CN113897060A - Grafted graphene heat dissipation silica gel composition, grafted graphene heat dissipation silica gel, and preparation method and application thereof - Google Patents
Grafted graphene heat dissipation silica gel composition, grafted graphene heat dissipation silica gel, and preparation method and application thereof Download PDFInfo
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Abstract
The present disclosure relates to a grafted graphene heat dissipation silica gel composition, a grafted graphene heat dissipation silica gel, a preparation method and an application thereof, wherein the grafted graphene heat dissipation silica gel composition comprises silicone rubber, grafted graphene powder, modified carbon nanotube powder, a crosslinking catalyst, a curing agent, a solvent and an adhesive; based on the total weight of the grafted graphene heat dissipation silica gel composition, the content of the silicone rubber is 30-60 wt%, the content of the grafted graphene powder is 5-15 wt%, the content of the modified carbon nanotube powder is 1-5 wt%, the content of the crosslinking catalyst is 0.3-3 wt%, the content of the curing agent is 3-10 wt%, the content of the solvent is 10-50 wt%, and the content of the adhesive is 0.1-2 wt%. According to the grafted graphene heat dissipation silica gel composition, the graphene filler particles are subjected to grafting modification, so that the structure of graphene can be maintained, the graphene filler particles are good in dispersibility in a silicon rubber matrix and not easy to accumulate, a heat conduction path is further formed, and the heat dissipation performance of a composite interface material is improved.
Description
Technical Field
The disclosure relates to the field of interface materials, in particular to a grafted graphene heat dissipation silica gel composition, a grafted graphene heat dissipation silica gel, and a preparation method and application thereof.
Background
Silicon rubber is a common sealing material, silicon element is introduced into rubber, Si-O bonds are alternately generated, the temperature resistance of the rubber is improved, but the heat dissipation of the rubber is extremely poor, and the heat dissipation performance of the packaging material is also higher along with the integration and high density of components. In order to meet the application requirements of the packaging material, a heat-conducting filler with high heat conductivity coefficient needs to be added into the silicone rubber. Common high thermal conductivity fillers include graphene, carbon fiber, carbon nanotube, zinc oxide (ZnO), magnesium oxide (MgO), and aluminum oxide (Al)2O3) Silicon carbide (SiC), Boron Nitride (BN), and the like. The single-layer graphene has the thermal conductivity of 5300W/m.k, exceeds all other materials, has extremely high research value in the aspects of heat conduction and electric conduction, is often used as an inorganic filler to be added into an organic matrix, and increases the heat dissipation performance of the matrix. Graphene is used as an inorganic filler, and due to strong pi-pi interaction between sheet layers, the graphene is added into a silicon rubber organic matrix, so that the graphene and the silicon rubber organic matrix have poor interface compatibility, interface scattering is enhanced, and a phonon propagation free path is shortened, and therefore the graphene is not beneficial to exerting the heat dissipation advantage of the graphene.
Disclosure of Invention
The purpose of the present disclosure is to provide a grafted graphene heat dissipation silica gel composition, a grafted graphene heat dissipation silica gel, and a preparation method and an application thereof.
The first aspect of the present disclosure provides a grafted graphene heat dissipation silica gel composition, which includes silicone rubber, grafted graphene powder, modified carbon nanotube powder, a crosslinking catalyst, a curing agent, a solvent, and an adhesive; based on the total weight of the grafted graphene heat dissipation silica gel composition, the content of the silicone rubber is 30-60 wt%, the content of the grafted graphene powder is 5-15 wt%, the content of the modified carbon nanotube powder is 1-5 wt%, the content of the crosslinking catalyst is 0.3-3 wt%, the content of the curing agent is 3-10 wt%, the content of the solvent is 10-50 wt%, and the content of the adhesive is 0.1-2 wt%.
Optionally, the weight ratio of the grafted graphene powder to the modified carbon nanotube powder is (6-10): 1; the average particle size of the grafted graphene powder is 3-6 mu m; the average particle size of the modified carbon nanotube powder is 5-15 μm.
Optionally, the grafted graphene powder is obtained by modifying graphene oxide with gamma-aminopropyltriethoxysilane; the modified carbon nano tube powder is obtained by modifying the surface of a carbon nano tube by adopting a silane coupling agent.
Optionally, the silicone rubber is alpha, omega-dihydroxy polydimethylsiloxane with viscosity of 6000-20000 cP at 25 ℃;
the crosslinking catalyst is organic tin, and the organic tin comprises one or more of dibutyl tin dilaurate, stannous octoate and dibutyltin diacetate; preferably, the organotin is dibutyl tin dilaurate;
the curing agent is tetraethoxysilane; the adhesive is KH-792.
A second aspect of the present disclosure provides a method for preparing a grafted graphene heat dissipation silica gel by using the grafted graphene heat dissipation silica gel composition according to the first aspect of the present disclosure, the method including: and mixing and stirring the grafted graphene powder, the modified carbon nanotube powder, the solvent, the silicon rubber, the curing agent and the adhesive, and adding the crosslinking catalyst for curing.
Optionally, the method further comprises: the preparation method comprises the following steps:
(1) preparing crystalline flake graphite, concentrated sulfuric acid, concentrated phosphoric acid and KMnO4Mixing to obtain a mixed material;
(2) adding H to the mixture2O2Washing to obtain graphene oxide;
(3) mixing the graphene oxide, gamma-aminopropyltriethoxysilane, chloroform and toluene for reaction and washing to obtain aminated graphene oxide;
(4) and mixing the aminated graphene oxide with hydrazine hydrate for reaction.
Optionally, the average particle size of the crystalline flake graphite in the step (1) is 40-60 mm;
the flake graphite, concentrated sulfuric acid, concentrated phosphoric acid and KMnO4The weight ratio of (1): (150-250): (15-25): (4-8);
said H in step (2)2O2The adding amount of (A) is that the dropwise adding is stopped when the mixed material turns golden yellow;
the volume of the gamma-aminopropyltriethoxysilane is 1-2 mL, the volume of the trichlorotoluene is 8-12 mL, and the volume of the toluene is 45-60 mL, which is equivalent to 1g of graphene oxide in the step (3); washing in the step (3) is carried out by adopting trichloromethane;
the reaction conditions in step (4) include: and (3) carrying out reaction in a reflux cooling device, wherein the reaction temperature is 70-90 ℃, and the reaction time is 8-24 h.
Optionally, the method further comprises: the modified carbon nano tube powder is prepared by the following steps: mixing the carbon nano tube and a silane coupling agent, stirring and ultrasonically treating, controlling the pH value to be 3.0-4.0, and drying to obtain modified carbon nano tube powder;
the conditions during the pH adjustment include: glacial acetic acid is used as a pH regulator;
the stirring conditions include: the stirring speed is 300-800rpm, and the stirring time is 3-5 h.
The third aspect of the present disclosure provides a grafted graphene heat dissipation silica gel prepared by the method of the second aspect of the present disclosure.
The fourth aspect of the present disclosure provides a use of the grafted graphene heat dissipation silica gel described in the third aspect of the present disclosure in an interface heat dissipation material.
By means of the technical scheme, the grafted graphene heat dissipation silica gel composition is provided, graphene filler particles in the grafted graphene heat dissipation silica gel composition are modified through grafting, the structure of graphene is maintained, the graphene filler particles can be well dispersed in a silicon rubber matrix, accumulation is not prone to occurring, further the formation of a heat conduction path is enhanced, the heat dissipation performance of silica gel is enhanced, and the grafted graphene heat dissipation silica gel composition can be used for interface heat dissipation materials.
Drawings
The accompanying drawings, which are included to provide a further understanding of the disclosure and are incorporated in and constitute a part of this specification, illustrate embodiments of the disclosure and together with the description serve to explain the disclosure without limiting the disclosure. In the drawings:
fig. 1 is a schematic diagram of a preparation method of a grafted graphene powder according to an embodiment of the grafted graphene heat-dissipating silica gel composition of the present disclosure;
fig. 2 is a schematic process flow diagram of one specific embodiment of the preparation of the grafted graphene heat dissipation silica gel according to the present disclosure.
Detailed Description
The following detailed description of specific embodiments of the present disclosure is provided in connection with the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating the present disclosure, are given by way of illustration and explanation only, not limitation.
The first aspect of the present disclosure provides a grafted graphene heat dissipation silica gel composition, which includes silicone rubber, grafted graphene powder, modified carbon nanotube powder, a crosslinking catalyst, a curing agent, a solvent, and an adhesive; based on the total weight of the grafted graphene heat dissipation silica gel composition, the content of the silicone rubber is 30-60 wt%, the content of the grafted graphene powder is 5-15 wt%, the content of the modified carbon nanotube powder is 1-5 wt%, the content of the crosslinking catalyst is 0.3-3 wt%, the content of the curing agent is 3-10 wt%, the content of the solvent is 10-50 wt%, and the content of the adhesive is 0.1-2 wt%.
Preferably, the silicone rubber is 40-60 wt%, the grafted graphene powder is 5-15 wt%, the modified carbon nanotube powder is 1-3 wt%, the crosslinking catalyst is 0.3-2 wt%, the curing agent is 3-6 wt%, the solvent is 20-35 wt%, and the adhesive is 0.2-1.5 wt%.
The grafted graphene heat dissipation silica gel composition disclosed by the invention contains grafted graphene powder and modified carbon nanotube powder, so that the dispersibility of graphene filler particles in a silicone rubber matrix is improved, the structure of graphene can be kept from being damaged, the capability of forming a conductive path in a composite interface material by the particles is enhanced, and the heat dissipation performance of the material is enhanced.
In one embodiment of the present disclosure, the weight ratio of the grafted graphene powder to the modified carbon nanotube powder is (6-10): 1; the average particle size of the grafted graphene powder is 3-6 mu m; the average particle size of the modified carbon nanotube powder is 5-15 μm.
In the above embodiment, by adopting the preferable ratio and particle diameter, the dispersibility of the nanoparticles in the silicone rubber matrix can be improved, and the heat dissipation capability of the material can be further enhanced.
In one embodiment of the present disclosure, the grafted graphene powder is obtained by modifying graphene oxide with γ -aminopropyltriethoxysilane; the modified carbon nano tube powder is obtained by modifying the surface of a carbon nano tube by adopting a silane coupling agent; wherein, the silane coupling agent is KH-792.
In the above embodiment, the functional group on the surface of graphene oxide and γ -aminopropyltriethoxysilane are chemically reacted to synthesize grafted graphene powder, and the silane coupling agent is used to modify the surface of the carbon nanotube to synthesize modified carbon nanotube powder, so that the dispersibility of graphene and carbon nanotube in the silicone rubber matrix can be improved, the graphene and carbon nanotube are not easily stacked, and the formation of the heat conduction path is enhanced.
In one embodiment of the present disclosure, the silicone rubber is selected from room temperature curing silicone rubber, and the room temperature curing silicone rubber comprises one or more of polydimethylsiloxane, alpha, omega-dihydroxy polydimethylsiloxane and ethyl polysilicate; preferably, the silicone rubber is alpha, omega-dihydroxy polydimethylsiloxane with viscosity of 6000-20000 cP at 25 ℃;
the crosslinking catalyst is organic tin, and the organic tin comprises one or more of dibutyl tin dilaurate, stannous octoate and dibutyltin diacetate; preferably, the organotin is dibutyl tin dilaurate;
the curing agent is an organic silicon curing agent, and the organic silicon curing agent is selected from one or more of ethyl orthosilicate, methyl orthosilicate and trimethoxy silane; preferably, the curing agent is tetraethoxysilane;
the adhesive is selected from one or more of KH-550, KH-560, KH-792 and DL-602; preferably KH-792;
the solvent is selected from one or more of acetone, ethyl acetate, hexane and toluene, and is preferably acetone.
In the above embodiment, room temperature curing silicone rubber is selected as the matrix material, and a preferable crosslinking catalyst, a curing agent and an adhesive are adopted for reaction, so that the mutual bonding force is enhanced, the crosslinking density is uniform, the heat-conducting filler particles can be effectively dispersed, a large number of heat-conducting channels are formed in the silicone rubber matrix, the internal heat is promoted to be timely dissipated, and the heat dissipation capability is enhanced.
A second aspect of the present disclosure provides a method for preparing a grafted graphene heat dissipation silica gel by using the grafted graphene heat dissipation silica gel composition according to the first aspect of the present disclosure, the method including: and mixing and stirring the grafted graphene powder, the modified carbon nanotube powder, the solvent, the silicon rubber, the curing agent and the adhesive, and adding the crosslinking catalyst for curing.
In the embodiment, the grafted graphene heat dissipation silica gel with high heat conductivity and good heat dissipation performance is prepared.
In one embodiment of the present disclosure, the method further comprises: the preparation method comprises the following steps:
(1) flake graphite,Concentrated sulfuric acid, concentrated phosphoric acid and KMnO4Mixing to obtain a mixed material;
(2) adding H to the mixture2O2Washing to obtain graphene oxide;
(3) mixing the graphene oxide, gamma-aminopropyltriethoxysilane, chloroform and toluene for reaction and washing to obtain aminated graphene oxide;
(4) and mixing the aminated graphene oxide with hydrazine hydrate for reaction.
In one embodiment of the present disclosure, the average particle size of the flake graphite in step (1) is 40 to 60mm, preferably, the average particle size of the flake graphite is 40 to 50 mm;
the flake graphite, concentrated sulfuric acid, concentrated phosphoric acid and KMnO4The weight ratio of (1): (150-250): (15-25): (4-8), preferably, the flake graphite, concentrated sulfuric acid, concentrated phosphoric acid and KMnO4The weight ratio of (1): (180-220): (16-23): (4-8);
said H in step (2)2O2The adding amount of (A) is that the dropwise adding is stopped when the mixed material turns golden yellow;
the volume of the gamma-aminopropyltriethoxysilane is 1-2 mL, the volume of the trichlorotoluene is 8-12 mL, and the volume of the toluene is 45-60 mL, which is equivalent to 1g of graphene oxide in the step (3); the washing in the step (3) is carried out by adopting trichloromethane;
the reaction conditions in step (4) include: and (3) carrying out reaction in a reflux cooling device, wherein the reaction temperature is 70-90 ℃, and the reaction time is 8-24 h.
In one embodiment of the present disclosure, the method further comprises: the modified carbon nano tube powder is prepared by the following steps: mixing the carbon nano tube and a silane coupling agent, stirring and ultrasonically treating, controlling the pH value to be 3.0-4.0, and drying to obtain modified carbon nano tube powder;
the conditions during the pH adjustment include: glacial acetic acid is used as a pH regulator;
the stirring conditions include: the stirring speed is 300-800rpm, and the stirring time is 3-5 h.
In the above embodiment, the functional group on the surface of graphene oxide is chemically reacted with γ -aminopropyltriethoxysilane, and then the unreacted oxide group is subjected to a reduction reaction, so that the dispersibility of the graphene filler particles in the silicone rubber matrix can be improved, and the structure of graphene can be kept from being damaged, so that the graphene can maintain good heat dissipation performance. The silane coupling agent reacts with the carbon nano tube, so that the dispersing capacity of the carbon nano tube heat conducting particles is improved, the silicon rubber substrate and the grafted graphene are better bridged, the dispersibility of the grafted graphene in the substrate is improved, the capacity of the particles for forming heat conducting paths in the composite interface material is improved, and the heat dissipation performance of the composite material is improved.
The third aspect of the present disclosure provides a grafted graphene heat dissipation silica gel prepared by the method of the second aspect of the present disclosure.
The fourth aspect of the present disclosure provides a use of the grafted graphene heat dissipation silica gel described in the third aspect of the present disclosure in an interface heat dissipation material.
According to the method, the grafted graphene heat dissipation silica gel with high heat conduction and high heat dissipation performance is prepared by adopting the grafted graphene powder and the modified carbon nanotube powder, and can be effectively used for heat dissipation of the composite interface material.
The present disclosure is further illustrated by the following examples, but is not to be construed as being limited thereby.
In the following examples, the raw materials used are all commercial products unless otherwise specified.
Alpha, omega-dihydroxy polydimethylsiloxane was purchased from Dow Corning, crystalline flake graphite was purchased from Qingdao Yan Xin graphite Co., Ltd, chemicals such as concentrated phosphoric acid, concentrated sulfuric acid, potassium permanganate, hydrogen peroxide, ethanol, acetone and the like were purchased from Chengdong chemical engineering Co., Ltd, carbon nanotube powder was purchased from Jiangsu Xifeng nanomaterial science & technology Co., Ltd, gamma-aminopropyltriethoxysilane and KH-792 were purchased from Hangzhou Jeccard chemical Co., Ltd, dibutyltin dilaurate was purchased from Guangzhou chemical engineering Co., Ltd, ethyl orthosilicate was purchased from Guangzhou chemical engineering Co., Ltd, hydrazine hydrate was purchased from Sigma-Aldrich, purity was analytically pure, and glacial acetic acid was purchased from Chengdong chemical engineering Co., Ltd.
In the following examples, the specific test methods are as follows:
average particle size tester: and testing by adopting a hundred-tex laser particle size distribution analyzer analysis system.
Thermogravimetric analysis test: thermogravimetric analysis (TGA) of the sample was measured using TA-Q50, manufactured by TA of America, cut into small pieces before the measurement, measuring 3-10mg in mass, and the weighed sample was placed in an alumina crucible for measurement. The gas flow speed of nitrogen gas is fixed at 50cm under nitrogen environment during test3The temperature rise rate is set to be 20 ℃/min, and the test temperature range is 100-800 ℃.
And (3) heat conduction testing: the thermal conductivity of the polymer-based composite was measured by a LAF447 thermal analyzer manufactured by NETZSCH, germany, and the sample was prepared in the form of a disc having a diameter of 12.7mm, a thickness of 1mm, and a test environment temperature of 25 ℃.
And (3) testing the viscosity of the sample: viscosity parameters were measured by a U.S. Brookfield rotational viscometer.
Example 1
This example illustrates that the method of the present disclosure is used to prepare a grafted graphene heat dissipation silica gel:
(1) preparing the modified carbon nano tube: the volume ratio of the KH-792 silane coupling agent to the absolute ethyl alcohol is 1:20, and the mixture is uniformly mixed and stirred; weighing an appropriate amount of XFQ039 carbon nanotube powder, dispersing XFQ039 carbon nanotube powder in a mixed solution of ethanol and KH-792 under ultrasonic and mechanical stirring, controlling the pH value to be 3.0-4.0, controlling the stirring speed of a magnetic stirrer to be 500rpm, after the reaction is finished, carrying out vacuum filtration on the mixture by using an organic filter membrane of 0.2um, carrying out ultrasonic-filtration washing for 3-5 times by using absolute ethanol, removing redundant KH-792, and finally carrying out vacuum drying for 24h to obtain modified carbon nanotubes (KH-CNTs);
(2) the preparation of the Graphene Oxide (GO) adopts an improved Hummers method, and the specific synthesis process is as follows: adding 4g of crystalline flake graphite into a 1000mL three-necked bottle provided with a stirring device, slowly adding 450mL of concentrated sulfuric acid and 54mL of concentrated phosphoric acid, slowly starting stirring, and then slowly adding the mixture into the mixed system24g KMnO4At this time, the mixture is added slowly, the heat is released during the reaction, the ultrasonic water bath is heated to 50 ℃, and the mixture is kept stirring and reacts for 12 hours under the ultrasonic condition. After the reaction is finished, when the reaction system is cooled to room temperature, slowly pouring the gray green suspension into a big beaker filled with 800mL of deionized water under the condition of stirring, and finally dropwise adding 30% H under the condition of stirring2O2The addition was stopped when the suspension turned golden yellow. Standing for 12 hr, pouring out the supernatant, centrifuging the solid substance with 30% concentrated hydrochloric acid, deionized water and ethanol at high speed for several times until the pH of the centrifuged supernatant reaches 6.5-7. Drying the solid matter in a vacuum oven at 80 ℃ for 24h to obtain a brown product GO;
(3) 1.2g of GO, 1.6mL of gamma-aminopropyltriethoxysilane, 11mL of trichloromethane and 65mL of toluene are sequentially added into a 250mL three-necked bottle provided with a cooling reflux device, mechanical stirring is slowly started, the mixed system is maintained to react for 48 hours at 100 ℃, black solid substances are obtained by filtration, and the gamma-aminopropyltriethoxysilane residual on the surface is removed by washing with trichloromethane. Finally, the solid matter is placed in a vacuum oven at 60 ℃ to be fully dried to obtain aminated graphene oxide NGO;
(4) adding 0.2g of NGO and 150mL of deionized water into a 250mL three-necked bottle placed in an ultrasonic environment, ultrasonically stirring and dispersing for 1h, slowly adding 2mL of hydrazine hydrate, maintaining the temperature at 80 ℃, installing a reflux cooling device, reacting for 12h, washing the product with absolute ethyl alcohol and deionized water for multiple times after the reaction is finished, and drying the product in a vacuum oven at 60 ℃ for 24h to obtain reduced aminated graphene oxide (RNGO), namely grafted graphene;
(5) weighing 3g of grafted graphene (with the average particle size of 5 microns) and adding the grafted graphene into a small glass bottle containing 10ml of acetone, and maintaining the mixture in an ultrasonic mode for 2 hours; weighing 0.5g of modified carbon nano tube (with the average particle size of 8 μm), adding into a small glass bottle with 3ml of acetone, and maintaining for 2h in ultrasonic;
(6) weighing 23.6g of alpha, omega-dihydroxy polydimethylsiloxane with the viscosity of 6000cP at 25 ℃, adding into a three-necked bottle, simultaneously adding 0.3g of KH-792 and 2.36g of tetraethoxysilane, starting mechanical stirring, and keeping the stirring speed of 1200rpm for 30 min. Adding the grafted graphene dispersion liquid and the modified carbon nanotube dispersion liquid into a three-necked bottle, mechanically stirring to 2000rpm, stirring for 2h, and discharging bubbles in vacuum to obtain a component A;
(7) and (3) weighing 0.236g of dibutyl tin dilaurate crosslinking catalyst, adding the dibutyl tin dilaurate crosslinking catalyst into the component A, uniformly stirring, carrying out vacuum bubble removal to obtain a mixture, and curing at room temperature for 24 hours to obtain the grafted graphene heat dissipation silica gel.
Example 2
Preparing grafted graphene powder and modified carbon nanotube powder according to the methods (1) to (4) in the embodiment 1;
(5) weighing 6g of grafted graphene (with the average particle size of 4 microns) and adding the grafted graphene into a small glass bottle containing 10ml of acetone, and maintaining the mixture in an ultrasonic mode for 2 hours; weighing 1g of modified carbon nano tube (with the average particle size of 12 mu m), adding the modified carbon nano tube into a small glass bottle with 3ml of acetone, and maintaining the mixture in an ultrasonic mode for 2 hours;
(6) 20.2g of alpha, omega-dihydroxy polydimethylsiloxane with viscosity of 20000cP at 25 ℃ is weighed and added into a three-necked flask, 0.6g of KH-792 and 2.02g of ethyl orthosilicate are simultaneously added, mechanical stirring is started, the stirring speed is 1200rpm, and the mixture is maintained for 30 min. Adding the grafted graphene dispersion liquid and the modified carbon nanotube dispersion liquid into a three-necked bottle, mechanically stirring to 2000rpm, stirring for 2h, and discharging bubbles in vacuum to obtain a component A;
(7) and (3) weighing 0.2g of dibutyl tin dilaurate crosslinking catalyst, adding the dibutyl tin dilaurate crosslinking catalyst into the component A, uniformly stirring, carrying out vacuum bubble removal to obtain a mixture, and curing at room temperature for 24 hours to obtain the grafted graphene heat dissipation silica gel.
Example 3
The method of example 1 is used, with the only difference that: weighing 3g of grafted graphene in the step (5), and weighing 0.2g of modified carbon nano tube for reaction.
Example 4
The method of example 1 is used, with the only difference that: and (4) weighing 0.5g of graphene oxide in the step (3) for reaction.
Example 5
The method of example 1 is used, with the only difference that: in the step (1), KH-792 silane coupling agent is replaced by concentrated sulfuric acid with equal weight to modify the carbon nano tube powder.
Example 6
The method of example 1 is used, with the only difference that: in the step (4), hydrazine hydrate is replaced by ethylenediamine with equal weight for reaction.
Comparative example 1
The method of example 1 is used, with the only difference that: and (5) replacing the grafted graphene powder with the equal-weight graphene oxide synthesized in the step (2) for reaction.
Comparative example 2
The method of example 1 is used, with the only difference that: and (5) replacing the modified carbon nano tube powder with unmodified carbon nano tubes with equal weight for reaction.
Comparative example 3
The method of example 1 is used, with the only difference that: and (5) replacing the modified carbon nano tubes with grafted graphene with equal weight for reaction.
Comparative example 4
The method of example 1 is used, with the only difference that: and (5) replacing the grafted graphene with the modified carbon nano tube with the same weight for reaction.
According to the data, in the embodiments 1 to 6, the grafted graphene powder and the modified carbon nanotube powder are used for reaction, so that the grafted graphene heat dissipation silica gel with good heat dissipation performance can be obtained, and can be used for heat dissipation of the composite interface material. The grafted graphene heat dissipation silica gel provided in the comparative examples 1-4 has poor heat dissipation performance and low heat conductivity coefficient, and is not beneficial to heat dissipation of materials. Therefore, the grafted graphene heat dissipation silica gel provided in the embodiments 1 to 6 of the present disclosure has more excellent performance than the grafted graphene heat dissipation silica gel provided in the comparative examples 1 to 4.
Comparing the data of example 1 and example 3, the weight ratio of the grafted graphene powder to the modified carbon nanotube powder preferred in the present disclosure is (6-10): 1, the grafted graphene heat dissipation silica gel prepared by the method disclosed by the invention has more excellent heat dissipation performance; comparing the data of example 1 and example 4, it can be seen that the grafted graphene heat dissipation silica gel prepared by the method disclosed herein has more excellent heat dissipation performance when the volume of gamma-aminopropyltriethoxysilane is 1-2 mL, the volume of trichlorotoluene is 8-12 mL, and the volume of toluene is 45-60 mL, which is preferably equivalent to 1g of graphene oxide; as can be seen from comparison of the data in example 1 and example 5, when the surface modification is performed on the carbon nanotubes by using the silane coupling agent, which is preferred in the present disclosure, the grafted graphene heat dissipation silica gel prepared by the method of the present disclosure has more excellent heat dissipation performance; comparing the data of example 1 and example 6, it can be seen that the grafted graphene heat dissipation silica gel prepared by the method of the present disclosure has more excellent heat dissipation performance when the graphene oxide is modified by γ -aminopropyltriethoxysilane, which is preferred in the present disclosure.
The preferred embodiments of the present disclosure are described in detail with reference to the accompanying drawings, however, the present disclosure is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present disclosure within the technical idea of the present disclosure, and these simple modifications all belong to the protection scope of the present disclosure.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. In order to avoid unnecessary repetition, various possible combinations will not be separately described in this disclosure.
In addition, any combination of various embodiments of the present disclosure may be made, and the same should be considered as the disclosure of the present disclosure, as long as it does not depart from the spirit of the present disclosure.
Claims (10)
1. The grafted graphene heat dissipation silica gel composition is characterized by comprising silicone rubber, grafted graphene powder, modified carbon nanotube powder, a crosslinking catalyst, a curing agent, a solvent and an adhesive; based on the total weight of the grafted graphene heat dissipation silica gel composition, the content of the silicone rubber is 30-60 wt%, the content of the grafted graphene powder is 5-15 wt%, the content of the modified carbon nanotube powder is 1-5 wt%, the content of the crosslinking catalyst is 0.3-3 wt%, the content of the curing agent is 3-10 wt%, the content of the solvent is 10-50 wt%, and the content of the adhesive is 0.1-2 wt%.
2. The grafted graphene heat dissipation silica gel composition according to claim 1, wherein the weight ratio of the grafted graphene powder to the modified carbon nanotube powder is (6-10): 1; the average particle size of the grafted graphene powder is 3-6 mu m; the average particle size of the modified carbon nanotube powder is 5-15 μm.
3. The grafted graphene heat dissipation silica gel composition according to claim 1, wherein the grafted graphene powder is obtained by modifying graphene oxide with gamma-aminopropyltriethoxysilane; the modified carbon nano tube powder is obtained by modifying the surface of a carbon nano tube by adopting a silane coupling agent.
4. The grafted graphene heat-dissipating silica gel composition according to claim 1, wherein the silicone rubber is α, ω -dihydroxy polydimethylsiloxane having a viscosity of 6000 to 20000cP at 25 ℃;
the crosslinking catalyst is organic tin, and the organic tin comprises one or more of dibutyl tin dilaurate, stannous octoate and dibutyltin diacetate; preferably, the organotin is dibutyl tin dilaurate;
the curing agent is tetraethoxysilane, and the adhesive is KH-792.
5. A method for preparing the grafted graphene heat dissipation silica gel by using the grafted graphene heat dissipation silica gel composition as claimed in any one of claims 1 to 4, the method comprising: and mixing and stirring the grafted graphene powder, the modified carbon nanotube powder, the solvent, the silicon rubber, the curing agent and the adhesive, and adding the crosslinking catalyst for curing.
6. The method of claim 5, further comprising: the preparation method comprises the following steps:
(1) preparing crystalline flake graphite, concentrated sulfuric acid, concentrated phosphoric acid and KMnO4Mixing to obtain a mixed material;
(2) adding H to the mixture2O2Washing to obtain graphene oxide;
(3) mixing the graphene oxide, gamma-aminopropyltriethoxysilane, chloroform and toluene for reaction and washing to obtain aminated graphene oxide;
(4) and mixing the aminated graphene oxide with hydrazine hydrate for reaction.
7. The method according to claim 6, wherein the average particle size of the flake graphite in step (1) is 40 to 60 mm;
the flake graphite, concentrated sulfuric acid, concentrated phosphoric acid and KMnO4The weight ratio of (1): (150-250): (15-25): (4-8);
said H in step (2)2O2The adding amount of (A) is that the dropwise adding is stopped when the mixed material turns golden yellow;
the volume of the gamma-aminopropyltriethoxysilane is 1-2 mL, the volume of the trichlorotoluene is 8-12 mL, and the volume of the toluene is 45-60 mL, which is equivalent to 1g of graphene oxide in the step (3); the washing in the step (3) is carried out by adopting trichloromethane;
the reaction conditions in step (4) include: and (3) carrying out reaction in a reflux cooling device, wherein the reaction temperature is 70-90 ℃, and the reaction time is 8-24 h.
8. The method of claim 5, further comprising: the modified carbon nano tube powder is prepared by the following steps: mixing the carbon nano tube and a silane coupling agent, stirring and ultrasonically treating, controlling the pH value to be 3.0-4.0, and drying to obtain modified carbon nano tube powder;
the conditions during the pH adjustment include: glacial acetic acid is used as a pH regulator;
the stirring conditions include: the stirring speed is 300-800rpm, and the stirring time is 3-5 h.
9. The grafted graphene heat dissipation silica gel is characterized by being prepared by the method of any one of claims 5-8.
10. Use of the grafted graphene thermal silica gel of claim 9 in an interfacial thermal material.
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