CN116218231A - Chitosan and silane coupling agent modified silicone oil-based flexible heat-conducting composite material and preparation method thereof - Google Patents
Chitosan and silane coupling agent modified silicone oil-based flexible heat-conducting composite material and preparation method thereof Download PDFInfo
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- 229920002545 silicone oil Polymers 0.000 title claims abstract description 137
- 229920001661 Chitosan Polymers 0.000 title claims abstract description 97
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- 239000006087 Silane Coupling Agent Substances 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title abstract description 17
- 239000000945 filler Substances 0.000 claims abstract description 103
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 74
- 239000002002 slurry Substances 0.000 claims abstract description 63
- 238000003756 stirring Methods 0.000 claims abstract description 58
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 42
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- 229910052582 BN Inorganic materials 0.000 claims description 5
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- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 5
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- 229910052581 Si3N4 Inorganic materials 0.000 claims description 4
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- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 2
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- 239000000395 magnesium oxide Substances 0.000 claims description 2
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- 229920001843 polymethylhydrosiloxane Polymers 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- MTEZSDOQASFMDI-UHFFFAOYSA-N 1-trimethoxysilylpropan-1-ol Chemical compound CCC(O)[Si](OC)(OC)OC MTEZSDOQASFMDI-UHFFFAOYSA-N 0.000 claims 1
- FSIJKGMIQTVTNP-UHFFFAOYSA-N bis(ethenyl)-methyl-trimethylsilyloxysilane Chemical compound C[Si](C)(C)O[Si](C)(C=C)C=C FSIJKGMIQTVTNP-UHFFFAOYSA-N 0.000 claims 1
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- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 4
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- DFGKGUXTPFWHIX-UHFFFAOYSA-N 6-[2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]acetyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)C1=CC2=C(NC(O2)=O)C=C1 DFGKGUXTPFWHIX-UHFFFAOYSA-N 0.000 description 2
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
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- WKWOFMSUGVVZIV-UHFFFAOYSA-N n-bis(ethenyl)silyl-n-trimethylsilylmethanamine Chemical compound C[Si](C)(C)N(C)[SiH](C=C)C=C WKWOFMSUGVVZIV-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K7/00—Constructional details common to different types of electric apparatus
- H05K7/20—Modifications to facilitate cooling, ventilating, or heating
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a silicone oil-based flexible heat-conducting composite material modified by chitosan and a silane coupling agent and a preparation method thereof, wherein the composite material is prepared by heating, solidifying and molding flowable slurry; the fluidity slurry is prepared by uniformly stirring a modified flaky filler, a modified granular filler, a silicone oil mixture and a platinum catalyst and then defoaming; the modified flaky filler or modified granular filler is prepared by adding chitosan, granular filler or flaky filler into ethanol water solution, adding glacial acetic acid, stirring uniformly, adding a silane coupling agent, stirring, and carrying out suction filtration, washing and drying after the reaction is finished. The silicon oil-based flexible heat-conducting composite material modified by the chitosan and the silane coupling agent has higher heat conductivity and lower hardness, can be well attached to the surfaces of electronic components and a radiator, and can effectively solve the heat dissipation problem of electronic equipment.
Description
Technical Field
The invention relates to the field of thermal interface materials, in particular to a silicone oil-based flexible heat-conducting composite material modified by chitosan and a silane coupling agent and a preparation method thereof.
Background
At present, electronic components are rapidly developing toward miniaturization, integration and intellectualization, and the higher the integration of the electronic components is, the more heat is generated in the operation process, the working temperature of the electronic equipment is inevitably increased, and the performance, the safety and the service life of the electronic equipment are greatly influenced. Therefore, the preparation of thermally conductive materials with efficient heat dissipation is critical to the construction of advanced modern microelectronic technologies.
The addition type liquid silicone rubber is formed by hydrosilylation reaction of vinyl-terminated silicone oil and side hydrogen-containing silicone oil under the action of a catalyst, is very favorable for industrial production due to low cost and easy processing, has excellent flexibility, can be well attached to the surfaces of electronic components and radiators, fills up tiny gaps on the surfaces of the electronic components and the radiators, is favorable for heat conduction, and has excellent corrosion resistance, ageing resistance and electrical insulation property, so that the addition type liquid silicone rubber is widely applied to electronic products. However, the intrinsic thermal conductivity of addition type liquid silicone rubber is low (0.1-0.2 W.multidot.m -1 ·K -1 ) This limits its application in the field of heat dissipation of electronic devices.
The introduction of thermally conductive fillers with high thermal conductivity into silicone rubber matrices is one of the most efficient methods for preparing highly thermally conductive composites. However, to prepare a thermally conductive composite material with higher thermal conductivity, it is necessary to fill enough thermally conductive filler to construct as many thermally conductive channels as possible in the silicone rubber matrix, and an excessively high filling rate of the thermally conductive filler tends to increase the hardness of the composite material while increasing the thermal conductivity of the composite material, resulting in a lack of flexibility of the material. Therefore, how to obtain a flexible heat-conducting composite material with high heat conductivity and moderate hardness is a difficult problem to be solved by researchers.
For example, chinese patent application CN101812233A discloses a double-component addition room temperature curing silicone rubber which is prepared by stirring, heating and curing allyl silicone oil, hydrogen-containing silicone oil, alumina, quartz powder, platinum catalyst, inhibitor and other substances, and has a thermal conductivity of 0.7-1.0W.m -1 ·K -1 While the shore a hardness is 45-64. However, the higher hardness can affect the adhesion of the heat conductive composite material to the surfaces of the electronic component and the radiator, so that a larger gap is formed, and a large amount of air with extremely low heat conductivity fills in the gap, which can prevent the electronic equipment from rapidly radiating.
Disclosure of Invention
In view of the above, the invention provides a chitosan and silane coupling agent modified silicone oil based flexible heat conduction composite material with higher heat conductivity and lower hardness and a preparation method thereof.
The invention uses chitosan and silane coupling agent to modify the flaky filler and the granular filler, and the flaky filler and the granular filler realize organic coordination. The chitosan inhibits the hydrosilylation reaction of vinyl-terminated silicone oil and hydrogen-containing silicone oil, and reduces the crosslinking between the two monomers, thereby reducing the hardness of the composite material; the grafting of the silane coupling agent on the surface of the heat conducting filler improves the compatibility of the silane coupling agent in the polymer matrix, reduces the thermal resistance of the interface between the filler and the matrix, the flaky filler is used as the main filler to construct a main heat conducting path, and the granular filler is used as the auxiliary filler to be inserted into gaps among the flaky fillers, so that the heat conducting channels in the polymer matrix are denser, and the chitosan and silicone oil-based flexible heat conducting composite material modified by the silane coupling agent with high heat conductivity and moderate hardness is obtained.
The invention is realized by the following technical scheme:
the silicone oil-based flexible heat-conducting composite material modified by chitosan and a silane coupling agent is obtained by heating, curing and molding a flowable slurry; the fluidity slurry is prepared by uniformly stirring a modified flaky filler, a modified granular filler, a silicone oil mixture and a platinum catalyst and then defoaming; the modified flaky filler or modified granular filler is prepared by adding chitosan, granular filler or flaky filler into ethanol water solution, adding glacial acetic acid, stirring uniformly, adding a silane coupling agent, stirring, and carrying out suction filtration, washing and drying after the reaction is finished.
To further achieve the object of the present invention, preferably, the silicone oil mixture accounts for 50 to 70% by mass of the raw material, the modified flaky filler and the modified particulate filler account for 30 to 50% by mass of the raw material, wherein the flaky filler accounts for 20 to 40% and the particulate filler accounts for 10 to 20%; the silicone oil mixture is obtained by uniformly stirring vinyl-terminated silicone oil, side hydrogen-containing silicone oil and an inhibitor; the mass ratio of the vinyl-terminated silicone oil to the side hydrogen-containing silicone oil is 4:1 to 5:1, a step of; the inhibitor is 0.1 to 1 percent of the mass of the mixture of vinyl silicone oil and side hydrogen silicone oil; the dosage of the platinum catalyst does not account for the total mass percent of the raw materials, and 20-30 mu L of the platinum catalyst is added into each 10g of the mixture of the vinyl-terminated silicone oil, the side hydrogen-containing silicone oil and the inhibitor.
Preferably, the granular filler is one or more of spherical alumina, spherical magnesia, aluminum nitride, silicon nitride and silicon carbide; the lamellar filler is one or more of lamellar graphite, hexagonal boron nitride, graphene oxide, graphene and graphene nano sheets.
Preferably, the viscosity of the chitosan is less than 200 mPa.s, and the use amount of the chitosan is 1-2% of the mass of the granular filler and the flaky filler; the volume ratio of deionized water to absolute ethyl alcohol of the ethyl alcohol aqueous solution is 3:1-5:1, the use amount of glacial acetic acid is 1-2 mL of ethyl alcohol aqueous solution added into every 100mL of ethyl alcohol aqueous solution, and 200-300 mL of ethyl alcohol aqueous solution is added into every 25g of filling material in the modification process of the flaky filling material; the dosage of the ethanol aqueous solution in the modification process of the granular filler is 100-150 ml of ethanol aqueous solution added into every 25g of filler.
Preferably, the silane coupling agent is one or more of gamma-aminopropyl triethoxysilane, gamma-glycidoxypropyl trimethoxysilane, gamma-methacryloxypropyl trimethoxysilane, vinyl trimethoxysilane and vinyl triethoxysilane.
Preferably, the usage amount of the silane coupling agent is 1-2% of the mass of the granular filler and the flaky filler, the reaction time after the silane coupling agent is added is 1-3 h, and the reaction temperature is room temperature.
Preferably, the vinyl-terminated silicone oil is divinyl-terminated polydimethylsiloxane, the viscosity of the vinyl-terminated silicone oil is 100-500 mPas, and the vinyl content is 0.30-1.10 wt%; the side hydrogen silicone oil is polymethylhydrosiloxane, and the hydrogen content is 0.1-0.8wt%.
Preferably, the inhibitor is ethynyl cyclohexanol, the catalyst is Karstedt platinum catalyst, a complex formed by zero-valent platinum and divinyl tetramethyl disilazane, and the concentration of the zero-valent platinum in the catalyst is 1000-5000 ppm. Further preferred is a zero valent platinum concentration of 3000ppm.
The preparation method of the silicone oil-based flexible heat-conducting composite material modified by chitosan and silane coupling agent comprises the following steps:
(1) Adding the chitosan, the granular filler or the flaky filler into an ethanol water solution, adding glacial acetic acid, uniformly stirring, adding a silane coupling agent and stirring after uniformly mixing, and carrying out suction filtration, deionized water washing and vacuum drying after the reaction is finished to obtain a modified flaky filler or a modified granular filler;
(2) Uniformly stirring vinyl-terminated silicone oil, side hydrogen-containing silicone oil and an inhibitor to obtain a silicone oil mixture;
(3) Adding the modified flaky filler and the modified granular filler obtained in the step (1), the silicone oil mixture obtained in the step (2) and the platinum catalyst into a container, and uniformly stirring to obtain a flowable slurry;
(4) Removing bubbles from the flowable slurry, and then injecting the flowable slurry into a mold;
(5) And (3) heating, solidifying and forming, cooling to room temperature, and demolding to obtain the silicone oil-based flexible heat-conducting composite material modified by the chitosan and the silane coupling agent.
Preferably, in the step (1), the stirring conditions before and after the silane coupling agent is added are 500-800 rpm, the temperature is room temperature, and the stirring time is 1-2 hours; the temperature of the vacuum drying is 80-100 ℃, the vacuum degree is-0.08 to-0.10 MPa, and the time of the vacuum drying is 12-24 hours;
in the step (2), stirring is performed at room temperature, the rotating speed of the stirrer is 400-600 rpm, and the stirring time is 2-6 h;
in the step (3), stirring is performed at room temperature, the rotating speed of the stirrer is 600-1000 rpm, and the stirring time is 0.5-2 h;
in the step (4), the defoaming is to put the flowable slurry into a vacuum drying oven for vacuum defoaming; the vacuum defoaming is performed for 0.5 to 1 hour under the conditions of room temperature and vacuum degree of minus 0.10 MPa;
in the step (5), the slurry and the mould are placed in a blast drier together for heating to solidify and shape the material; the heating temperature of the blast drier is 60-80 ℃ and the heating time is 1-2 h.
Compared with the prior art, the invention has the advantages and beneficial technical effects that:
1) According to the invention, the heat-conducting filler is modified by using the chitosan and the silane coupling agent, so that the hardness of the heat-conducting composite material is greatly reduced compared with that of the heat-conducting composite material before being modified under the condition of higher filler filling mass fraction, and meanwhile, the heat conductivity of the heat-conducting composite material is better improved, and the problem that the heat-conducting composite material is difficult to achieve both high heat conductivity and proper hardness is effectively solved.
2) The flaky filler is taken as main filler, the mass fraction of the flaky filler is 20-40%, the granular filler is taken as auxiliary filler, the mass fraction of the granular filler is 10-20%, and the total filling mass fraction of the two fillers is 30-50%; the flaky fillers serve as main fillers to construct a main heat conduction path, and the granular fillers serve as auxiliary fillers to be inserted into gaps among the flaky fillers, so that heat conduction channels in the polymer matrix are denser.
3) The chitosan and the silane coupling agent obtained by the inventionIn the modified silicone oil-based flexible heat-conducting composite material, the heat conductivity can reach 1.309 W.m at most -1 ·K -1 The Shore hardness A of the material prepared by using the filler modified by Chitosan (CTS) and a silane coupling agent is about 35-40, and the hardness reduction amplitude of the material prepared by using the unmodified filler is more than 25 percent, probably because the chitosan inhibits the hydrosilylation reaction of vinyl-terminated silicone oil and hydrogen-containing silicone oil, and the crosslinking between the two monomers is reduced; compared with the material prepared by using the unmodified filler, the thermal conductivity of the silicone oil-based flexible heat-conducting composite material modified by the chitosan and the silane coupling agent is improved by 8-10%, probably because the grafting of the silane coupling agent on the surface of the filler improves the compatibility of the filler on a matrix, reduces phonon scattering at the interface of the filler and the matrix, and simultaneously, the two types of fillers are matched for use to produce positive effects.
4) Under the condition of the same heat conductivity, the heat-conducting composite material with lower hardness can be attached to the surfaces of the electronic components and the radiator, so that the actual heat dissipation of the electronic equipment is facilitated. The silicon oil-based flexible heat-conducting composite material modified by the chitosan and the silane coupling agent has higher heat conductivity and lower hardness, can be well attached to the surfaces of electronic components and a radiator, and can effectively solve the heat dissipation problem of electronic equipment.
5) The invention does not use toxic and harmful reagent in the modification process of the heat conducting filler, is environment-friendly, has lower cost of the used materials and is easy to carry out industrial production.
Drawings
FIG. 1 is a Fourier infrared spectrum of the flake graphite before and after modification obtained in example 1.
FIG. 2 is a Fourier infrared spectrum of spherical alumina before and after modification obtained in example 1.
Detailed Description
For a better understanding of the present invention, the following description will be given with reference to the accompanying drawings and specific examples, but the scope of the present invention is not limited to the specific examples.
Example 1
A preparation method of a silicone oil-based flexible heat-conducting composite material modified by chitosan and a silane coupling agent comprises the following steps:
(1) Adding 0.25g of chitosan (CTS, viscosity < 200 mPa.s) and 25g of flake graphite (FG, particle size 200 meshes) into 200ml of ethanol water solution (volume ratio of ethanol to deionized water is 1:3), then adding 2ml of glacial acetic acid, magnetically stirring at 700rpm at room temperature for 2h, further adding 0.5g of gamma-methacryloxypropyl trimethoxysilane (KH 570), continuously stirring for 2h, filtering and washing with absolute ethanol, transferring to a vacuum drying oven, and drying at 100 ℃ and-0.10 MPa for 12h to obtain flake graphite modified by chitosan and gamma-methacryloxypropyl trimethoxysilane, and marking as FG-CTS-KH570;
similarly, the same method as used for modification of the flake graphite was used for the spherical alumina (S-Al 2 O 3 Particle size of 50 μm), except that in the modification of the particulate filler such as spherical alumina, the amount of ethanol aqueous solution was reduced to 100ml and the amount of glacial acetic acid was reduced to 1ml, and finally spherical alumina modified with chitosan and gamma-methacryloxypropyl trimethoxysilane was obtained, denoted as Al 2 O 3 -CTS-KH570；
(2) 180.00g of vinyl-terminated silicone oil (with the viscosity of 100 mPas and the vinyl content of 0.98 wt%) and 42.15g of side hydrogen-containing silicone oil (with the hydrogen content of 0.18 wt%) and 0.89g of ethynyl cyclohexanol (with the purity of 98%) are taken, and are placed in a container, and magnetically stirred at room temperature for 2 hours at 500rpm to obtain a silicone oil mixture;
(3) FG-CTS-KH570 and Al obtained in step (1) 2 O 3 Placing 12g and 8g of CTS-KH570 in a container respectively, adding 20g of the silicone oil mixture obtained in the step (2) and 50 mu L of Karstedt platinum catalyst (the zero-valent platinum concentration is 3000 ppm) at the same time, stirring uniformly at room temperature by a high-speed stirrer, stirring at a high-speed stirrer rotating speed of 800rpm for 1h, and obtaining uniform slurry with fluidity;
(4) Placing the slurry obtained in the step (3) into a vacuum drying oven, removing bubbles for 0.5h at room temperature under the vacuum degree of-0.10 MPa, and injecting the slurry into a die after the bubbles are removed;
(5) And (3) placing the slurry and the mould in a blast drier, heating at 80 ℃ for 2 hours to solidify and shape the slurry, cooling to room temperature, and demoulding to obtain the silicone oil-based flexible heat-conducting composite material modified by chitosan and the silane coupling agent.
FG-CTS-KH570 and Al in example 1 2 O 3 The filling mass fractions of CTS-KH570 were 30% and 20%, respectively.
FIG. 1 is a Fourier infrared spectrum of FG before and after modification obtained in example 1, as shown in FIG. 1, FG after modification with Chitosan (CTS), 3440cm -1 The increase in the intensity of the stretching vibration peak of hydroxyl (-OH) groups is probably caused by adsorption of CTS containing rich-OH groups on FG surface, FG modified by CTS and gamma-methacryloxypropyl trimethoxysilane (KH 570), 3440cm -1 The stretching vibration peak intensity of the hydroxyl group (-OH) was reduced at 1086cm -1 An infrared characteristic peak of Si-O-Si appears at 1161cm -1 Si-O-C infrared characteristic peaks appear, which prove that KH570 is successfully grafted on the FG surface;
FIG. 2 shows the S-Al before and after modification obtained in example 1 2 O 3 As shown in FIG. 2, al before and after CTS modification 2 O 3 There was no significant difference in the IR spectrum, possibly Al of CTS 2 O 3 Al modified by CTS and KH570 due to small surface adsorption 2 O 3 At 1623cm -1 An infrared characteristic peak of carbon-carbon double bond (c=c) appears, indicating that KH570 was successfully grafted onto Al 2 O 3 A surface.
Example 2
A preparation method of a silicone oil-based flexible heat-conducting composite material modified by chitosan and a silane coupling agent comprises the following steps:
(1) Adding 0.5g of chitosan (CTS, viscosity < 200 mPas) and 25g of flake graphite (FG, particle size 200 meshes) into 200ml of ethanol water solution (volume ratio of ethanol to deionized water is 1:4), then adding 2ml of glacial acetic acid, magnetically stirring at 700rpm at room temperature for 2h, adding 0.25g of vinyltrimethoxysilane (KH 171), continuously stirring for 2h, transferring to a vacuum drying oven after suction filtration and washing with absolute ethyl alcohol, and drying at 100 ℃ and-0.10 MPa for 12h to obtain flake graphite modified by chitosan and vinyltrimethoxysilane, and marking as FG-CTS-KH171;
similarly, the same method was used for spherical alumina (S-Al 2 O 3 Particle size of 50 μm), except that the amount of ethanol aqueous solution was reduced to 100ml and the amount of glacial acetic acid to 1ml, to obtain spherical alumina modified with chitosan and vinyltrimethoxysilane, denoted as Al 2 O 3 -CTS-KH171；
(2) 180.00g of vinyl-terminated silicone oil (with the viscosity of 100 mPas and the vinyl content of 0.98 wt%) and 42.15g of side hydrogen-containing silicone oil (with the hydrogen content of 0.18 wt%) and 0.89g of ethynyl cyclohexanol (with the purity of 98%) are taken, and are placed in a container, and magnetically stirred at room temperature for 2 hours at 500rpm to obtain a silicone oil mixture;
(3) FG-CTS-KH171 and Al obtained in step (1) 2 O 3 Placing 12g and 8g of CTS-KH171 into a container respectively, adding 20g of the silicone oil mixture obtained in the step (2) and 50 mu L of Karstedt platinum catalyst (the zero-valent platinum concentration is 3000 ppm) at the same time, stirring uniformly at room temperature by a high-speed stirrer, stirring at a high-speed stirrer rotating speed of 800rpm for 1h, and obtaining uniform slurry with fluidity;
(4) Placing the slurry obtained in the step (3) into a vacuum drying oven, removing bubbles for 0.5h at room temperature under the vacuum degree of-0.10 MPa, and injecting the slurry into a die after the bubbles are removed;
(5) And (3) placing the slurry and the mould in a blast drier, heating at 80 ℃ for 2 hours to solidify and shape the slurry, cooling to room temperature, and demoulding to obtain the silicone oil-based flexible heat-conducting composite material modified by chitosan and the silane coupling agent.
FG-CTS-KH171 and Al in example 2 2 O 3 The filling mass fractions of CTS-KH171 were 30% and 20%, respectively.
Example 3
A preparation method of a silicone oil-based flexible heat-conducting composite material modified by chitosan and a silane coupling agent comprises the following steps:
(1) Adding 0.5g of chitosan (CTS, viscosity < 200 mPas) and 25g of flake graphite (FG, particle size 200 meshes) into 200ml of ethanol water solution (volume ratio of ethanol to deionized water is 1:5), then adding 4ml of glacial acetic acid, magnetically stirring at 700rpm at room temperature for 2h, adding 0.5g of vinyltriethoxysilane (KH 151), continuously stirring for 2h, transferring to a vacuum drying oven after suction filtration and washing with absolute ethyl alcohol, and drying at 100 ℃ and-0.10 MPa for 12h to obtain flake graphite modified by chitosan and vinyltriethoxysilane, and marking as FG-CTS-KH151;
similarly, the same method was used for spherical alumina (S-Al 2 O 3 Particle size of 50 μm), except that the amount of ethanol aqueous solution was reduced to 100ml and the amount of glacial acetic acid was reduced to 2ml, to obtain spherical alumina modified with chitosan and vinyltriethoxysilane, denoted as Al 2 O 3 -CTS-KH151；
(2) 180.00g of vinyl-terminated silicone oil (with the viscosity of 100 mPas and the vinyl content of 0.98 wt%) and 42.15g of side hydrogen-containing silicone oil (with the hydrogen content of 0.18 wt%) and 0.89g of ethynyl cyclohexanol (with the purity of 98%) are taken, and are placed in a container, and magnetically stirred at room temperature for 2 hours at 500rpm to obtain a silicone oil mixture;
(3) FG-CTS-KH151 obtained in step (1) and Al 2 O 3 Placing 12g and 8g of CTS-KH151 in a container respectively, adding 20g of the silicone oil mixture obtained in the step (2) and 50 mu L of Karstedt platinum catalyst (the zero-valent platinum concentration is 3000 ppm) at the same time, stirring uniformly at room temperature by a high-speed stirrer, stirring at a high-speed stirrer rotating speed of 800rpm for 1h, and obtaining uniform slurry with fluidity;
(4) Placing the slurry obtained in the step (3) into a vacuum drying oven, removing bubbles for 0.5h at room temperature under the vacuum degree of-0.10 MPa, and injecting the slurry into a die after the bubbles are removed;
(5) And (3) placing the slurry and the mould in a blast drier, heating at 80 ℃ for 2 hours to solidify and shape the slurry, cooling to room temperature, and demoulding to obtain the silicone oil-based flexible heat-conducting composite material modified by chitosan and the silane coupling agent.
FG-CTS-KH151 and Al in example 3 2 O 3 Filling mass fraction of CTS-KH151The numbers were 30% and 20%, respectively.
Example 4
A preparation method of a silicone oil-based flexible heat-conducting composite material modified by chitosan and a silane coupling agent comprises the following steps:
(1) Adding 0.375g of chitosan (CTS, viscosity is less than 200 mPa.s) and 25g of hexagonal boron nitride (h-BN, particle size is 20-30 mu m) into 200ml of ethanol water solution (volume ratio of ethanol to deionized water is 1:3), then adding 2ml of glacial acetic acid, magnetically stirring at room temperature at 700rpm for 2h, adding 0.375g of gamma-glycidoxypropyl trimethoxysilane (KH 560), continuously stirring for 2h, filtering and washing by absolute ethyl alcohol, transferring to a vacuum drying oven, and drying at 100 ℃ and minus 0.10MPa for 12h to obtain hexagonal boron nitride modified by chitosan and gamma-glycidoxypropyl trimethoxysilane, which is marked as BN-CTS-KH560;
similarly, the same method was used for spherical alumina (S-Al 2 O 3 Particle size of 50 μm), except that the amount of ethanol aqueous solution was reduced to 100ml and the amount of glacial acetic acid to 1ml, to obtain spherical alumina modified with chitosan and gamma-glycidoxypropyl trimethoxysilane, denoted as Al 2 O 3 -CTS-KH560；
(2) 180.00g of vinyl-terminated silicone oil (with the viscosity of 100 mPas and the vinyl content of 0.98 wt%) and 42.15g of side hydrogen-containing silicone oil (with the hydrogen content of 0.18 wt%) and 0.89g of ethynyl cyclohexanol (with the purity of 98%) are taken, and are placed in a container, and magnetically stirred at room temperature for 2 hours at 500rpm to obtain a silicone oil mixture;
(3) The BN-CTS-KH560 and Al obtained in the step (1) are mixed 2 O 3 Placing 14g and 6g of CTS-KH560 into a container respectively, adding 20g of the silicone oil mixture obtained in the step (2) and 50 mu L of Karstedt platinum catalyst (the zero-valent platinum concentration is 3000 ppm) at the same time, stirring uniformly at room temperature by a high-speed stirrer, stirring at a high-speed stirrer rotating speed of 800rpm for 1h, and obtaining uniform slurry with fluidity;
(4) Placing the slurry obtained in the step (3) into a vacuum drying oven, removing bubbles for 0.5h at room temperature under the vacuum degree of-0.10 MPa, and injecting the slurry into a die after the bubbles are removed;
(5) And (3) placing the slurry and the mould in a blast drier, heating at 80 ℃ for 2 hours to solidify and shape the slurry, cooling to room temperature, and demoulding to obtain the silicone oil-based flexible heat-conducting composite material modified by chitosan and the silane coupling agent.
BN-CTS-KH560 and Al in example 4 2 O 3 The filling mass fractions of CTS-KH560 were 35% and 15%, respectively.
Example 5
A preparation method of a silicone oil-based flexible heat-conducting composite material modified by chitosan and a silane coupling agent comprises the following steps:
(1) Adding 0.5g of chitosan (CTS, viscosity < 200 mPas) and 25g of flake graphite (FG, particle size 200 meshes) into 200ml of ethanol water solution (volume ratio of ethanol to deionized water is 1:3), then adding 2ml of glacial acetic acid, magnetically stirring at 700rpm at room temperature for 2h, adding 0.5g of gamma-aminopropyl triethoxysilane (KH 550), continuously stirring for 2h, transferring to a vacuum drying oven after suction filtration and absolute ethanol washing, and drying at 100 ℃ and-0.10 MPa for 12h to obtain flake graphite modified by chitosan and gamma-aminopropyl triethoxysilane, and marking as FG-CTS-KH550;
similarly, the same method is used for silicon nitride (Si 3 N 4 Particle size of 20-30 μm), except that the amount of ethanol aqueous solution was reduced to 100ml and the amount of glacial acetic acid to 1ml, to obtain spherical alumina modified with chitosan and gamma-aminopropyl triethoxysilane, denoted Si 3 N 4 -CTS-KH550；
(2) 180.00g of vinyl-terminated silicone oil (with the viscosity of 100 mPas and the vinyl content of 0.98 wt%) and 42.15g of side hydrogen-containing silicone oil (with the hydrogen content of 0.18 wt%) and 0.89g of ethynyl cyclohexanol (with the purity of 98%) are taken, and are placed in a container, and magnetically stirred at room temperature for 2 hours at 500rpm to obtain a silicone oil mixture;
(3) FG-CTS-KH550 and Si obtained in step (1) 3 N 4 Placing 16g and 4g of CTS-KH550 respectively in a container, and simultaneously adding 20g of silicone oil mixture obtained in step (2) and Karstedt platinum catalyst (zero-valent platinum concentration)A degree of 3000 ppm) 50 μl, stirring at room temperature with a high-speed stirrer at 800rpm for 1 hr to obtain a uniform and flowable slurry;
(4) Placing the slurry obtained in the step (3) into a vacuum drying oven, removing bubbles for 0.5h at room temperature under the vacuum degree of-0.10 MPa, and injecting the slurry into a die after the bubbles are removed;
(5) And (3) placing the slurry and the mould in a blast drier, heating at 80 ℃ for 2 hours to solidify and shape the slurry, cooling to room temperature, and demoulding to obtain the silicone oil-based flexible heat-conducting composite material modified by chitosan and the silane coupling agent.
FG-CTS-KH550 and Si in example 5 3 N 4 The filling mass fractions of CTS-KH550 were 40% and 10%, respectively.
Comparative example 1
A preparation method of a chitosan modified silicone oil-based flexible heat-conducting composite material comprises the following steps:
(1) Adding 0.25g of chitosan (CTS, viscosity is less than 200 mPa.s) and 25g of flake graphite (FG, particle size is 200 meshes) into 200ml of ethanol water solution (volume ratio of ethanol to deionized water is 1:3), then adding 2ml of glacial acetic acid, magnetically stirring at 700rpm at room temperature for 4 hours, transferring to a vacuum drying oven after suction filtration and washing by absolute ethyl alcohol, and drying at 100 ℃ and minus 0.10MPa for 12 hours to obtain flake graphite modified by chitosan, and recording as FG-CTS;
similarly, the same method was used for spherical alumina (S-Al 2 O 3 Particle size of 50 μm), except that the amount of ethanol aqueous solution used was reduced to 100ml and the amount of glacial acetic acid to 1ml, to obtain chitosan-modified spherical alumina, designated as Al, for the spherical alumina-like particulate filler 2 O 3 -CTS；
(2) 180.00g of vinyl-terminated silicone oil (with the viscosity of 100 mPas and the vinyl content of 0.98 wt%) and 42.15g of side hydrogen-containing silicone oil (with the hydrogen content of 0.18 wt%) and 0.89g of ethynyl cyclohexanol (with the purity of 98%) are taken, and are placed in a container, and magnetically stirred at room temperature for 2 hours at 500rpm to obtain a silicone oil mixture;
(3) FG-CTS and Al obtained in step (1) 2 O 3 Placing 12g and 8g of CTS in a container respectively, adding 20g of the silicone oil mixture obtained in the step (2) and 50 mu L of Karstedt platinum catalyst (the zero-valent platinum concentration is 3000 ppm) at the same time, stirring uniformly at room temperature by a high-speed stirrer, stirring at a high-speed stirrer rotating speed of 800rpm for 1h, and obtaining uniform slurry with fluidity;
(4) Placing the slurry obtained in the step (3) into a vacuum drying oven, removing bubbles for 0.5h at room temperature under the vacuum degree of-0.10 MPa, and injecting the slurry into a die after the bubbles are removed;
(5) And (3) placing the slurry and the mould in a blast drier, heating at 80 ℃ for 2 hours to solidify and shape the slurry, cooling to room temperature, and demoulding to obtain the chitosan modified silicone oil-based flexible heat-conducting composite material.
FG-CTS and Al in comparative example 1 2 O 3 The filling mass fraction of CTS is 30% and 20%, respectively.
Comparative example 2
A preparation method of a silicone oil-based flexible heat-conducting composite material modified by a silane coupling agent comprises the following steps:
(1) 25g of flake graphite (FG, particle size 200 mesh) was added to 200ml of an aqueous ethanol solution (volume ratio of ethanol to deionized water 1:3), then 2ml of glacial acetic acid and 0.5g of gamma-methacryloxypropyl trimethoxysilane (KH 570) were added, magnetically stirred at 700rpm at room temperature for 2 hours, and after suction filtration and washing with absolute ethanol, transferred to a vacuum oven and dried at 100 ℃ and-0.10 MPa for 12 hours to give gamma-methacryloxypropyl trimethoxysilane modified flake graphite, designated FG-KH570;
similarly, the same method was used for spherical alumina (S-Al 2 O 3 Particle size of 50 μm), except that the amount of ethanol aqueous solution was reduced to 100ml and the amount of glacial acetic acid to 1ml, to obtain gamma-methacryloxypropyl trimethoxysilane modified spherical alumina, designated as Al, as a particulate filler such as spherical alumina 2 O 3 -KH570；
(2) 180.00g of vinyl-terminated silicone oil (with the viscosity of 100 mPas and the vinyl content of 0.98 wt%) and 42.15g of side hydrogen-containing silicone oil (with the hydrogen content of 0.18 wt%) and 0.89g of ethynyl cyclohexanol (with the purity of 98%) are taken, and are placed in a container, and magnetically stirred at room temperature for 2 hours at 500rpm to obtain a silicone oil mixture;
(3) FG-KH570 and Al obtained in step (1) 2 O 3 Putting 12g and 8g of KH570 into a container respectively, adding 20g of the silicone oil mixture obtained in the step (2) and 50 mu L of Karstedt platinum catalyst (the zero-valent platinum concentration is 3000 ppm) at the same time, stirring uniformly at room temperature by a high-speed stirrer, stirring at a high-speed stirrer rotating speed of 800rpm for 1h, and obtaining uniform slurry with fluidity;
(4) Placing the slurry obtained in the step (3) into a vacuum drying oven, removing bubbles for 0.5h at room temperature under the vacuum degree of-0.10 MPa, and injecting the slurry into a die after the bubbles are removed;
(5) And (3) placing the slurry and the mould in a blast drier, heating at 80 ℃ for 2 hours to solidify and shape the slurry, cooling to room temperature, and demoulding to obtain the silicone oil-based flexible heat-conducting composite material modified by the silane coupling agent. FG-KH570 and Al in comparative example 2 2 O 3 The filling mass fraction of KH570 is 30% and 20%, respectively.
Comparative example 3
A preparation method of a silicone oil-based flexible heat-conducting composite material comprises the following steps:
(1) 180.00g of vinyl-terminated silicone oil (with the viscosity of 100 mPas and the vinyl content of 0.98 wt%) and 42.15g of side hydrogen-containing silicone oil (with the hydrogen content of 0.18 wt%) and 0.89g of ethynyl cyclohexanol (with the purity of 98%) are taken, and are placed in a container, and magnetically stirred at room temperature for 2 hours at 500rpm to obtain a silicone oil mixture;
(2) 12g of flake graphite (FG, particle size 200 mesh) and spherical alumina (S-Al) 2 O 3 The particle size is 50 mu m) 8g, the silicone oil mixture obtained in the step (1) is 20g, and 50 mu L of Karstedt platinum catalyst (the zero-valent platinum concentration is 3000 ppm) are stirred uniformly at room temperature by a high-speed stirrer, the rotating speed of the high-speed stirrer is 800rpm, and the stirring is carried out for 1h, so that uniform slurry with fluidity is obtained;
(3) Placing the slurry obtained in the step (2) into a vacuum drying oven, and removing bubbles for 0.5h at room temperature under the vacuum degree of-0.10 MPa; injecting the foam into a die after the foam is removed;
(4) And (3) placing the slurry and the mould in a blast drier, heating at 80 ℃ for 2 hours to solidify and shape the slurry, cooling to room temperature, and demoulding to obtain the silicone oil-based flexible heat-conducting composite material. FG and S-Al in comparative example 3 2 O 3 The filling mass fractions of (2) are 30% and 20%, respectively.
Comparative example 4
A preparation method of a silicone oil-based flexible heat-conducting composite material comprises the following steps:
(1) 180.00g of vinyl-terminated silicone oil (with the viscosity of 100 mPas and the vinyl content of 0.98 wt%) and 42.15g of side hydrogen-containing silicone oil (with the hydrogen content of 0.18 wt%) and 0.89g of ethynyl cyclohexanol (with the purity of 98%) are taken, and are placed in a container, and magnetically stirred at room temperature for 2 hours at 500rpm to obtain a silicone oil mixture;
(2) 14g of hexagonal boron nitride (h-BN, particle size of 20-30 μm) and spherical alumina (S-Al) 2 O 3 The particle size is 50 mu m) 6g, the silicone oil mixture obtained in the step (1) is 20g, and 50 mu L of Karstedt platinum catalyst (the zero-valent platinum concentration is 3000 ppm) are stirred uniformly at room temperature by a high-speed stirrer, the rotating speed of the high-speed stirrer is 800rpm, and the stirring is carried out for 1h, so that uniform slurry with fluidity is obtained;
(3) Placing the slurry obtained in the step (2) into a vacuum drying oven, and removing bubbles for 0.5h at room temperature under the vacuum degree of-0.10 MPa; injecting the foam into a die after the foam is removed;
(4) And (3) placing the slurry and the mould in a blast drier, heating at 80 ℃ for 2 hours to solidify and shape the slurry, cooling to room temperature, and demoulding to obtain the silicone oil-based flexible heat-conducting composite material. h-BN and S-Al in comparative example 4 2 O 3 The filling mass fractions of (2) were 35% and 15%, respectively.
Comparative example 5
A preparation method of a silicone oil-based flexible heat-conducting composite material comprises the following steps:
(1) 180.00g of vinyl-terminated silicone oil (with the viscosity of 100 mPas and the vinyl content of 0.98 wt%) and 42.15g of side hydrogen-containing silicone oil (with the hydrogen content of 0.18 wt%) and 0.89g of ethynyl cyclohexanol (with the purity of 98%) are taken, and are placed in a container, and magnetically stirred at room temperature for 2 hours at 500rpm to obtain a silicone oil mixture;
(2) 16g of flake graphite (FG, particle size 200 mesh) and silicon nitride (Si) 3 N 4 The mixture of silicone oil with the particle size of 20-30 mu m) and the silicone oil mixture obtained in the step (1) are stirred uniformly at room temperature by a high-speed stirrer at the speed of 800rpm for 1h with 50 mu L of Karstedt platinum catalyst (the zero-valent platinum concentration is 3000 ppm) to obtain uniform slurry with fluidity;
(3) Placing the slurry obtained in the step (2) into a vacuum drying oven, and removing bubbles for 0.5h at room temperature under the vacuum degree of-0.10 MPa; injecting the foam into a die after the foam is removed;
(4) And (3) placing the slurry and the mould in a blast drier, heating at 80 ℃ for 2 hours to solidify and shape the slurry, cooling to room temperature, and demoulding to obtain the silicone oil-based flexible heat-conducting composite material. FG and Si in comparative example 5 3 N 4 The filling mass fractions of (2) are 40% and 10%, respectively.
To verify the performance of the product of the invention, the following tests were performed:
thermal conductivity test
The heat conductivity of the silicone oil-based flexible heat conductive composite materials modified by the chitosan and the silane coupling agent of examples 1-5 and comparative examples 1-5 was tested by using a Hot-Disk heat conductivity tester (TPS-2500S).
(II) hardness test
The hardness of the silicone oil-based flexible heat-conducting composite materials modified by the chitosan and the silane coupling agent of examples 1-5 and comparative examples 1-5 is tested by adopting a digital display Shore durometer type A.
The test results are shown in table 1 below.
TABLE 1
As can be seen from the test results of table 1, the thermal conductivities and shore hardness of examples 1-5 are both better than those of comparative examples 1-5, and have a significant improvement. Wherein the thermal conductivity of example 1 can reach 1.309 W.m -1 ·K -1 The Shore hardness is as low as 34.5, which indicates that the silicone oil-based heat conduction composite material has the following characteristicsHas better heat-conducting property and flexibility. The main reason for improving the heat conductivity of the silicone oil-based flexible heat-conducting composite material modified by chitosan and the silane coupling agent is that the silane coupling agent grafted on the surface of the filler improves the compatibility of the filler in the silicone oil matrix, thereby reducing the interface thermal resistance between the filler and the matrix. And the chitosan attached to the surface of the filler increases the compatibility of the filler in the matrix, so that the hydroxyl on the surface of the filler is increased, grafting of the silane coupling agent on the surface of the filler is facilitated, and the thermal conductivity of the composite material is further improved. The main reason why the hardness of the silicone oil-based flexible heat-conducting composite material modified by chitosan and the silane coupling agent is reduced is that the chitosan attached to the surface of the filler inhibits the hydrosilylation reaction of vinyl-terminated silicone oil and hydrogen-containing silicone oil, and the crosslinking between the two monomers is reduced.
As can be seen from the comparison of the test results of the example 1 and the comparative examples 1 and 2, compared with the single chitosan modified or silane coupling agent modified filler, the hardness of the composite material prepared by the chitosan and the silane coupling agent modified filler is reduced more by 37 percent, the heat conductivity of the composite material is improved more by 10.7 percent, and the addition of the chitosan and the silane coupling agent in the filler modification process has better synergistic effect on the heat conductivity improvement and the Shore hardness reduction of the silicone oil-based flexible heat-conducting composite material modified by the chitosan and the silane coupling agent.
The Chinese patent CN101812233A discloses a double-component addition room temperature curing silicone rubber, which takes allylsilicone oil and hydrogen-containing silicone oil as a matrix, aluminum oxide and quartz powder as heat conducting fillers, and the heat conductivity is only 0.7-1.0 W.m -1 ·K -1 The hardness ShorA reaches 45-64, and the performance of the composite is far inferior to that of the silicon oil-based flexible heat-conducting composite material modified by chitosan and the silane coupling agent.
By comparing the test results of the examples 1-5 with the test results of the comparative examples 1-5, the addition of the chitosan and the silane coupling agent in the modification process of the heat conduction filler can effectively reduce the hardness of the silicone oil-based flexible heat conduction composite material modified by the chitosan and the silane coupling agent, improve the heat conductivity of the material, and effectively solve the problem that the heat conduction composite material has high heat conduction and low hardness and is difficult to be compatible. Therefore, the silicon oil-based flexible heat-conducting composite material modified by the chitosan and the silane coupling agent has better flexibility and higher heat conductivity, and can well solve the heat dissipation problem of electronic components.
Claims (10)
1. The silicone oil-based flexible heat-conducting composite material modified by chitosan and a silane coupling agent is characterized by being obtained by heating, solidifying and forming a flowable slurry; the fluidity slurry is prepared by uniformly stirring a modified flaky filler, a modified granular filler, a silicone oil mixture and a platinum catalyst and then defoaming; the modified flaky filler or modified granular filler is prepared by adding chitosan, granular filler or flaky filler into ethanol water solution, adding glacial acetic acid, stirring uniformly, adding a silane coupling agent, stirring, and carrying out suction filtration, washing and drying after the reaction is finished.
2. The silicone oil-based flexible heat-conducting composite material modified by chitosan and a silane coupling agent is characterized in that the silicone oil mixture accounts for 50-70% of the mass of the raw material, the modified flaky filler and the modified granular filler account for 30-50% of the mass of the raw material, the flaky filler accounts for 20-40% and the granular filler accounts for 10-20%; the silicone oil mixture is obtained by uniformly stirring vinyl-terminated silicone oil, side hydrogen-containing silicone oil and an inhibitor; the mass ratio of the vinyl-terminated silicone oil to the side hydrogen-containing silicone oil is 4:1 to 5:1, a step of; the inhibitor is 0.1 to 1 percent of the mass of the mixture of vinyl silicone oil and side hydrogen silicone oil; the dosage of the platinum catalyst does not account for the total mass percent of the raw materials, and 20-30 mu L of the platinum catalyst is added into each 10g of the mixture of the vinyl-terminated silicone oil, the side hydrogen-containing silicone oil and the inhibitor.
3. The flexible heat conducting composite material based on silicon oil modified by chitosan and silane coupling agent according to claim 1, wherein the granular filler is one or more of spherical alumina, spherical magnesia, aluminum nitride, silicon nitride and silicon carbide; the lamellar filler is one or more of lamellar graphite, hexagonal boron nitride, graphene oxide, graphene and graphene nano sheets.
4. The chitosan and silane coupling agent modified silicone oil-based flexible heat-conducting composite material according to claim 1, wherein the viscosity of the chitosan is less than 200 mPa.s, and the use amount of the chitosan is 1-2% of the mass of the granular filler and the flaky filler; the volume ratio of deionized water to absolute ethyl alcohol of the ethyl alcohol aqueous solution is 3:1-5:1, the use amount of glacial acetic acid is 1-2 mL of ethyl alcohol aqueous solution added into every 100mL of ethyl alcohol aqueous solution, and 200-300 mL of ethyl alcohol aqueous solution is added into every 25g of filling material in the modification process of the flaky filling material; the dosage of the ethanol aqueous solution in the modification process of the granular filler is 100-150 ml of ethanol aqueous solution added into every 25g of filler.
5. The flexible heat-conducting composite material based on silicone oil modified by chitosan and a silane coupling agent according to claim 1, wherein the silane coupling agent is one or more of gamma-aminopropyl triethoxysilane, gamma-glycidol ether oxypropyl trimethoxysilane, gamma-methacryloxypropyl trimethoxysilane, vinyl trimethoxysilane and vinyl triethoxysilane.
6. The flexible heat conducting composite material based on silicone oil, which is modified by chitosan and silane coupling agent according to claim 5, wherein the usage amount of the silane coupling agent is 1-2% of the mass of the granular filler and the flaky filler, the reaction time after the silane coupling agent is added is 1-3 h, and the reaction temperature is room temperature.
7. The flexible heat conducting composite material based on silicone oil modified by chitosan and silane coupling agent according to claim 1, wherein the vinyl-terminated silicone oil is divinyl terminated polydimethylsiloxane, the viscosity of the composite material is 100-500 mPa.s, and the vinyl content is 0.30-1.10 wt%; the side hydrogen silicone oil is polymethylhydrosiloxane, and the hydrogen content is 0.1-0.8wt%.
8. The flexible heat-conducting composite material based on silicone oil modified by chitosan and silane coupling agent according to claim 1, wherein the inhibitor is ethynyl cyclohexanol, the catalyst is Karstedt platinum catalyst, a complex formed by zero-valent platinum and divinyl tetramethyl disiloxane, and the concentration of the zero-valent platinum in the catalyst is 1000-5000 ppm.
9. The method for preparing the chitosan and silane coupling agent modified silicone oil-based flexible heat-conducting composite material as claimed in any one of claims 1 to 8, which is characterized by comprising the following steps:
(1) Adding the chitosan, the granular filler or the flaky filler into an ethanol water solution, adding glacial acetic acid, uniformly stirring, adding a silane coupling agent and stirring after uniformly mixing, and carrying out suction filtration, deionized water washing and vacuum drying after the reaction is finished to obtain a modified flaky filler or a modified granular filler;
(2) Uniformly stirring vinyl-terminated silicone oil, side hydrogen-containing silicone oil and an inhibitor to obtain a silicone oil mixture;
(3) Adding the modified flaky filler and the modified granular filler obtained in the step (1), the silicone oil mixture obtained in the step (2) and the platinum catalyst into a container, and uniformly stirring to obtain a flowable slurry;
(4) Removing bubbles from the flowable slurry, and then injecting the flowable slurry into a mold;
(5) And (3) heating, solidifying and forming, cooling to room temperature, and demolding to obtain the silicone oil-based flexible heat-conducting composite material modified by the chitosan and the silane coupling agent.
10. The method for preparing the chitosan and silane coupling agent modified silicone oil-based flexible heat-conducting composite material according to claim 9, which is characterized in that:
in the step (1), the stirring conditions before and after the silane coupling agent is added are 500-800 rpm, the temperature is room temperature, and the stirring time is 1-2 h; the temperature of the vacuum drying is 80-100 ℃, the vacuum degree is-0.08 to-0.10 MPa, and the time of the vacuum drying is 12-24 hours;
in the step (2), stirring is performed at room temperature, the rotating speed of the stirrer is 400-600 rpm, and the stirring time is 2-6 h;
in the step (3), stirring is performed at room temperature, the rotating speed of the stirrer is 600-1000 rpm, and the stirring time is 0.5-2 h;
in the step (4), the defoaming is to put the flowable slurry into a vacuum drying oven for vacuum defoaming; the vacuum defoaming is performed for 0.5 to 1 hour under the conditions of room temperature and vacuum degree of minus 0.10 MPa;
in the step (5), the slurry and the mould are placed in a blast drier together for heating to solidify and shape the material; the heating temperature of the blast drier is 60-80 ℃ and the heating time is 1-2 h.
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