CN107778865A - A kind of CNT composite heat conducting material and preparation method thereof - Google Patents

A kind of CNT composite heat conducting material and preparation method thereof Download PDF

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Publication number
CN107778865A
CN107778865A CN201610794639.0A CN201610794639A CN107778865A CN 107778865 A CN107778865 A CN 107778865A CN 201610794639 A CN201610794639 A CN 201610794639A CN 107778865 A CN107778865 A CN 107778865A
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cnt
conducting material
heat conducting
composite heat
heat
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张立强
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Have New Materials (huizhou) Co Ltd
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Have New Materials (huizhou) Co Ltd
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Priority to CN201610794639.0A priority Critical patent/CN107778865A/en
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00Compositions 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
    • C08L83/04Polysiloxanes
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00Heat-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
    • C09K5/08Materials not undergoing a change of physical state when used
    • C09K5/14Solid materials, e.g. powdery or granular
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/01Magnetic additives
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/011Nanostructured additives
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00Applications
    • C08L2203/20Applications use in electrical or conductive gadgets
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/02Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure

Abstract

The invention discloses a kind of CNT composite heat conducting material and preparation method thereof, raw material mainly includes machine silicones, CNT, heat filling, coupling agent and other auxiliary agents, by being pre-mixed the techniques such as vacuum, field orientation, calendering, the excellent heat-conductive composite material of excellent in mechanical performance, heat-conducting effect is prepared.The fundamental propertys such as the surface tension of the invention based on organic siliconresin is small, compressibility is high, gas permeability is high, and there is the excellent specific properties such as high-low temperature resistant, electric insulation, resistance to oxidation stability, weatherability, fire retardant, hydrophobic, corrosion-resistant, nonpoisonous and tasteless and physiological inertia, increase certain proportion carbon nano-tube material and high heat conduction agent, CNT is orientated with field orientation technology, improve the heat conductivility of organosilicon material simultaneously, strengthen its mechanical property, more efficient practical material is provided for LED and the application of electronics field of heat transfer.

Description

A kind of CNT composite heat conducting material and preparation method thereof
Technical field
The present invention relates to a kind of CNT composite heat conducting material and preparation method thereof.
Background technology
Organosilicon product is using silicon-oxygen (Si-O) key as backbone structure, so organosilicon product has heat endurance The features such as height, weatherability height, electrical apparatus insulation performance, low surface tension and low-surface-energy, physiological inertia, due to organosilicon have it is upper These excellent performances are stated, therefore its application is very extensive.It serves not only as aviation, sophisticated technology, military technology portion The special material of door uses, and is also used for each department of national economy, and its application has diffused into:Building, electric, spinning Knit, automobile, machinery, leather papermaking, chemical industry light industry, metal and paint, medical medical treatment etc..
Domestic and international researcher has carried out substantial amounts of research and development and modification to organosilicon Heat Conduction Material, gradually forms a series of heat conduction Silicon materials.The research that super-high heat-conductive composite is prepared using inorganic filler (glass fibre, carbon fiber, whisker etc.) in recent years is got over More to attract attention, and it is widely used in electronics industry.CNT is due to big with draw ratio, high temperature resistant, anti-chemistry Burn into intensity is high, and heat conductivility is high, easily surface treatment advantage, with organosilicon it is compound after polymeric system performance is obtained very Big raising.
Meanwhile in terms of Electronic Packaging and computer chip, the physical dimension of equipment constantly reduces, energy output is continuous Increase so that the research of Heat Conduction Material becomes more and more important in this field.The shaping of conventional thermal conductive material easy processing, price are low It is honest and clean, but thermal conductivity is relatively low.By adding the functional stuffing of high heat conductance in organosilicon material, such as aluminium nitride, boron nitride, oxygen Change magnesium and aluminum oxide etc., be expected to significantly improve the heat conductivility of polymer, while and can keeps the insulating properties of polymer.
So far, numerous patents have been reported that addition certain proportion carbon nano-tube material, and use organic siliconresin For matrix, high heat conduction filler, but it is to use conventional method mostly, heat transfer efficiency is relatively low.Therefore, the carbon nanometer that the present invention is developed Pipe handling process is significant to enhancing Heat Conduction Material, has broad application prospects.
The content of the invention
The technical problems to be solved by the invention are the defects of overcoming prior art, there is provided a kind of CNT composite heat-conducting Material and preparation method thereof, using CNT superelevation anisotropic thermal ability, with high-intensity magnetic field intervention means, directional orientation CNT, the CNT capacity of heat transmission is given full play to, be equipped with metal-powder enhancing magnetic sensitivity, prepare low-density, height Pliability, the organic siliconresin of high heat conduction are material modified.
The present invention solves above-mentioned technical problem and adopted the technical scheme that:A kind of CNT composite heat conducting material, including The raw material of following parts by weight:Organic siliconresin 15~50, thermal conducting agent 10~40, CNT 0.5~10, catalyst 0.05~1, Curing agent 0.05~1, other auxiliary agents 0.1~15.
Preferably, the organic siliconresin is clear viscous liquids.
Preferably, the thermal conducting agent is Preparation of Metallic Strontium, metal niobium, magnetic powder, aluminum oxide, magnesia, aluminium nitride, nitridation One or more in boron and carborundum are compounded.
Preferably, described CNT is the mixed of one or both of single-walled carbon nanotube and multi-walled carbon nanotube Compound.
Preferably, the catalyst is platinum catalyst.
Preferably, the curing agent is containing hydrogen silicone oil, hydrogen content is 0.05~1.
Preferably, other described auxiliary agents include the one or more in fire retardant, coupling agent and releasing agent.
A kind of preparation method of CNT composite heat conducting material, comprises the following steps:
Step 1:Heat filling is surface-treated using coupling agent, is dispersed with stirring, heat filling surface is uniformly wrapped Cover one layer of coupling agent, reinforcer and the compatibility of organic siliconresin matrix;
Step 2:Treated heat filling and organic siliconresin, CNT, fire retardant, which load dispersion machine, to be mixed Scattered 1min~60min is closed, forms mixture one;
Step 3:Catalyst and curing agent are separately added into dispersion machine again, stirring 1min is disperseed together with mixture one ~60min, vacuum degassing, form mixture two;
Step 4:Mixture two is subjected to calendering production, then to the additional high-intensity magnetic field of product, to carbon nano-tube oriented orientation 30min~120min, finally by product sulfidization molding.
After employing above-mentioned technical proposal, the present invention has following beneficial effect:A kind of carbon involved in the present invention is received Mitron strengthens organosilicon Heat Conduction Material, and 1. using the excellent mechanics of CNT, heat transfer, electrical property, physical property, by it with having The progress of machine silicones is compound, can not only improve the intensity of matrix material, improve its toughness, can improve its heat conductivility;2. Addition compounding thermal conducting agent, the heat conductivility of its material is significantly improved, it is met LED increasingly in great demand and electronics heat transfer neck Domain;3. be orientated with additional high-intensity magnetic field (field orientation) to CNT, make full use of in terms of CNT heat conduction respectively to The characteristics of different in nature, improve material vertical direction thermal conductivity factor.
Embodiment
In order that present disclosure is easier to be clearly understood, below according to specific embodiment, the present invention is made into One step is described in detail.
A kind of CNT composite heat conducting material, include the raw material of following parts by weight:Organic siliconresin 15~50, thermal conducting agent 10~40, CNT 0.5~10, catalyst 0.05~1, curing agent 0.05~1, other auxiliary agents 0.1~15.
The organic siliconresin is clear viscous liquids.
The thermal conducting agent is Preparation of Metallic Strontium, metal niobium, magnetic powder, aluminum oxide, magnesia, aluminium nitride, boron nitride and carbonization One or more in silicon are compounded, preferably Preparation of Metallic Strontium, metal niobium, magnetic powder, aluminum oxide, aluminium nitride and boron nitride.
Described CNT is the mixture of one or both of single-walled carbon nanotube and multi-walled carbon nanotube, preferably Single-walled carbon nanotube, diameter and length are respectively 0.75~3nm and 1~50 μm.
The catalyst is platinum catalyst.
The curing agent is containing hydrogen silicone oil, and hydrogen content is 0.05~1.
Other described auxiliary agents include the one or more in fire retardant, coupling agent and releasing agent.
A kind of preparation method of CNT composite heat conducting material, comprises the following steps:
Step 1:Heat filling is surface-treated using coupling agent, is dispersed with stirring, heat filling surface is uniformly wrapped Cover one layer of coupling agent, reinforcer and the compatibility of organic siliconresin matrix;
Step 2:Treated heat filling and organic siliconresin, CNT, fire retardant, which load dispersion machine, to be mixed Scattered 1min~60min is closed, forms mixture one;
Step 3:Catalyst and curing agent are separately added into dispersion machine again, stirring 1min is disperseed together with mixture one ~60min, vacuum degassing, form mixture two;
Step 4:Mixture two is subjected to calendering production, then to the additional high-intensity magnetic field of product, to carbon nano-tube oriented orientation 30min~120min, finally by product sulfidization molding.
Embodiment:Including following four embodiment
Table 1
Composition Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4
Organic siliconresin 40 40 40 40
Thermal conducting agent 48.6 48.1 47.6 47.1
CNT 1 1.5 2 2.5
Catalyst 0.15 0.15 0.15 0.15
Curing agent 0.25 0.25 0.25 0.25
Other auxiliary agents 10 10 10 10
The raw material proportioning of four embodiments in table 1 is prepared according to above-mentioned preparation method.
According to the product prepared by the formula in four embodiments in table 1 under identical environment temperature test performance result It is as follows:
Table 2
The test result that embodiment 1 is formulated to embodiment 4 from table 2 can be seen that the increase with CNT ratio, institute Prepare that thermal conductivity factor and the tensile strength of material are in rising trend, the proof voltage of material can be on a declining curve;With carbon nanometer The increase of pipe ratio, the increase of material Hybrid Production Process difficulty.
It is contemplated that using CNT superelevation anisotropic thermal ability, with high-intensity magnetic field intervention means, orientation takes To CNT, give full play to the CNT capacity of heat transmission, be equipped with metal-powder enhancing magnetic sensitivity, prepare low-density, High-flexibility, the organic siliconresin of high heat conduction are material modified.
Particular embodiments described above, pair present invention solves the technical problem that, technical scheme and beneficial effect carry out It is further described, should be understood that the specific embodiment that the foregoing is only the present invention, is not limited to this Invention, within the spirit and principles of the invention, any modification, equivalent substitution and improvements done etc., should be included in this hair Within bright protection domain.

Claims (8)

  1. A kind of 1. CNT composite heat conducting material, it is characterised in that:Include the raw material of following parts by weight:Organic siliconresin 15~ 50, thermal conducting agent 10~40, CNT 0.5~10, catalyst 0.05~1, curing agent 0.05~1, other auxiliary agents 0.1~15.
  2. A kind of 2. CNT composite heat conducting material according to claim 1, it is characterised in that:The organic siliconresin is Clear viscous liquids.
  3. A kind of 3. CNT composite heat conducting material according to claim 1, it is characterised in that:The thermal conducting agent is metal One or more in strontium, metal niobium, magnetic powder, aluminum oxide, magnesia, aluminium nitride, boron nitride and carborundum are compounded.
  4. A kind of 4. CNT composite heat conducting material according to claim 1, it is characterised in that:Described CNT is The mixture of one or both of single-walled carbon nanotube and multi-walled carbon nanotube.
  5. A kind of 5. CNT composite heat conducting material according to claim 1, it is characterised in that:The catalyst is platinum Catalyst.
  6. A kind of 6. CNT composite heat conducting material according to claim 1, it is characterised in that:The curing agent is hydrogeneous Silicone oil, hydrogen content are 0.05~1.
  7. A kind of 7. CNT composite heat conducting material according to claim 1, it is characterised in that:Other described auxiliary agents include One or more in fire retardant, coupling agent and releasing agent.
  8. A kind of 8. preparation method of CNT composite heat conducting material, it is characterised in that:Comprise the following steps:
    Step 1:Heat filling is surface-treated using coupling agent, is dispersed with stirring, makes heat filling coated with uniform one Layer coupling agent, reinforcer and the compatibility of organic siliconresin matrix;
    Step 2:Treated heat filling and organic siliconresin, CNT, fire retardant load dispersion machine and carry out mixing point 1min~60min is dissipated, forms mixture one;
    Step 3:Catalyst and curing agent are separately added into dispersion machine again, together with mixture one disperse stirring 1min~ 60min, vacuum degassing, form mixture two;
    Step 4:Mixture two is subjected to calendering production, then to the additional high-intensity magnetic field of product, to carbon nano-tube oriented orientation 30min~120min, finally by product sulfidization molding.
CN201610794639.0A 2016-08-31 2016-08-31 A kind of CNT composite heat conducting material and preparation method thereof Pending CN107778865A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108659537A (en) * 2018-04-12 2018-10-16 中科广化(重庆)新材料研究院有限公司 A kind of carbon nanotube and boron nitride collaboration enhancing organosilicon Heat Conduction Material and its preparation method and application
CN110282974A (en) * 2019-06-28 2019-09-27 华南理工大学 Oriented alignment magnetic carbon fiber graphene composite film and its preparation method and application
CN110330947A (en) * 2019-06-06 2019-10-15 东莞市盛元新材料科技有限公司 A kind of thermally conductive gel of carbon nanotubes and its preparation and application
CN113276487A (en) * 2020-02-19 2021-08-20 国家能源投资集团有限责任公司 High-thermal-conductivity composite film and preparation method thereof
CN114836037A (en) * 2022-06-07 2022-08-02 惠州东铭新能源材料股份有限公司 Silica gel foaming material with heat conduction performance and preparation method thereof

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108659537A (en) * 2018-04-12 2018-10-16 中科广化(重庆)新材料研究院有限公司 A kind of carbon nanotube and boron nitride collaboration enhancing organosilicon Heat Conduction Material and its preparation method and application
CN110330947A (en) * 2019-06-06 2019-10-15 东莞市盛元新材料科技有限公司 A kind of thermally conductive gel of carbon nanotubes and its preparation and application
CN110282974A (en) * 2019-06-28 2019-09-27 华南理工大学 Oriented alignment magnetic carbon fiber graphene composite film and its preparation method and application
CN110282974B (en) * 2019-06-28 2020-12-29 华南理工大学 Oriented magnetic carbon fiber graphene composite membrane and preparation method and application thereof
CN113276487A (en) * 2020-02-19 2021-08-20 国家能源投资集团有限责任公司 High-thermal-conductivity composite film and preparation method thereof
CN114836037A (en) * 2022-06-07 2022-08-02 惠州东铭新能源材料股份有限公司 Silica gel foaming material with heat conduction performance and preparation method thereof

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