CN113087971A - Heterostructure heat-conducting filler, preparation method and application thereof, silicon rubber heat-conducting and insulating composite material and preparation method thereof - Google Patents
Heterostructure heat-conducting filler, preparation method and application thereof, silicon rubber heat-conducting and insulating composite material and preparation method thereof Download PDFInfo
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Abstract
The invention provides a heterostructure heat-conducting filler, a preparation method and application thereof, a silicone rubber heat-conducting and insulating composite material and a preparation method thereof, and belongs to the technical field of heat-conducting and insulating materials. The invention adopts gamma-Glycidoxypropyltrimethoxysilane (GPTMS) and gamma-Aminopropyltriethoxysilane (APTES) to respectively treat boron nitride nanosheets and Al2O3Surface functional modification is carried out to oxidize the modificationCompared with single boron nitride nanosheets and alumina particles, the heat-conducting filler with the point-surface heterostructure can increase the contact and lap joint probability of the heat-conducting filler in a silicon rubber matrix, form more heat-conducting passages or networks, improve the construction efficiency of the heat-conducting passages of the heat-conducting filler in the matrix, facilitate the obtainment of a composite material with high heat-conducting performance when the consumption of the heat-conducting filler is low, and ensure the mechanical performance of the heat-conducting composite material.
Description
Technical Field
The invention relates to the technical field of heat-conducting and insulating materials, in particular to a heterostructure heat-conducting filler, a preparation method and application thereof, a silicone rubber heat-conducting and insulating composite material and a preparation method thereof.
Background
The silicon rubber has high flexibility, excellent high and low temperature resistance, corrosion resistance and outstanding electrical insulation performance, can play roles in sealing, insulation and shock absorption, and is widely applied to preparation of thermal interface materials and other composite materials. However, the silicon rubber body has a low thermal conductivity (about 0.2W/mK), and thus cannot meet the requirements of high power, high density and high-efficiency and rapid heat conduction/dissipation of highly integrated electronic components. In order to meet the increasing heat conduction/dissipation requirements in industry, improving the performance of silicone rubber becomes an important research topic.
The traditional preparation of the heat-conducting composite material mainly comprises simple filling of heat-conducting filler. However, the filling of a large amount of heat conductive filler is not only ineffective, but also inevitably weakens the mechanical properties of the composite material, and increases the production cost and the process difficulty; moreover, the conventional heat-conducting composite material needs to be added with more than 60 wt% of heat-conducting filler, which can obviously reduce the volume resistance of the material and reduce the insulating property of the material. Therefore, the heat-conducting property of the silicone rubber is effectively improved under the condition of ensuring the properties of insulation, mechanics and the like as far as possible, and the silicone rubber heat-conducting insulation composite material which is high in heat conduction and insulation and has good mechanical properties has important market significance and technical value.
Disclosure of Invention
The invention aims to provide a heterostructure heat-conducting filler, a preparation method and application thereof, a silicone rubber heat-conducting insulating composite material and a preparation method thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a heterostructure heat-conducting filler, which comprises the following steps:
mixing the boron nitride nanosheet dispersion liquid with a gamma-glycidyl ether oxypropyl trimethoxy silanol solution, and carrying out first modification to obtain modified boron nitride nanosheets;
mixing the alumina dispersion liquid with the gamma-aminopropyl triethoxy silanol solution for second modification to obtain modified alumina;
and mixing the modified boron nitride nanosheets, the modified alumina and the dispersing agent, and grafting to obtain the heterostructure heat-conducting filler.
Preferably, the mass ratio of the boron nitride nanosheet in the boron nitride nanosheet dispersion to the gamma-glycidoxypropyltrimethoxysilane in the gamma-glycidoxypropyltrimethoxysilane alcoholic solution is (1-10): (0.1 to 1); the temperature of the first modification is 25-90 ℃, and the time is 6-36 h.
Preferably, the mass ratio of the alumina in the alumina dispersion liquid to the gamma-aminopropyltriethoxysilane in the gamma-aminopropyltriethoxysilane solution is (1-10): (0.1 to 1); the temperature of the second modification is 25-90 ℃, and the time is 6-36 h.
Preferably, the mass ratio of the modified boron nitride nanosheet to the modified alumina is (0.5-5): (0.5 to 5); the grafting temperature is 25-100 ℃, and the grafting time is 6-36 h.
The invention provides a heterostructure heat-conducting filler prepared by the preparation method in the technical scheme, which comprises modified aluminum oxide and modified boron nitride nanosheets, wherein the modified aluminum oxide and the modified boron nitride nanosheets form a point-surface heterostructure, the modified aluminum oxide is a point, the modified boron nitride nanosheets are surfaces, and the modified aluminum oxide is grafted on the surfaces of the modified boron nitride nanosheets.
The invention provides application of the heterostructure heat-conducting filler in the technical scheme in a heat-conducting composite material.
The invention provides a preparation method of a silicon rubber heat-conducting and insulating composite material, which comprises the following steps:
mixing the heterostructure heat-conducting filler, the silicon rubber matrix, the cross-linking agent and the catalyst, shearing and coating the obtained mixture, and curing to obtain the silicon rubber heat-conducting insulating composite material; the heterostructure heat conduction filler is the heterostructure heat conduction filler in the technical scheme.
Preferably, the silicon rubber matrix comprises dealcoholization type room temperature vulcanized silicon rubber, dehydrogenation type room temperature vulcanized silicon rubber or deamination type room temperature vulcanized silicon rubber; the crosslinking agent comprises a silane crosslinking agent; the silane crosslinking agent comprises methyl triacetoxysilane, methyl trimethoxy silane, methyl triethoxy silane or methyl tributyrine oxime silane; the catalyst includes an organotin-based catalyst.
Preferably, the mass ratio of the heterostructure heat-conducting filler to the silicon rubber matrix to the cross-linking agent to the catalyst is (0-3): 2-10): 0.05-0.8): 0.03-0.5, and the dosage of the heterostructure heat-conducting filler is not 0.
The invention provides a silicon rubber heat-conducting and insulating composite material prepared by the preparation method in the technical scheme, which comprises a silicon rubber solidified body and a heterostructure heat-conducting filler uniformly dispersed in the silicon rubber solidified body.
The invention provides a preparation method of a heterostructure heat-conducting filler, which comprises the following steps: mixing the boron nitride nanosheet dispersion liquid with a gamma-glycidyl ether oxypropyl trimethoxy silanol solution, and carrying out first modification to obtain modified boron nitride nanosheets; mixing the alumina dispersion liquid with the gamma-aminopropyl triethoxy silanol solution for second modification to obtain modified alumina; nano-mixing the modified boron nitrideAnd mixing the sheet, the modified alumina and the dispersing agent, and grafting to obtain the heterostructure heat-conducting filler. The invention adopts gamma-Glycidoxypropyltrimethoxysilane (GPTMS) and gamma-Aminopropyltriethoxysilane (APTES) to respectively treat Boron Nitride Nanosheets (BNNS) and Al2O3Surface functional modification is carried out, the obtained modified alumina can be grafted on the surface of the modified boron nitride nanosheet, and thus the BNNS @ Al with a point-surface heterostructure is obtained2O3Thermally conductive filler, compared to single boron nitride nanosheet layer and Al2O3Particle, thermally conductive filler BNNS @ Al with a "point-face" heterostructure2O3The contact lapping probability of the heat-conducting filler in the silicon rubber matrix can be increased, and more efficient Al is formed2O3-Al2O3、BNNS-BNNS、Al2O3-BNNS-Al2O3Or BNNS-Al2O3The BNNS heat conduction path or network improves the heat conduction path construction efficiency of the heat conduction filler in the matrix, further improves the heat conduction performance of the heat conduction composite material, is beneficial to obtaining the composite material with high heat conduction performance when the using amount of the heat conduction filler is low, and ensures the mechanical property of the heat conduction composite material.
The invention provides a preparation method of a silicon rubber heat-conducting and insulating composite material, which comprises the following steps: mixing the heterostructure heat-conducting filler, the silicon rubber matrix, the cross-linking agent and the catalyst, shearing and coating the obtained mixture, and curing to obtain the silicon rubber heat-conducting insulating composite material; the heterostructure heat conduction filler is the heterostructure heat conduction filler in the technical scheme. According to the invention, the heterostructure heat-conducting filler can be effectively promoted to be oriented along the shearing direction by the shearing coating method, the aggregation effect of the heat-conducting filler in a silicon rubber matrix is reduced, the filling efficiency of the heat-conducting filler is improved, the orderliness of the heat-conducting filler in the silicon rubber matrix is effectively improved, the heat-conducting property in the orientation direction is favorably improved, the heat-conducting insulating composite material has obvious heat-conducting anisotropy, and the polymer heat-conducting composite material with high heat-conducting property and excellent mechanical property can be obtained under the condition of low using amount of the heat-conducting filler; moreover, the composite material still maintains good insulating property at the low dosage (30 wt%) of the heat-conducting filler. The results of the examples show that when the amount of the heat-conducting filler is 30 wt%, the in-plane heat conductivity coefficient of the prepared silicone rubber heat-conducting and insulating composite material is 2.51-2.86W/mK, and the inter-plane heat conductivity coefficient of the prepared silicone rubber heat-conducting and insulating composite material is 0.77-1.08W/mK; when the dosage of the heat-conducting filler is 10 wt%, the in-plane heat conductivity coefficient is 1.67W/mK, the inter-plane heat conductivity coefficient is 0.47W/mK, and the heat-conducting filler has excellent heat-conducting property.
Detailed Description
The invention provides a preparation method of a heterostructure heat-conducting filler, which comprises the following steps:
mixing the boron nitride nanosheet dispersion liquid with a gamma-glycidyl ether oxypropyl trimethoxy silanol solution, and carrying out first modification to obtain modified boron nitride nanosheets;
mixing the alumina dispersion liquid with the gamma-aminopropyl triethoxy silanol solution for second modification to obtain modified alumina;
and mixing the modified boron nitride nanosheets, the modified alumina and the dispersing agent, and grafting to obtain the heterostructure heat-conducting filler.
In the present invention, unless otherwise specified, all the starting materials required for the preparation are commercially available products well known to those skilled in the art.
According to the invention, boron nitride nanosheet dispersion liquid and gamma-glycidyl ether oxypropyl trimethoxysilanol solution are mixed for first modification to obtain modified boron nitride nanosheets. The source and specification of the Boron Nitride Nanosheet (BNNS) are not particularly limited in the present invention, and commercially available products well known in the art are sufficient; in an embodiment of the invention, the average diameter of the boron nitride nanosheets is preferably 500 nm. In the invention, the preparation method of the boron nitride nanosheet dispersion liquid is preferably to disperse Boron Nitride Nanosheets (BNNS) in ethanol, the dispersion is preferably carried out under ultrasonic conditions, and the dispersion time is preferably 30 min; the conditions of the ultrasound are not particularly limited in the present invention, and the ultrasound process well known in the art may be used. In the invention, the dosage ratio of the boron nitride nanosheet to the ethanol is preferably (1-10) g: (50-100) mL, more preferably (3-8) g: (60-80) mL; the ethanol is preferably anhydrous ethanol.
In the invention, the preparation process of the gamma-glycidoxypropyltrimethoxysilane alcohol solution is preferably to dissolve gamma-Glycidoxypropyltrimethoxysilane (GPTMS) in alcohol and perform ultrasonic treatment for 20 min; the conditions of the ultrasound are not particularly limited in the present invention, and the ultrasound process well known in the art may be used. In the present invention, the alcohol is preferably ethanol; the ethanol is preferably anhydrous ethanol. In the invention, the dosage ratio of the gamma-glycidoxypropyltrimethoxysilane to the alcohol is preferably (0.1-1) g: (5-50) mL, more preferably (0.3-0.8) g: (10-30) mL.
The process of mixing the boron nitride nanosheet dispersion and the gamma-glycidoxypropyltrimethoxysilane solution is not particularly limited, and the materials can be uniformly mixed according to the process known in the art.
In the invention, the mass ratio of the boron nitride nanosheet in the boron nitride nanosheet dispersion to the gamma-glycidoxypropyltrimethoxysilane in the gamma-glycidoxypropyltrimethoxysilane alcoholic solution is preferably (1-10): (0.1-1), more preferably (3-8): (0.2-0.8), more preferably (4-6): (0.3-0.6).
In the invention, the temperature of the first modification is preferably 25-90 ℃, more preferably 35-80 ℃, and further preferably 45-60 ℃; the time is preferably 6 to 36 hours, more preferably 10 to 30 hours, and further preferably 15 to 25 hours. In the first modification, Si-O-CH on gamma-glycidoxypropyltrimethoxysilane3Reacts with the hydroxyl groups on BNNS to graft gamma-glycidoxypropyltrimethoxysilane onto BNNS.
After the first modification is completed, the obtained material is preferably subjected to centrifugation, washing and drying in sequence to obtain a modified boron nitride nanosheet (marked as GPTMS-g-BNNS). In the invention, the rotation speed of the centrifugation is preferably 500-6000 rmp, more preferably 1000-5000 rmp, and further preferably 2000-3000 rmp; the time is preferably 5 to 60min, and more preferably 20 to 50 min. In the present invention, the washing reagent is preferably commercially available ethanol, and the number of times of washing is not particularly limited in the present invention, and may be adjusted according to actual needs. In the invention, the drying mode is preferably vacuum drying, and the drying temperature is preferably 25-100 ℃, and more preferably 30-80 ℃; the time is preferably 6 to 36 hours, and more preferably 10 to 30 hours.
The invention mixes the alumina dispersion liquid and the gamma-aminopropyl triethoxy silanol solution for the second modification to obtain the modified alumina. In the present invention, the method for preparing the alumina dispersion is preferably that Al is mixed with2O3Dispersing in ethanol. The source and specification of the alumina are not particularly limited in the present invention, and commercially available products well known in the art may be used; in the embodiment of the present invention, the alumina is preferably in an alpha crystal form, and the average diameter of the alumina is preferably 80 nm. The dispersion is preferably carried out under ultrasonic conditions, and the dispersion time is preferably 30 min; the conditions of the ultrasound are not particularly limited in the present invention, and the ultrasound process well known in the art may be used. In the invention, the dosage ratio of the alumina to the ethanol is preferably (1-10) g: (50-100) mL, more preferably (3-8) g: (60-80) mL; the ethanol is preferably anhydrous ethanol.
In the invention, the preparation method of the gamma-aminopropyl triethoxy silanol solution is preferably that gamma-aminopropyl triethoxy silane (APTES) is dissolved in alcohol and is subjected to ultrasonic treatment for 20 min; the conditions of the ultrasound are not particularly limited in the present invention, and the ultrasound process well known in the art may be used. In the present invention, the alcohol is preferably ethanol; the ethanol is preferably anhydrous ethanol. In the present invention, the amount ratio of the γ -aminopropyltriethoxysilane to the alcohol is preferably (0.1 to 1) g: (5-50) mL, more preferably (0.3-0.8) g: (10-30) mL.
The process of mixing the alumina dispersion and the gamma-aminopropyltriethoxy silanol solution is not particularly limited in the present invention, and the materials can be uniformly mixed according to the process well known in the art.
In the invention, the mass ratio of the alumina in the alumina dispersion liquid to the gamma-aminopropyltriethoxysilane in the gamma-aminopropyltriethoxysilane solution is (1-10): (0.1-1), more preferably (3-8): (0.2-0.8), more preferably (4-6): (0.3-0.6).
In the invention, the temperature of the second modification is preferably 25-90 ℃, more preferably 35-80 ℃, and further preferably 45-60 ℃; the time is preferably 6 to 36 hours, more preferably 10 to 30 hours, and further preferably 15 to 25 hours. In the second modification process, Si-O-CH on gamma-aminopropyltriethoxysilane3Reacts with hydroxyl groups on the surface of the alumina to graft gamma-aminopropyltriethoxysilane onto the alumina.
After the second modification is finished, the obtained material is preferably centrifuged, washed and dried in sequence to obtain modified alumina (APTES-g-Al)2O3). In the invention, the rotation speed of the centrifugation is preferably 500-6000 rmp, more preferably 1000-5000 rmp, and further preferably 2000-3000 rmp; the time is preferably 5 to 60min, and more preferably 20 to 50 min. In the present invention, the washing reagent is preferably commercially available ethanol, and the number of times of washing is not particularly limited in the present invention, and may be adjusted according to actual needs. In the invention, the drying mode is preferably vacuum drying, and the drying temperature is preferably 25-100 ℃, and more preferably 30-80 ℃; the time is preferably 6 to 36 hours, and more preferably 10 to 30 hours.
After the modified boron nitride nanosheet and the modified alumina are obtained, the modified boron nitride nanosheet, the modified alumina and the dispersing agent are mixed and grafted to obtain the heterostructure heat-conducting filler. In the invention, the mass ratio of the modified boron nitride nanosheet to the modified alumina is preferably (0.5-5): (0.5-5), more preferably (1-4): (1-4), more preferably (2-3): (2-3);
in the invention, the dispersant is preferably absolute ethyl alcohol, and the dosage ratio of the modified boron nitride nanosheet to the dispersant is preferably (0.5-5): (20-300 mL), more preferably (1-4): (100-200 mL), more preferably (2-3): (150-180 mL).
The process of mixing the modified boron nitride nanosheet, the modified alumina and the dispersing agent is not particularly limited, and the materials can be uniformly mixed according to the process well known in the art.
After the modified boron nitride nanosheets, the modified alumina and the dispersing agent are mixed, grafting is preferably performed on the obtained mixed material; the grafting is preferably carried out under the condition of stirring, and the rotating speed of the stirring is preferably 500-4000 rmp, and more preferably 1000-3000 rpm; the grafting temperature is preferably 25-100 ℃, more preferably 35-80 ℃, and further preferably 50-60 ℃; the time is preferably 6 to 36 hours, more preferably 10 to 30 hours, and further preferably 15 to 20 hours.
In the grafting process, an epoxy group on GPTMS (gamma-glycidoxypropyltrimethoxysilane) in the modified boron nitride nanosheet is grafted with an amino group on APTES (3-aminopropyltriethoxysilane) in the modified alumina, so that smaller-particle Al is obtained2O3Attached to the BNNS plate to form a "dot-plane" structure.
After the grafting is finished, the obtained material is preferably centrifuged, washed and dried in sequence to obtain the heterostructure heat-conducting filler BNNS @ Al2O3. In the invention, the rotation speed of the centrifugation is preferably 500-6000 rmp, more preferably 1000-5000 rmp, and further preferably 2000-3000 rmp; the time is preferably 5 to 60min, and more preferably 20 to 50 min. In the present invention, the washing reagent is preferably commercially available ethanol, and the number of times of washing is not particularly limited in the present invention, and may be adjusted according to actual needs. In the invention, the drying mode is preferably vacuum drying, and the drying temperature is preferably 25-100 ℃, and more preferably 30-80 ℃; the time is preferably 6 to 36 hours, and more preferably 10 to 30 hours. .
The invention provides a heterostructure heat-conducting filler prepared by the preparation method in the technical scheme, which comprises modified aluminum oxide and modified boron nitride nanosheets, wherein the modified aluminum oxide and the modified boron nitride nanosheets form a point-surface heterostructure, the modified aluminum oxide is a point, the modified boron nitride nanosheets are surfaces, and the modified aluminum oxide is grafted on the surfaces of the modified boron nitride nanosheets.
The invention provides application of the heterostructure heat-conducting filler in the technical scheme in a heat-conducting composite material. The method of the present invention is not particularly limited, and the heterostructure thermal conductive filler is used as a thermal conductive filler in a thermal conductive composite material according to a method well known in the art.
The invention provides a preparation method of a silicon rubber heat-conducting and insulating composite material, which comprises the following steps:
mixing the heterostructure heat-conducting filler, the silicon rubber matrix, the cross-linking agent and the catalyst, shearing and coating the obtained mixture, and curing to obtain the silicon rubber heat-conducting insulating composite material; the heterostructure heat conduction filler is the heterostructure heat conduction filler in the technical scheme.
The invention mixes the heterogeneous structure heat conduction filler, the silicon rubber matrix, the cross-linking agent and the catalyst. In the present invention, the silicone rubber base preferably includes dealcoholized type room temperature vulcanized silicone rubber, dehydrogenated type room temperature vulcanized silicone rubber or deaminated type room temperature vulcanized silicone rubber; the silicon rubber matrix is preferably hydroxyl-terminated polydimethylsiloxane silicon rubber; the specific types of the dealcoholized type room temperature vulcanized silicone rubber, the dehydrogenated type room temperature vulcanized silicone rubber or the deaminated type room temperature vulcanized silicone rubber are not specially limited, and the dealcoholized type room temperature vulcanized silicone rubber, the dehydrogenated type room temperature vulcanized silicone rubber or the deaminated type room temperature vulcanized silicone rubber can be prepared by the hydroxyl-terminated polydimethylsiloxane type silicone rubber which is well known in the field and is limited according to the molecular weight; in the examples of the present invention, a dealcoholized room temperature vulcanized silicone rubber RTV-2SR was used.
In the present invention, the crosslinking agent preferably includes a silane-based crosslinking agent; the silane-based crosslinking agent preferably includes methyltriacetoxysilane, methyltrimethoxysilane, methyltriethoxysilane, or methyltributanone oxime silane.
In the present invention, the catalyst preferably includes an organotin-based catalyst, and the organotin-based catalyst preferably includes dibutyltin dilaurate, dibutyltin diacetate, or stannous octoate.
In the invention, the mass ratio of the heterostructure heat-conducting filler, the silicon rubber matrix, the cross-linking agent and the catalyst is preferably (0-3): 2-10): 0.05-0.8): 0.03-0.5, and the dosage of the heterostructure heat-conducting filler is not 0, more preferably (0.5-2.5): 3-8): 0.1-0.6): 0.1-0.4), and further preferably (1.0-2.0): 4-6): 0.3-0.5): 0.2-0.3.
In the invention, the process of mixing the heterostructure heat-conducting filler, the silicon rubber matrix, the cross-linking agent and the catalyst is preferably to add the heterostructure heat-conducting filler into the silicon rubber matrix, add the cross-linking agent, and stir at the speed of 500-4000 rmp for 10-90 min at the temperature of 25-60 ℃; and adding a catalyst, and stirring at the speed of 500-4000 rmp for 5-20 min at the temperature of 25-60 ℃ to obtain a mixture.
In the invention, when the dosage of the heterostructure heat conduction filler is more than or equal to 20 wt%, a diluent is preferably added at the same time when a cross-linking agent is added in the mixing process; the diluent preferably comprises n-hexane or anhydrous tetrahydrofuran. The invention utilizes the diluent to overcome the problem that the viscosity of the system is increased and the stirring and the mixing are difficult to realize due to the increase of the addition amount of the heterostructure heat-conducting filler.
In the invention, the mass ratio of the diluent to the heterostructure heat-conducting filler is preferably (0-5): 0-3, and the amount of the heterostructure heat-conducting filler is not 0, more preferably (0.5-4): 0.2-2.5), and further preferably (1-3): 0.5-2.0.
After the mixture is obtained, the obtained mixture is subjected to shear coating; the mode of the shear coating preferably comprises blade coating, and the invention preferably uniformly pours the mixture on a glass plate and blade coats the mixture until the surface is flat; the size of the glass plate is not specially limited, and the glass plate can be adjusted according to actual requirements; in an embodiment of the invention, the glass plate has a dimension of 20cm × 15cm × 0.5 cm. The knife coating is preferably carried out using a four-side coater. According to the invention, the silicon rubber heat-conducting insulating composite material is prepared in a shearing coating mode, so that the orderliness of the heterostructure heat-conducting filler in a silicon rubber matrix is effectively improved, the heat-conducting property in the orientation direction is favorably improved, and the material has obvious heat-conducting anisotropy.
After the shear coating is completed, the present invention cures the resulting coating film. In the invention, the curing temperature is preferably 25-90 ℃, more preferably 35-80 ℃, and the time is preferably 1-12 h, more preferably 3-10 h, and further preferably 5-8 h.
In the curing process, the silicon rubber matrix reacts with the cross-linking agent under the action of the catalyst, and the silicon rubber cured body is formed through self dealcoholization and curing, and the heterostructure heat-conducting filler does not participate in the reaction and is uniformly dispersed in the cured body of the silicon rubber matrix.
The invention provides a silicon rubber heat-conducting and insulating composite material prepared by the preparation method in the technical scheme, which comprises a silicon rubber solidified body and a heterostructure heat-conducting filler uniformly dispersed in the silicon rubber solidified body.
The invention constructs the heat-conducting filler BNNS @ Al with a point-surface heterostructure2O3Compared with single lamella and particles, the contact lapping probability of the heat-conducting filler in the silicon rubber matrix is increased, and more efficient Al is formed2O3-Al2O3、BNNS-BNNS、Al2O3-BNNS-Al2O3Or BNNS-Al2O3BNNS heat conduction paths or networks, which improves the heat conduction path construction efficiency of the heat conduction filler in the silicon rubber matrix; the invention can effectively promote the orientation of the heat-conducting filler along the shearing direction by a shearing coating method, reduces the aggregation effect of the heat-conducting filler in the silicon rubber matrix, improves the filling efficiency of the heat-conducting filler, simultaneously effectively improves the orderliness of the heat-conducting filler in the silicon rubber matrix, is beneficial to improving the heat-conducting property in the orientation direction, and ensures that the heat-conducting insulating composite material has obvious heat-conducting anisotropy.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the following examples, boron nitride nanoplates having an average diameter of 500nm were used; the used alumina is alpha crystal form, and the average diameter is 80 nm; the ethanol is anhydrous ethanol.
Example 1
Dispersing 8g of BNNS in 80mL of ethanol, and performing ultrasonic dispersion for 30min to obtain a BNNS dispersion liquid; dissolving 0.8g of GPTMS in 20mL of ethanol, performing ultrasonic treatment for 20min to uniformly dissolve the GPTMS, pouring the obtained solution into the BNNS dispersion solution, and reacting for 12h at 70 ℃; after the reaction is finished, centrifuging the obtained material for 15min under the condition of 3000rmp, washing the obtained product with ethanol for multiple times until the product is cleaned, and then drying the product in vacuum at 60 ℃ for 12h to obtain modified BNNS which is marked as GPTMS-g-BNNS;
adding 8gAl2O3Dispersing in 80mL ethanol, and ultrasonically dispersing for 30min to obtain Al2O3A dispersion liquid; dissolving 0.8g APTES in 20mL ethanol, performing ultrasonic treatment for 20min, and pouring the obtained solution into Al2O3Reacting in the dispersion liquid for 12 hours at 70 ℃; after the reaction is finished, centrifuging the obtained material for 15min under the condition of 3000rmp, washing the obtained product with ethanol for multiple times until the product is cleaned, and then drying the product in vacuum at 60 ℃ for 12h to obtain modified alumina, which is marked as APTES-g-Al2O3；
3g of GPTMS-g-BNNS and 1.5g of APTES-g-Al are added2O3Dispersing in 100mL ethanol, and reacting at 70 ℃ at a stirring speed of 2500rmp for 12 h; after the reaction is finished, centrifuging the obtained material for 15min under the condition of 3000rmp, washing the obtained product with ethanol for multiple times until the product is cleaned, and then drying the product in vacuum at 60 ℃ for 12h to obtain the heterostructure heat-conducting filler BNNS @ Al2O3；
1.5g of the heat-conducting filler BNNS @ Al2O3Adding into 3.1g silicon rubber matrix (RTV-2SR), adding 0.25g crosslinking agent (methyl triethoxysilane) and 4g n-hexane, stirring at 2000rmp for 30min at 60 deg.C, adding 0.15g catalyst (dibutyltin dilaurate) into the obtained mixture, stirring at 2000rmp for 10min at 60 deg.C, pouring the obtained mixture onto glass plate with size of 20cm × 15cm × 0.5cm, scraping with four-side coater to smooth surface, and curing at 70 deg.C for 2h to obtain BNNS @ Al2O3Silicon rubber heat-conducting insulating composite material.
Example 2
Preparing modified BNNS according to the conditions of the embodiment 1, and marking as GPTMS-g-BNNS;
modified alumina, reported as APTES-g-Al, was prepared according to the conditions of example 12O3；
1.5g of GPTMS-g-BNNS and 3g of APTES-g-Al are added2O3Dispersing in 100mL ethanol, and reacting at 70 ℃ at a stirring speed of 2500rmp for 12 h; after the reaction is finished, centrifuging the obtained material for 15min under the condition of 3000rmp, washing the obtained product with ethanol for multiple times until the product is cleaned, and then drying the product in vacuum at 60 ℃ for 12h to obtain the heterostructure heat-conducting filler BNNS @ Al2O3；
1.5g of the heat-conducting filler BNNS @ Al2O3Adding into 3.1g silicon rubber matrix (RTV-2SR), adding 0.25g crosslinking agent (methyl triethoxysilane) and 4g n-hexane, stirring at 2000rmp for 30min at 60 deg.C, adding 0.15g catalyst (dibutyltin dilaurate) into the obtained mixture, stirring at 2000rmp for 10min at 60 deg.C, pouring the obtained mixture onto glass plate with size of 20cm × 15cm × 0.5cm, scraping with four-side coater to smooth surface, and curing at 70 deg.C for 2h to obtain BNNS @ Al2O3Silicon rubber heat-conducting insulating composite material.
Example 3
Preparing modified BNNS according to the conditions of the embodiment 1, and marking as GPTMS-g-BNNS;
modified alumina, reported as APTES-g-Al, was prepared according to the conditions of example 12O3；
3g of GPTMS-g-BNNS and 3g of APTES-g-Al are added2O3Dispersing in 100mL ethanol, and reacting at 70 ℃ at a stirring speed of 2500rmp for 12 h; after the reaction is finished, centrifuging the obtained material for 15min under the condition of 3000rmp, washing the obtained product with ethanol for multiple times until the product is cleaned, and then drying the product in vacuum at 60 ℃ for 12h to obtain the heterostructure heat-conducting filler BNNS @ Al2O3；
0.5g of the heat conductive fillerBNNS@Al2O3Adding into 4g silicon rubber matrix (RTV-2SR), adding 0.3g cross-linking agent (methyl triethoxysilane) and 1g n-hexane, stirring at 60 deg.C and 2000rmp for 30min, adding 0.2g catalyst (dibutyltin dilaurate) into the obtained mixture, stirring at 60 deg.C and 2000rmp for 10min, pouring the obtained mixture onto glass plate with size of 20cm × 15cm × 0.5cm, scraping with four-side coater to smooth surface, and curing at 70 deg.C for 2h to obtain BNNS @ Al2O3Silicon rubber heat-conducting insulating composite material.
Example 4
Preparing modified BNNS according to the conditions of the embodiment 1, and marking as GPTMS-g-BNNS;
modified alumina, reported as APTES-g-Al, was prepared according to the conditions of example 12O3；
3g of GPTMS-g-BNNS and 3g of APTES-g-Al are added2O3Dispersing in 100mL ethanol, and reacting at 70 ℃ at a stirring speed of 2500rmp for 12 h; after the reaction is finished, centrifuging the obtained material for 15min under the condition of 3000rmp, washing the obtained product with ethanol for multiple times until the product is cleaned, and then drying the product in vacuum at 60 ℃ for 12h to obtain the heterostructure heat-conducting filler BNNS @ Al2O3；
1.5g of the heat-conducting filler BNNS @ Al2O3Adding into 3.1g silicon rubber matrix (RTV-2SR), adding 0.25g crosslinking agent (methyl triethoxysilane) and 4g n-hexane, stirring at 2000rmp for 30min at 60 deg.C, adding 0.15g catalyst (dibutyltin dilaurate) into the obtained mixture, stirring at 2000rmp for 10min at 60 deg.C, pouring the obtained mixture onto glass plate with size of 20cm × 15cm × 0.5cm, scraping with four-side coater to smooth surface, and curing at 70 deg.C for 2h to obtain BNNS @ Al2O3Silicon rubber heat-conducting insulating composite material.
Comparative example 1
3.1g of silicon rubber matrix (RTV-2SR) and 0.25g of crosslinking agent (methyl triethoxysilane) are blended and stirred uniformly, then 0.15g of catalyst (dibutyltin dilaurate) is added, then the mixture is stirred at the speed of 2000rmp for 10min at the temperature of 60 ℃, the obtained mixture is poured uniformly on a glass plate with the size of 20cm multiplied by 15cm multiplied by 0.5cm, the surface is scraped by a four-side coater to be flat, and the mixture is cured for 2h at the temperature of 70 ℃ to obtain pure RTV-2 SR.
Comparative example 2
Adding 1.5g of BNNS into 3.1g of silicon rubber matrix (RTV-2SR), adding 0.25g of crosslinking agent (methyl triethoxysilane) and 4g of n-hexane, stirring at the speed of 2000rmp for 30min at 60 ℃, adding 0.15g of catalyst (dibutyltin dilaurate) into the obtained mixture, stirring at the speed of 2000rmp for 10min at 60 ℃, uniformly pouring the obtained mixture onto a glass plate with the size of 20cm multiplied by 15cm multiplied by 0.5cm, scraping the mixture by a four-side film coater until the surface is smooth, and curing for 2h at 70 ℃ to obtain the BNNS/heat-conducting silicon rubber insulating composite material.
Comparative example 3
1.5gAl2O3Adding into 3.1g silicon rubber matrix (RTV-2SR), adding 0.25g cross-linking agent (methyl triethoxysilane) and 4g n-hexane, stirring at 2000rmp for 30min at 60 deg.C, adding 0.15g catalyst (dibutyltin dilaurate) into the obtained mixture, stirring at 2000rmp for 10min at 60 deg.C, pouring the obtained mixture onto glass plate with size of 20cm × 15cm × 0.5cm, scraping with four-side coater until surface is flat, and curing at 70 deg.C for 2 hr to obtain Al2O3Silicon rubber heat-conducting insulating composite material.
Comparative example 4
1.5g of blended heat-conducting filler BNNS/Al2O3(wt/wt, 1/1) was added to 3.1g of a silicone rubber base (RTV-2SR), 0.25g of a crosslinking agent (methyltriethoxysilane) and 4g of n-hexane were added, followed by stirring at 60 ℃ and 2000rmp for 30min, 0.15g of a catalyst (dibutyltin dilaurate) was added to the resulting mixture, followed by stirring at 2000rmp for 10min at 60 ℃, the resulting mixture was poured uniformly onto a glass plate having a size of 20 cm. times.15 cm. times.0.5 cm, knife-coated with a four-side coater until the surface was flat, and cured at 70 ℃ for 2h to obtain BNNS/Al2O3Silicon rubber heat-conducting insulating composite material.
Performance testing
1) The thermal conductivity test was performed on the thermally conductive and insulating materials prepared in examples 1 to 4 and comparative examples 1 to 4, wherein the thermal conductivity was measured according to ISO 22007-2: the measurement of the in-plane and inter-plane thermal conductivity was carried out by the method described in 2008 standard (measurement of thermal conductivity and thermal diffusivity of plastic), and the thermal conductivity (. lamda.) of the sample was measured by a Hot Disk TPS2200 model thermal constant analyzer from AB, Sweden, and the results are shown in Table 1.
2) The thermal conductive and insulating composite materials prepared in examples 1 to 4 and comparative examples 1 to 4 were tested for tensile properties using a model 3342 electronic universal tester, manufactured by Instron, USA, according to GB/T1040.3-2006 Standard (test for tensile properties of plastics), and the results are shown in Table 1.
3) According to the GB/T1408-2016 standard (test method for the volume resistivity and the surface resistivity of the solid insulating material), the volume resistivity (rho v) of the heat-conducting and insulating composite materials prepared in the examples 1-4 and the comparative examples 1-4 is tested by adopting a ZC-36 high-resistance meter of Shanghai precision instruments Limited, and the insulation performance is verified, and the results are shown in Table 1.
TABLE 1 Performance data for composites prepared in examples 1-4 and comparative examples 1-4
As can be seen from Table 1, when the amount of the heat-conducting filler is 30 wt%, compared with comparative examples 1 to 4, the heat-conducting insulating composite material prepared in examples 1 to 4 of the present invention has a significantly improved heat-conducting coefficient under the condition of ensuring that the changes in tensile strength, elongation at break and volume resistivity are small, which indicates that the heat-conducting property of the material is significantly improved. When the amount of the thermal conductive filler is 10 wt% (example 3), the thermal conductive insulation composite material of the present invention still has excellent mechanical properties, thermal conductive properties and insulation properties.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The preparation method of the heterostructure heat-conducting filler is characterized by comprising the following steps:
mixing the boron nitride nanosheet dispersion liquid with a gamma-glycidyl ether oxypropyl trimethoxy silanol solution, and carrying out first modification to obtain modified boron nitride nanosheets;
mixing the alumina dispersion liquid with the gamma-aminopropyl triethoxy silanol solution for second modification to obtain modified alumina;
and mixing the modified boron nitride nanosheets, the modified alumina and the dispersing agent, and grafting to obtain the heterostructure heat-conducting filler.
2. The preparation method according to claim 1, wherein the mass ratio of the boron nitride nanosheet in the boron nitride nanosheet dispersion to the gamma-glycidoxypropyltrimethoxysilane in the gamma-glycidoxypropyltrimethoxysilane alcohol solution is (1-10): (0.1 to 1); the temperature of the first modification is 25-90 ℃, and the time is 6-36 h.
3. The method according to claim 1, wherein the mass ratio of the alumina in the alumina dispersion to the γ -aminopropyltriethoxysilane in the γ -aminopropyltriethoxysilanol solution is (1-10): (0.1 to 1); the temperature of the second modification is 25-90 ℃, and the time is 6-36 h.
4. The preparation method according to claim 1, wherein the mass ratio of the modified boron nitride nanosheet to the modified alumina is (0.5-5): (0.5 to 5); the grafting temperature is 25-100 ℃, and the grafting time is 6-36 h.
5. The heterostructure heat-conducting filler prepared by the preparation method of any one of claims 1 to 4 comprises modified aluminum oxide and modified boron nitride nanosheets, the modified aluminum oxide and the modified boron nitride nanosheets form a point-face heterostructure, the modified aluminum oxide is a point, the modified boron nitride nanosheets are faces, and the modified aluminum oxide is grafted on the faces of the modified boron nitride nanosheets.
6. Use of the heterostructure thermally conductive filler of claim 5 in a thermally conductive composite.
7. The preparation method of the silicon rubber heat-conducting and insulating composite material is characterized by comprising the following steps of:
mixing the heterostructure heat-conducting filler, the silicon rubber matrix, the cross-linking agent and the catalyst, shearing and coating the obtained mixture, and curing to obtain the silicon rubber heat-conducting insulating composite material; the heterostructure thermal conductive filler is the heterostructure thermal conductive filler of claim 5.
8. The production method according to claim 7, wherein the silicone rubber base comprises a dealcoholized type room temperature vulcanized silicone rubber, a dehydrogenated type room temperature vulcanized silicone rubber, or a deaminated type room temperature vulcanized silicone rubber; the crosslinking agent comprises a silane crosslinking agent; the silane crosslinking agent comprises methyl triacetoxysilane, methyl trimethoxy silane, methyl triethoxy silane or methyl tributyrine oxime silane; the catalyst includes an organotin-based catalyst.
9. The method according to claim 7 or 8, wherein the mass ratio of the heterostructure heat-conducting filler to the silicone rubber matrix to the cross-linking agent to the catalyst is (0-3): 2-10): 0.05-0.8): 0.03-0.5, and the amount of the heterostructure heat-conducting filler is not 0.
10. The silicone rubber heat-conducting and insulating composite material prepared by the preparation method of any one of claims 7 to 9 comprises a cured silicone rubber body and a heterostructure heat-conducting filler uniformly dispersed in the cured silicone rubber body.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113881250A (en) * | 2021-10-20 | 2022-01-04 | 广州集泰化工股份有限公司 | Heat-conducting filler and surface treatment method thereof |
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| CN115028892A (en) * | 2022-06-10 | 2022-09-09 | 安徽建筑大学 | Three-dimensional structure modified boron nitride and preparation method and application thereof |
| CN116102886A (en) * | 2022-09-07 | 2023-05-12 | 西北橡胶塑料研究设计院有限公司 | High-heat-conductivity insulating silicon rubber composite material and preparation method thereof |
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- 2021-04-07 CN CN202110371409.4A patent/CN113087971A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| HAN YAN ET AL.: "Flexible thermally conductive and electrically insulating silicone rubber composite films with BNNS@A12O3 fillers", 《ADVANCED COMPOSITES AND HYBRID MATERIALS》 * |
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