CN116102886A - High-heat-conductivity insulating silicon rubber composite material and preparation method thereof - Google Patents
High-heat-conductivity insulating silicon rubber composite material and preparation method thereof Download PDFInfo
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Images
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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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/08—Materials not undergoing a change of physical state when used
- C09K5/14—Solid materials, e.g. powdery or granular
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/382—Boron-containing compounds and nitrogen
- C08K2003/385—Binary compounds of nitrogen with boron
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The invention provides a high heat conduction insulating silicon rubber composite material and a preparation method thereof, wherein the composite material comprises 60-100 parts of methyl vinyl silicon rubber, 10-50 parts of silanized boron nitride nanosheets, 3-15 parts of filling reinforcing agent, 2-10 parts of structure control agent, 2-5 parts of coupling agent, 2, 5-dimethyl-2 of vulcanizing agent and 1-2 parts of bis (bi) penta (bi) 2), and the composite material is prepared into an oligomeric nano filler with the thickness of about 2.5nm by covalent grafting trimethyl/triethyl silane groups on the surface of boron nitride, so that the dispersion and interface combination of the oligomeric nano filler in a silicon rubber matrix are enhanced. According to the composite material and the preparation method thereof, the oligose trimethyl/triethylsilane functionalized boron nitride nano sheet is added into the silicon rubber, the oligose nano filler with the thickness of about 2.5nm is prepared, the affinity between the layered boron nitride filler and the silicon rubber is improved, and the mechanical property of the silicon rubber is improved while the heat conductivity and the insulativity of the silicon rubber are improved.
Description
Technical Field
The invention belongs to the technical field of rubber processing, and particularly relates to a high-heat-conductivity insulating silicon rubber composite material and a preparation method thereof.
Background
With the rapid development of modern electronic products, the development of electronic packaging materials with high efficiency is becoming a global challenge. Improving the thermal conductivity of electronic packaging materials is critical to extending the useful life of electronic devices. At the same time, electrical insulation is also important for electronic packaging materials. Silicone rubber has excellent insulating properties, is a commonly used electronic packaging material, and its poor thermal conductivity hinders its development. For most saturated system polymers, the thermal conductivity is improved by filling with a thermally conductive filler. A large amount of high thermal conductivity filler such as MWNTs, graphene oxide, alN, al2O3, h-BN (original boron nitride) has been compounded with the polymer matrix. Among them, h-BN is attracting attention due to its excellent properties. A similar hexagonal structure is also present between h-BN and graphene. Compared with other high heat conduction fillers, the high heat conduction filler has high heat conduction, high chemical stability, excellent electrical insulation performance and mechanical performance.
Although it is common to improve the thermal conductivity of the material, it is difficult to expand the application range because h-BN is an inorganic filler and has poor affinity with silicone rubber, and adding pure boron nitride into silicone rubber is not easy to form good dispersion. The preparation of the boron nitride nano-sheet and the proper chemical functionalization of the nano-sheet are beneficial to overcoming the strong interaction between the nano-sheet layers and improving the dispersion stability of the nano-sheet. Many researchers have done a lot of work with these problems. Unfortunately, although these methods are effective, the h-BN modification process is complex and harsh, the grafting rate is low, the nanosheets are easy to agglomerate secondarily, the thicker sheets are unfavorable for dispersion and heat conduction, and the method is not suitable for large-scale use. In this regard, it is desirable to develop a new and convenient method of functionalizing boron nitride nanoplatelets to enhance their dispersion and interfacial bonding in silicone rubber to enhance thermal conductivity.
Disclosure of Invention
The invention provides a high-heat-conductivity insulating silicon rubber composite material and a preparation method thereof, and solves the problems in the prior art.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
the high-heat-conductivity insulating silicon rubber composite material comprises the following components in parts by weight:
60-100 parts of methyl vinyl silicone rubber;
3-15 parts of filling reinforcing agent;
10-50 parts of silanized boron nitride nano-sheets;
2-10 parts of a structure control agent;
2-5 parts of a coupling agent;
1-2 parts of a bis-dipentaerythritol vulcanizing agent.
Further, the silanized boron nitride nano-sheet is one or a mixture of two of trimethyl iodinated silane functionalized boron nitride nano-sheet and triethyl iodinated silane functionalized boron nitride nano-sheet.
Further, the filling reinforcing agent is one or more of N550, N990, white carbon black and N774.
Further, the structure control agent is one or more of diphenyl silicon glycol, hydroxyl silicone oil, methoxy silicone oil, methyl silicone oil, vinyl trimethoxy silane A-171, vinyl triethoxy silane A-151, vinyl tri-2-methoxyethoxy silane A-172 and gamma-methacryloxypropyl trimethoxy silane A-174.
Further, the coupling agent is a mixture of one or more of silane coupling agents KH550, KH560, KH570 and titanate coupling agent NDZ 201.
A preparation method of a high-heat-conductivity insulating composite material comprises the following steps:
preparing silanized boron nitride nanosheets;
weighing the following materials in parts by weight: 60-100 parts of methyl vinyl silicone rubber, 10-50 parts of silanized boron nitride nano-sheets, 3-15 parts of filling reinforcing agent, 2-10 parts of structure control agent, 2-5 parts of coupling agent and 1-2 parts of vulcanizing agent for standby;
adding 60-100 parts of methyl vinyl silicone rubber raw rubber to a roller of a double-roller open mill, and adding 3-15 parts of filling reinforcing agent after roller wrapping;
adding 2-10 parts of structure control agent and 2-5 parts of coupling agent, then adding 10-50 parts of silanized boron nitride nanosheets, and repeatedly mixing until the mixture is uniform;
adding 1-2 parts of bi-di-penta vulcanizing agent, and continuously and uniformly mixing to obtain the high heat conduction insulating composite material.
Further, preparing a silanized boron nitride nano-sheet, comprising the following steps:
adding original boron nitride, sodium hydroxide and deionized water into a ball milling tank of an vertical planetary ball mill, stirring and mixing uniformly, then loading agate balls into the vertical planetary ball mill, and starting up for ball milling;
after ball milling, neutralizing the mixed solution with dilute hydrochloric acid, and performing centrifugal washing with deionized water for a plurality of times to enable the pH value of the mixed solution to be close to neutral;
standing, precipitating, filtering and drying the mixed solution to obtain boron nitride nanosheets OH-BNNS grafted with hydroxyl groups on the surfaces;
adding dried OH-BNNS and anhydrous tetrahydrofuran into a flask, and performing ultrasonic dispersion by using an ultrasonic cell grinder to form uniform dispersion; transferring the dispersion liquid into a three-neck flask, blowing nitrogen to exhaust air in the flask, slowly adding trimethyl iodosilane or triethyl iodosilane in an ice water bath while stirring, reacting, adding absolute ethyl alcohol and deionized water, and neutralizing residual free radicals on OH-BNNS;
filtering the mixed solution through a PTFE filter membrane, and fully washing the mixed solution with tetrahydrofuran, water and absolute ethyl alcohol;
and (5) fully drying in a vacuum oven to obtain the silanized boron nitride nano-sheet.
Further, 100 parts by weight of original boron nitride, 40-60 parts by weight of sodium hydroxide and 500-1000 parts by weight of deionized water are added into a ball milling tank of an vertical planetary ball mill, and after stirring and mixing uniformly, agate balls are filled into the vertical planetary ball mill, the ball milling is started, the rotating speed of the planetary ball mill is set to 200-420 revolutions per minute, and the cumulative ball milling is carried out for 24-48 hours.
Further, adding the dried OH-BNNS and 170-270 parts of anhydrous tetrahydrofuran by weight into a flask, and performing ultrasonic dispersion for 1-2 hours by using an ultrasonic cell grinder; 25-75 parts by weight of trimethyliodosilane or triethyliodosilane was slowly added to the ice water bath with stirring, and reacted for 2 hours.
Further, the mixture was filtered through a 0.2 μm PTFE filter.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the heat-conducting insulating silicon rubber composite material added with the silanized boron nitride nanosheets and the preparation method thereof, the oligose trimethyl/triethylsilane functionalized boron nitride nanosheets are added into the silicon rubber, and the oligose nanofiller with the thickness of about 2.5nm is prepared by covalently grafting trimethyl/triethylsilane groups on the surface of the boron nitride, so that the dispersion and interface combination of the oligose nanofiller in a silicon rubber matrix are enhanced, the affinity between the lamellar boron nitride filler and the silicon rubber is improved, and the mechanical property of the silicon rubber is greatly improved while the heat conductivity and the insulativity of the silicon rubber are improved.
2. The invention introduces the group unit similar to the matrix on the heat conduction nanometer filler, which is beneficial to the cross-linking polymerization of the layered filler and the matrix to form a heat conduction network structure in the vulcanization process, and is beneficial to the formation of a synergistic resonance effect with the molecular chain, crystal lattice and the like of the silicon rubber matrix to improve the heat conduction efficiency of the composite material.
It is, of course, not necessary for all of the above advantages to be achieved simultaneously in the practice of the various aspects of the invention.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other embodiments of the drawings can be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a flow chart of the preparation of examples 1 and 2 of the present invention;
FIG. 2 is an atomic force microscope image of silane functionalized boron nitride nanoplatelets prepared according to an embodiment of the present invention dispersed in an acetone solvent;
Detailed Description
In order that the invention may be readily understood, a more complete description of the invention will be rendered by reference to the appended drawings. The drawings illustrate preferred embodiments of the invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
In the description of this patent, it should be understood that the terms "center," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," and the like indicate orientations or positional relationships based on the orientation or positional relationships shown in the drawings, merely to facilitate describing the patent and simplify the description, and do not indicate or imply that the devices or elements being referred to must have a particular orientation, be configured and operated in a particular orientation, and are therefore not to be construed as limiting the patent.
In the description of this patent, it should be noted that, unless explicitly stated and limited otherwise, the terms "mounted," "connected," and "disposed" are to be construed broadly, and may be fixedly connected, disposed, detachably connected, disposed, or integrally connected, disposed, for example. The specific meaning of the terms in this patent will be understood by those of ordinary skill in the art as the case may be. The present invention will be described in detail with reference to the accompanying drawings and examples.
Example 1:
the embodiment provides a heat-conducting insulating silicon rubber composite material added with silanized boron nitride nano sheets and a preparation method thereof, wherein the preparation method comprises the following steps:
step 1, preparing a trimethyliodized silanized boron nitride nano sheet:
adding 100g of boron nitride raw material, 40g of sodium hydroxide and 800ml of deionized water into a ball milling tank of an upright planetary ball mill, stirring and mixing uniformly, and then filling agate balls with diameters of 2mm and 6mm into the ball milling tank, wherein the weights of the agate balls are 700g and 300g respectively; setting the rotating speed of the planetary ball mill to 300 revolutions per minute, performing cumulative ball milling for 48 hours, neutralizing residues with dilute hydrochloric acid solution, and performing centrifugal washing with deionized water for a plurality of times until the pH value of the mixed solution is close to neutral; standing, precipitating, filtering, and finally drying in a vacuum drying oven at 70 ℃ to obtain boron nitride nanosheets (OH-BNNS) with hydroxyl (-OH) groups grafted on the surfaces;
adding dried OH-BNNS and 200ml anhydrous tetrahydrofuran into a flask, and performing ultrasonic dispersion for 2 hours by using an ultrasonic cell grinder to form uniform dispersion; transferring the dispersion into a three-necked flask, blowing nitrogen to exhaust air in the flask, and slowly adding 25ml of trimethyliodosilane into the three-necked flask while stirring in an ice water bath; after 2 hours of reaction, adding a small amount of anhydrous ethanol and deionized water to neutralize the residual free radicals on the boron nitride nano-sheet, so as to prevent side reaction; the mixture was filtered through a 0.2 μm PTFE filter membrane and washed thoroughly with Tetrahydrofuran (THF), water and absolute ethanol; and drying in a vacuum oven for 2 days to obtain the trimethyliodized silanized boron nitride nanosheets. FIG. 2 is an atomic force microscope image of a silanized boron nitride nanosheet dispersed in an acetone solvent, where it can be seen that the prepared silanized boron nitride nanosheet has a diameter of about 300nm, a thickness of about 2.5nm, is uniformly dispersed and does not undergo agglomeration.
Step 2, preparing a high-heat-conductivity silicon rubber composite material:
adding 200g of raw methyl vinyl silicone rubber into a roller of a two-roller open mill, firstly adding 30g of N550 carbon black after roller wrapping, then adding 8g of hydroxyl silicone oil and 5g of silane coupling agent KH550, and then adding 60g of trimethyliodinated boron nitride nano-sheets; repeatedly mixing until the mixture is uniform; finally, adding 2.5g of 5-bis (tert-butylperoxy) hexane (abbreviated as a bis-dipentaerythritol vulcanizing agent); and continuously and uniformly mixing to obtain the high-heat-conductivity silicon rubber composite material. The flow chart of the preparation process is shown in fig. 1, and the heat conduction network structure of the composite material is also shown in the figure.
Comparative example 1:
200g of raw methyl vinyl silicone rubber is added to a roll of a two-roll mill, and 30g of N550 carbon black is added after roll coating. Then 8g of hydroxyl silicone oil and 5g of silane coupling agent KH550 are added, followed by 60g of original boron nitride; repeatedly mixing until the mixture is uniform; finally adding 2.5g of bis-dipentaerythritol vulcanizing agent; and (5) continuing to uniformly mix to obtain the composite material of the comparative example 1.
Example 2:
the embodiment provides a heat-conducting insulating silicon rubber composite material added with silanized boron nitride nano sheets and a preparation method thereof, wherein the preparation method comprises the following steps:
step 1, preparing triethylsilane functionalized boron nitride nano-sheets:
adding 100g of boron nitride raw material, 40g of sodium hydroxide and 800ml of deionized water into a ball milling tank of an upright planetary ball mill, stirring and mixing uniformly, and then filling agate balls with diameters of 2mm and 6mm into the ball milling tank, wherein the weights of the agate balls are 700g and 300g respectively; setting the rotating speed of the planetary ball mill to 300 revolutions per minute, performing cumulative ball milling for 48 hours, neutralizing residues with dilute hydrochloric acid solution, and performing centrifugal washing with deionized water for a plurality of times until the pH value of the mixed solution is close to neutral; standing, precipitating, filtering, and finally drying in a vacuum drying oven at 70 ℃ to obtain the boron nitride nanosheets (OH-BNNS) with hydroxyl (-OH) groups grafted on the surfaces.
Adding dried OH-BNNS and 200ml anhydrous tetrahydrofuran into a flask, and performing ultrasonic dispersion for 2 hours by using an ultrasonic cell grinder to form uniform dispersion; transferring the dispersion into a three-necked flask, blowing nitrogen to exhaust air in the flask, and slowly adding 25ml of triethyliodosilane in an ice-water bath while stirring; after 2 hours of reaction, a small amount of anhydrous ethanol and deionized water are added to neutralize the residual free radicals on the boron nitride nano-sheet, so as to prevent side reaction. The mixture was filtered through a 0.2 μm PTFE filter and washed thoroughly with Tetrahydrofuran (THF), water and absolute ethanol. Drying in a vacuum oven for 2 days to obtain triethylsilane functionalized boron nitride nano sheets;
step 2, preparing a high-heat-conductivity silicon rubber composite material:
adding 200g of raw methyl vinyl silicone rubber into a roller of a two-roller open mill, and adding 30g of N550 carbon black after roller wrapping; then 8g of hydroxyl silicone oil and 5g of silane coupling agent KH550 are added, and then 60g of triethyl silanized boron nitride nano-sheet is added; repeatedly mixing until the mixture is uniform; finally adding 2.5g of bis-dipentaerythritol vulcanizing agent; and continuously and uniformly mixing to obtain the high-heat-conductivity silicon rubber composite material. Referring to fig. 1, a flow chart of the above preparation process is shown, and a composite material heat conducting network structure is also shown.
Comparative example 2:
200g of raw methyl vinyl silicone rubber is added to a roll of a two-roll mill, and 30g of N550 carbon black is added after roll coating. Then 8g of hydroxyl silicone oil and 5g of silane coupling agent KH550 are added, followed by 60g of alumina powder; repeatedly mixing until the mixture is uniform; finally adding 2.5g of bis-dipentaerythritol vulcanizing agent; and (5) continuing to uniformly mix to obtain the composite material of the comparative example 2.
Example 3:
the embodiment provides a heat-conducting insulating silicon rubber composite material added with silanized boron nitride nano sheets and a preparation method thereof, wherein the preparation method comprises the following steps:
step 1, preparing a silane functionalized boron nitride nano-sheet:
trimethyl silanized boron nitride nanoplatelets and triethyl silanized boron nitride nanoplatelets were prepared by the methods of example 1 and example 2, respectively, described above.
Step 2, preparing a high-heat-conductivity silicon rubber composite material:
200g of raw methyl vinyl silicone rubber is added to a roller of a two-roller open mill, and 30g of fumed silica is added after roller wrapping. Then adding 4g of hydroxyl silicone oil, 4g of vinyl tri-2-methoxyethoxysilane A-172 and 5g of silane coupling agent KH550, and then adding 60g of trimethyl silanized boron nitride nano-plate and 40g of triethyl silanized boron nitride nano-plate; repeatedly mixing until the mixture is uniform; finally adding 2.5g of bis-dipentaerythritol vulcanizing agent; and continuously and uniformly mixing to obtain the high-heat-conductivity silicon rubber composite material.
Comparative example 3:
200g of raw methyl vinyl silicone rubber is added to a roller of a two-roller open mill, and 30g of fumed silica is added after roller wrapping. Then 4g of hydroxy silicone oil, 4g of vinyl tri-2-methoxyethoxysilane A-172 and 5g of silane coupling agent KH550 are added, followed by 100g of aluminum nitride; repeatedly mixing until the mixture is uniform; finally adding 2.5g of bis-dipentaerythritol vulcanizing agent; and (5) continuing to uniformly mix to obtain the composite material of the comparative example 3.
The results of the performance test of the insulating and heat conducting silicone rubber composite materials obtained in the above three examples and the composite materials obtained in the above three comparative examples are shown in the following table:
as can be seen from the table, the addition of the silane group grafted oligolayer boron nitride nanosheets in the silicone rubber improves the thermal conductivity and insulation properties of the silicone rubber and improves the mechanical properties of the silicone rubber. The invention synthesizes a novel oligose trimethyl/triethylsilane functionalized boron nitride nano sheet, and as the surface of the oligose trimethyl/triethylsilane functionalized boron nitride nano sheet is grafted with rich silane organic groups, the second agglomeration of the nano sheet is effectively avoided, the peeling of the nano sheet is promoted, and the dispersion, compatibility and interface combination of the nano sheet in silicon rubber are enhanced.
Meanwhile, the invention introduces the group unit similar to the matrix on the heat conduction nano filler, which is beneficial to the cross-linking polymerization of the layered filler and the matrix to form a heat conduction network structure in the vulcanization process and is beneficial to the formation of synergistic resonance with the molecular chain, crystal lattice and the like of the silicon rubber matrix to improve the heat conduction efficiency.
Example 4:
the embodiment provides a high-heat-conductivity insulating silicon rubber composite material which comprises the following components in parts by weight:
60 parts of methyl vinyl silicone rubber;
3 parts of filling reinforcing agent;
10 parts of silanized boron nitride nanosheets;
2 parts of a structure control agent;
2 parts of a coupling agent;
1 part of a bis-dipentaerythritol vulcanizing agent.
The silanized boron nitride nano-sheet is one or a mixture of two of trimethyl iodinated silane functionalized boron nitride nano-sheet and triethyl iodinated silane functionalized boron nitride nano-sheet.
The filling reinforcing agent is one or more of N550, N990, white carbon black and N774.
The structure control agent is one or more of diphenyl silicon glycol, hydroxyl silicone oil, methoxy silicone oil, methyl silicone oil, vinyl trimethoxy silane A-171, vinyl triethoxy silane A-151, vinyl tri-2-methoxyethoxy silane A-172 and gamma-methacryloxypropyl trimethoxy silane A-174.
The coupling agent is a mixture of one or more of silane coupling agents KH550, KH560, KH570 and titanate coupling agent NDZ 201.
Example 5:
the embodiment provides a high-heat-conductivity insulating silicon rubber composite material which comprises the following components in parts by weight:
100 parts of methyl vinyl silicone rubber;
15 parts of filling reinforcing agent;
50 parts of silanized boron nitride nano-sheets;
10 parts of a structure control agent;
5 parts of a coupling agent;
2 parts of a bis-dipentaerythritol vulcanizing agent.
The silanized boron nitride nano-sheet is one or a mixture of two of trimethyl iodinated silane functionalized boron nitride nano-sheet and triethyl iodinated silane functionalized boron nitride nano-sheet.
The filling reinforcing agent is one or more of N550, N990, white carbon black and N774.
The structure control agent is one or more of diphenyl silicon glycol, hydroxyl silicone oil, methoxy silicone oil, methyl silicone oil, vinyl trimethoxy silane A-171, vinyl triethoxy silane A-151, vinyl tri-2-methoxyethoxy silane A-172 and gamma-methacryloxypropyl trimethoxy silane A-174.
The coupling agent is a mixture of one or more of silane coupling agents KH550, KH560, KH570 and titanate coupling agent NDZ 201.
Example 6:
the embodiment provides a high-heat-conductivity insulating silicon rubber composite material which comprises the following components in parts by weight:
75 parts of methyl vinyl silicone rubber;
filling 8 parts of a reinforcing agent;
35 parts of silanized boron nitride nano-sheets;
7 parts of a structure control agent;
4 parts of a coupling agent;
1.5 parts of bis-dipentaerythritol vulcanizing agent.
The silanized boron nitride nano-sheet is one or a mixture of two of trimethyl iodinated silane functionalized boron nitride nano-sheet and triethyl iodinated silane functionalized boron nitride nano-sheet.
The filling reinforcing agent is one or more of N550, N990, white carbon black and N774.
The structure control agent is one or more of diphenyl silicon glycol, hydroxyl silicone oil, methoxy silicone oil, methyl silicone oil, vinyl trimethoxy silane A-171, vinyl triethoxy silane A-151, vinyl tri-2-methoxyethoxy silane A-172 and gamma-methacryloxypropyl trimethoxy silane A-174.
The coupling agent is a mixture of one or more of silane coupling agents KH550, KH560, KH570 and titanate coupling agent NDZ 201.
In conclusion, the silicon rubber composite material prepared by the invention has good thermal conductivity, high insulativity and excellent mechanical property, and the technical route can be expanded to various composite material applications.
The foregoing description of the invention has been presented for purposes of illustration and description, and is not intended to be limiting. Several simple deductions, modifications or substitutions may also be made by a person skilled in the art to which the invention pertains, based on the idea of the invention.
Claims (10)
1. The high-heat-conductivity insulating silicon rubber composite material is characterized by comprising the following components in parts by weight:
60-100 parts of methyl vinyl silicone rubber;
3-15 parts of filling reinforcing agent;
10-50 parts of silanized boron nitride nano-sheets;
2-10 parts of a structure control agent;
2-5 parts of a coupling agent;
1-2 parts of a bis-dipentaerythritol vulcanizing agent.
2. The high thermal conductivity insulating silicone rubber composite of claim 1, wherein the silanized boron nitride nanoplatelets are one or a mixture of two of trimethyliodosilane functionalized boron nitride nanoplatelets and triethyliodosilane functionalized boron nitride nanoplatelets.
3. The high thermal conductivity insulating silicone rubber composite according to claim 1, wherein the filling reinforcing agent is a mixture of one or more of N550, N990, white carbon black, N774.
4. The high thermal conductivity insulating silicone rubber composite according to claim 1, wherein the structure controlling agent is one or more of diphenyl silicon glycol, hydroxy silicone oil, methoxy silicone oil, methyl silicone oil, vinyl trimethoxysilane a-171, vinyl triethoxysilane a-151, vinyl tri-2-methoxyethoxysilane a-172, gamma-methacryloxypropyl trimethoxysilane a-174.
5. The high thermal conductivity insulating silicone rubber composite according to claim 1, wherein the coupling agent is a mixture of one or more of silane coupling agents KH550, KH560, KH570 and titanate coupling agent NDZ 201.
6. The preparation method of the high-heat-conductivity insulating composite material is characterized by comprising the following steps of:
preparing silanized boron nitride nanosheets;
weighing the following materials in parts by weight: 60-100 parts of methyl vinyl silicone rubber, 10-50 parts of silanized boron nitride nano-sheets, 3-15 parts of filling reinforcing agent, 2-10 parts of structure control agent, 2-5 parts of coupling agent and 1-2 parts of vulcanizing agent for standby;
adding 60-100 parts of methyl vinyl silicone rubber raw rubber to a roller of a double-roller open mill, and adding 3-15 parts of filling reinforcing agent after roller wrapping;
adding 2-10 parts of structure control agent and 2-5 parts of coupling agent, then adding 10-50 parts of silanized boron nitride nanosheets, and repeatedly mixing until the mixture is uniform;
adding 1-2 parts of bi-di-penta vulcanizing agent, and continuously and uniformly mixing to obtain the high heat conduction insulating composite material.
7. The method for preparing the high thermal conductivity insulating silicon rubber composite material according to claim 6, wherein the preparation of the silanized boron nitride nano-sheet comprises the following steps:
adding original boron nitride, sodium hydroxide and deionized water into a ball milling tank of an vertical planetary ball mill, stirring and mixing uniformly, then loading agate balls into the vertical planetary ball mill, and starting up for ball milling;
after ball milling, neutralizing the mixed solution with dilute hydrochloric acid, and performing centrifugal washing with deionized water for a plurality of times to enable the pH value of the mixed solution to be close to neutral;
standing, precipitating, filtering and drying the mixed solution to obtain boron nitride nanosheets OH-BNNS grafted with hydroxyl groups on the surfaces;
adding dried OH-BNNS and anhydrous tetrahydrofuran into a flask, and performing ultrasonic dispersion by using an ultrasonic cell grinder to form uniform dispersion; transferring the dispersion liquid into a three-neck flask, blowing nitrogen to exhaust air in the flask, slowly adding trimethyl iodosilane or triethyl iodosilane in an ice water bath while stirring, reacting, adding absolute ethyl alcohol and deionized water, and neutralizing residual free radicals on OH-BNNS;
filtering the mixed solution through a PTFE filter membrane, and fully washing the mixed solution with tetrahydrofuran, water and absolute ethyl alcohol;
and (5) fully drying in a vacuum oven to obtain the silanized boron nitride nano-sheet.
8. The method for preparing the high-heat-conductivity insulating silicon rubber composite material according to claim 7, wherein 100 parts by weight of original boron nitride, 40-60 parts by weight of sodium hydroxide and 500-1000 parts by weight of deionized water are added into a ball milling tank of an vertical planetary ball mill, and after the raw boron nitride, the sodium hydroxide and the deionized water are stirred and mixed uniformly, agate balls are filled into the vertical planetary ball mill, the vertical planetary ball mill is started for ball milling, the rotating speed of the planetary ball mill is set to be 200-420 revolutions per minute, and the cumulative ball milling is carried out for 24-48 hours.
9. The method for preparing the high thermal conductivity insulating silicon rubber composite material according to claim 8, wherein the dried OH-BNNS and 170-270 parts by weight of anhydrous tetrahydrofuran are added into a flask, and the mixture is dispersed for 1-2 hours by ultrasonic waves by an ultrasonic cell grinder; 25-75 parts by weight of trimethyliodosilane or triethyliodosilane was slowly added to the ice water bath with stirring, and reacted for 2 hours.
10. The method for preparing a high thermal conductivity insulating silicone rubber composite according to claim 9, wherein the mixed solution is filtered through a 0.2 μm PTFE filter membrane.
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