IEC 61006), and the results are shown in Table 1.
TABLE 1
The modified products of the examples were subjected to Transmission Electron Microscope (TEM) characterization (results shown in FIGS. 2-5), thermal weight loss (TGA) experiments (results shown in FIGS. 6-7), and Fourier Transform Infrared (FTIR) detection (results shown in FIGS. 8-9), respectively, to find that dopamine was successfully coated on h-BN and Al 2 O 3 A surface; the composite materials of examples and comparative examples were cured and then subjected to X-ray diffraction (XRD) test (results shown in fig. 10) and Scanning Electron Microscope (SEM) test (results shown in fig. 11 (example 4) and fig. 12 (comparative example 4)) respectively, and it was found that the thermally conductive composite filler was uniformly distributed in the polymer matrix.
In summary, it is known that, based on the process according to the invention, by reacting the thermally conductive inorganic fillers h-BN and Al 2 O 3 Surface modification is carried out to prepare the heat conduction particles h-BN and Al with the nano-scale thickness core-shell structure 2 O 3 Improving the heat conduction inorganic filler h-BN and Al 2 O 3 By adjusting the composition and the proportion of the composite powder, the low-viscosity heat-conducting insulating composite powder is prepared, and then the composite powder is compounded with a polymer material to prepare the low-viscosity heat-conducting polymer electronic packaging material, so that the heat conductivity of the polymer composite material (example 4) is 1.176W/m.K, compared with a matrix (comparative example 5), 0.182W/m.K is improved by 546%, the viscosity is only 20443mPa.s at 30 ℃, and compared with an unmodified (comparative example 4), 102281mPa.s is reduced by 400%. Can solve the problem of low viscosity and high heat conductivity when the polymer is filled with high amount (40 wt% or more). The surface modification method related by the invention does not relate to the use of harmful solvents, is a simple green micro-nano particle surface modification method, and accords with the current timeAnd the environment protection requirement of green development is replaced.
The stirring in the above embodiments is magnetic stirring; of course, other stirring methods than magnetic stirring can be used in the prior art.
The above embodiments are merely examples, and for example, the polymer matrix may be modified according to actual requirements, other types of polymer matrices in the prior art may be used in addition to the JY 257; the polymer may be crosslinked by physical or chemical crosslinking.
It will be readily appreciated by those skilled in the art that the foregoing description is merely a preferred embodiment of the invention and is not intended to limit the invention, but any modifications, equivalents, improvements or alternatives falling within the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (8)
1. A polymer composite material with high heat conduction and low viscosity characteristics based on aromatic compound modified heat conduction and insulation composite powder is characterized in that the polymer composite material is obtained by adding aromatic compound modified insulation composite powder into a polymer matrix material;
the aromatic compound modified insulating composite powder is prepared from at least 2 heat conduction micro-nano insulating powder serving as a raw material, an aromatic compound serving as a modifier, and an aqueous solution stirring method, wherein under the action of shearing force, the modifier is adsorbed to the surface of the powder by utilizing pi-pi interaction and covalent interaction between the modifier and the micro-nano insulating powder; wherein, for any one of the heat conduction micro-nano insulating powder, the heat conduction rate of the compound corresponding to the micro-nano insulating powder is not lower than 10W/mK; the mass ratio of the modifier to the powder is 20:1-5:1;
the at least 2 heat conduction micro-nano insulating powder is h-BN and Al 2 O 3 h-BN and Al 2 O 3 The mass ratio of (2) is 1:1-4:1, the grain diameter of the powder is not more than 50um, and the purity is more than 99 percent;
the aromatic compound is dopamine;
the polymer matrix material is epoxy resin;
the addition amount of the aromatic compound modified insulating composite powder accounts for 10-40 wt% of the polymer matrix material.
2. The polymer composite of claim 1, wherein h-BN and Al 2 O 3 The mass ratio of (2): 1.
3. the method for preparing the polymer composite material with high heat conduction and low viscosity characteristics based on the aromatic compound modified heat conduction and insulation composite powder as claimed in claim 1 or 2, comprising the following steps:
(1) Each heat-conducting micro-nano insulating powder is taken as a raw material, an aromatic compound is taken as a modifier, an aqueous solution stirring method is adopted, and under the action of shearing force, the modifier is adsorbed to the surface of the powder by utilizing pi-pi interaction and covalent interaction between the modifier and the micro-nano insulating powder, so that the corresponding aromatic compound modified insulating powder is obtained respectively; wherein, for each heat conduction micro-nano insulating powder, the mass ratio of the modifier to the powder in the aqueous solution system corresponding to the aqueous solution stirring method is 20:1-5:1;
(2) According to preset proportioning requirements, fully drying and uniformly mixing the aromatic compound modified insulating powder corresponding to at least 2 heat conduction micro-nano insulating powder, and grinding and sieving to obtain aromatic compound modified insulating composite powder;
(3) And (3) adding the aromatic compound modified insulating composite powder obtained in the step (2) into a prepolymer corresponding to a polymer matrix material, and carrying out blending molding with a polymer to obtain the polymer composite material.
4. The method of claim 3, wherein in step (1), for each thermally conductive micro-nano insulating powder:
the reaction temperature corresponding to the aqueous solution stirring method is room temperature-90 ℃, the stirring speed is 500-1000r/min, and the reaction time is 12-48 h;
the aromatic compound modified insulating powder obtained by the reaction is separated from an aqueous solution system by adopting a centrifugal machine to carry out centrifugal treatment for 10-30min at the rotating speed of 3000-6000 r/min;
in the step (1), the aromatic compound is dopamine, and Tris-HCl buffer solution and ammonia water are also added into an aqueous solution system corresponding to the aqueous solution stirring method, wherein the pH value of the aqueous solution system is 8.5-10.
5. The method of claim 3, wherein in the step (1), the mass ratio of the modifier to the powder in the aqueous solution system corresponding to the aqueous solution stirring method is 10:1.
6. The method according to claim 3, wherein the aromatic compound-modified insulating powder obtained in the step (1) has a thickness of the aromatic compound-modified layer on the surface of not more than 10nm.
7. The method according to claim 3, wherein in the step (3), the blending and molding is specifically: firstly, dispersing an aromatic compound modified insulating composite powder and a prepolymer mixed system, uniformly dispersing the aromatic compound modified insulating composite powder in the prepolymer, removing bubbles, and curing to obtain a cured polymer composite material;
the dispersion treatment is carried out at a high speed, the rotating speed is 600-2500 r/min, and the dispersion treatment time is 30-60 min.
8. Use of a polymer composite material with both high thermal conductivity and low viscosity characteristics based on aromatic compound modified thermal conductive insulating composite powder according to claim 1 or 2, characterized in that it is used in encapsulation of electronic packages or as thermal conductive gaskets.
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