CN109880297A - A kind of heat conductive insulating epoxy resin composite material and preparation method thereof - Google Patents
A kind of heat conductive insulating epoxy resin composite material and preparation method thereof Download PDFInfo
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- CN109880297A CN109880297A CN201910168203.4A CN201910168203A CN109880297A CN 109880297 A CN109880297 A CN 109880297A CN 201910168203 A CN201910168203 A CN 201910168203A CN 109880297 A CN109880297 A CN 109880297A
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Abstract
The present invention provides a kind of heat conductive insulating epoxy resin composite materials and preparation method thereof, belong to technical field of polymer composite materials, are prepared by the raw material for including following mass percentage: hexagonal boron nitride/2~20wt.% of gold nano grain compound；Modified 1~20wt.% of cubic boron nitride micro mist；30~49wt.% of epoxy resin；30~49wt.% of curing agent.The present invention is using hexagonal boron nitride/gold nano grain compound and modified cubic boron nitride micro mist as heat filling, the boron nitride filler of different sizes and shapes forms effective thermally conductive chain and thermal conductive network in the epoxy, prepared heat conductive insulating polymer composite, the thermal conductivity of epoxy resin is significantly improved, and insulating properties is good.
Description
Technical field
The present invention relates to technical field of polymer composite materials, in particular to a kind of heat conductive insulating epoxy resin composite material
And preparation method thereof.
Background technique
Hexagonal boron nitride have with layer structure as graphite-phase and lattice constant, have the title of " white graphite ", along face
Thermal conductivity be up to 300W/ (mk), be the ideal filler for preparing heat conductive insulating composite material.Layer structure is very big due to having
Specific surface area, therefore can be very good carried metal nano particle.The boron nitride nanosheet conduct of carried metal nano particle
Heat filling is more advantageous, inside resin matrix, can reduce the effective passage of heat of internal thermal resistance in the epoxy
It is formed, the heating conduction of composite material can be made to be significantly improved.Another common boron nitride is cubic boron nitride, knot
Structure is the substance that the hardness being currently known is only second to diamond similar to diamond, while having very high thermal conductivity, up to
1300W/(m·k)。
Currently, having some researchs for being used for Heat Conduction Material about hexagonal boron nitride compound silver nanometer particle, such as graphite
Alkene/thermally conductive special polymer material of boron nitride loading nano silvery and preparation method (application number: CN201710251764.1), the material
In material, silver nitrate is added in graphene and hexagonal boron nitride nanometer sheet dispersion liquid, is formed by the reduction of dimethylformamide
Graphene/hexagonal boron nitride loading nano silvery obtains graphene/hexagonal boron nitride loading nano silvery compound.The method needs
Dimethylformamide is as reducing agent, and wherein dimethylformamide is toxic and not environmentally, is not easy to operate.
Research about hexagonal boron nitride composite gold nano particles is less, wherein preparing hexagonal boron nitride-gold about a kind of
The method (application number: CN201310249937.8) of nano-complex, it is direct using hexagonal boron nitride nanometer sheet under ultrasonic radiation
Reduction gold chloride prepares hexagonal boron nitride-golden nano-complexes, but in terms of the compound does not relate to heat-conducting insulation material
Application.
Summary of the invention
In view of this, it is an object of that present invention to provide and a kind of heat conductive insulating epoxy resin composite material and its preparation side
Method, the present invention by hexagonal boron nitride/gold nano grain compound and modified cubic boron nitride micro mist with epoxy resin is compound obtains
Thermal insulation epoxy resin composite material, the thermal conductivity of the composite material is high, insulating properties is good.
To achieve the goals above, the present invention provides following technical solutions.
The present invention provides a kind of heat conductive insulating epoxy resin composite materials, are prepared by the raw material for including following percentage composition
It obtains:
Hexagonal boron nitride/2~20wt.% of gold nano grain compound；
Modified 1~20wt.% of cubic boron nitride micro mist；
30~49wt.% of epoxy resin；
30~49wt.% of curing agent.
Preferably, the hexagonal boron nitride/gold nano grain compound preparation method the following steps are included:
Hexagonal boron nitride is successively carried out to the first annealing and the first silane coupling agent surface modification treatment, is modified
Hexagonal boron nitride；The hexagonal boron nitride is hexagonal boron nitride nanometer sheet and/or hexagonal boron nitride micro mist；
The modified hexagonal boron nitride is mixed with nanogold particle solution, gained mixed liquor is dry, obtain hexagonal nitrogen
Change boron/gold nano grain compound.
Preferably, the diameter of the hexagonal boron nitride nanometer sheet is 0.5~10 μm, with a thickness of 1~100nm；The hexagonal
The diameter of boron nitride micro mist is 1~45 μm, with a thickness of 1~5 μm.
Preferably, the temperature of first annealing is 900~1100 DEG C, and the time is 1~2h.
Preferably, the partial size of nanogold particle is 1~20nm in the nano-Au solution；The quality of the nanogold particle
Concentration is 0.1~0.3%.
Preferably, the modified hexagonal boron nitride and the mass ratio of nanogold in nanogold particle solution are 50~150:1.
Preferably, the modified cubic boron nitride micro mist preparation method the following steps are included:
Cubic boron nitride micro mist is successively carried out to the second annealing and the second silane coupling agent surface modification treatment, is obtained
Modified cubic boron nitride micro mist.
Preferably, the partial size of the cubic boron nitride micro mist is 1~100 μm.
Preferably, the curing agent is 650 polyamide curing agents, and the amine value of the curing agent is 180~200mgKOH/g.
The present invention also provides the preparation methods of above-mentioned heat conductive insulating epoxy resin composite material, comprising the following steps:
By the epoxy resin, hexagonal boron nitride/gold nano grain compound, modified cubic boron nitride micro mist and curing agent
Vacuum defoamation, precuring and solidification are successively carried out after mixing, obtain heat conductive insulating epoxy resin composite material.
Advantageous effects: the present invention provides a kind of heat conductive insulating epoxy resin composite material and preparation method thereof, by
Raw material including following percentage composition is prepared: hexagonal boron nitride/2~20wt.% of gold nano grain compound；Modified cube
1~20wt.% of boron nitride micro mist；30~49wt.% of epoxy resin；30~49wt.% of curing agent.The present invention nitrogenizes hexagonal
As heat filling, the boron nitride filler of different sizes and shapes exists for boron/gold nano grain compound and cubic boron nitride micro mist
Effective thermally conductive chain is formed in epoxy resin and thermal conductive network, prepared heat conductive insulating polymer composite significantly improve
The thermal conductivity of epoxy resin, and insulating properties is good.Embodiment experimental data shows that its thermal conductivity is 0.66W/ (mk), insulating properties
It can be good.
Detailed description of the invention
Fig. 1 is that hexagonal boron nitride/gold nano grain compound transmission electron microscope (TEM) figure and original hexagonal nitrogenize
The photo of boron powder, hexagonal boron nitride and gold nano grain solution mixture；
Fig. 2 is hexagonal boron nitride/gold nano grain compound high resolution transmission electron microscope (HRTEM) figure；
Fig. 3 is section scanning electron microscope (SEM) figure that sample is prepared in embodiment 2.
Specific embodiment
The present invention provides a kind of heat conductive insulating epoxy resin composite materials, are prepared by the raw material for including following percentage composition
It obtains:
Hexagonal boron nitride/2~20wt.% of gold nano grain compound；
Modified 1~20wt.% of cubic boron nitride micro mist；
30~49wt.% of epoxy resin；
30~49wt.% of curing agent.
In terms of mass percentage, the raw material of heat conductive insulating epoxy resin composite material of the present invention includes hexagonal nitridation
Boron/gold nano grain compound 2~20%, preferably 5~15%.
In the present invention, the hexagonal boron nitride/gold nano grain compound preparation method preferably includes following steps:
Hexagonal boron nitride is successively carried out to the first annealing and the first silane coupling agent surface modification treatment, is modified
Hexagonal boron nitride；The hexagonal boron nitride is hexagonal boron nitride nanometer sheet and/or hexagonal boron nitride micro mist；
The modified hexagonal boron nitride is mixed with nanogold particle solution, gained mixed liquor is dry, obtain hexagonal nitrogen
Change boron/gold nano grain compound.
Hexagonal boron nitride is successively carried out to the first annealing and the first silane coupling agent surface modification treatment, is modified
Hexagonal boron nitride；The hexagonal boron nitride is hexagonal boron nitride nanometer sheet and/or hexagonal boron nitride micro mist；
In the present invention, the diameter of the hexagonal boron nitride nanometer sheet be preferably 0.5~10 μm, more preferably 1~8 μm,
Most preferably 5 μm；The thickness of the hexagonal boron nitride nanometer sheet is preferably 1~100nm, more preferably 10~80nm, most preferably
For 30~50nm；The diameter of the hexagonal boron nitride micro mist is preferably 1~45 μm, and more preferably 5~40 μm, most preferably 10~
30μm；The thickness of the hexagonal boron nitride micro mist is preferably 1~5 μm.In the present invention, when the hexagonal boron nitride is hexagonal nitrogen
When the mixture of change boron nanometer sheet and hexagonal boron nitride micro mist, the present invention is to hexagonal boron nitride nanometer sheet and hexagonal boron nitride micro mist
Amount ratio be not particularly limited, mixed with arbitrary proportion.
The present invention is not particularly limited the source of hexagonal boron nitride nanometer sheet and hexagonal boron nitride micro mist, selects this field
Preparation method known to technical staff is prepared.As chemical stripping method, adhesive tape stripping method, ball-milling method, plasma are carved
Erosion method or fluid stripping method.
In the present invention, the hexagonal boron nitride nanometer sheet and hexagonal boron nitride micro mist are as heat filling, partial size phase
To larger, different sizes and heat filling of different shapes are added in heat conduction substrate, thermal conductive network easy to form, are improved thermally conductive
Performance.
In the present invention, the temperature of first annealing is preferably 900~1100 DEG C, and more preferably 1000 DEG C；Institute
The time for stating the first annealing is preferably 1~3h, more preferably 2h.Specifically, the present invention heats the hexagonal boron nitride
It is cooling after keeping the temperature the time for reaching the first annealing to the first annealing temperature.The present invention does not have heating and cooling rate
Particular determination selects heating well known to those skilled in the art and cooling rate.In the present invention, first annealing
Processing preferably carries out in air, and the present invention is effectively repaired by carrying out the first annealing in air in nitridation boron surface
Adorn hydroxyl, be conducive to it is subsequent reacted with silane coupling agent, further chained including silane coupling agent etc. on the surface of boron nitride
Other each organic molecular species chains.In the present invention, the specific steps of the first silane coupling agent surface modification treatment are preferred are as follows:
Silane coupling agent, ethyl alcohol and hydromagnetic power are stirred, silane coupling agent hydrolyzate is obtained；By the silane coupling agent hydrolyzate
It is stirred with gained hexagonal boron nitride after annealing, gained mixed liquor is successively filtered, washed and dried, is changed
Property hexagonal boron nitride.
In the present invention, the silane coupling agent is preferably KH-550；The mass ratio of the silane coupling agent, second alcohol and water
Preferably 1:130~150:10~20, more preferably 1:135~145:15~17；The time of the magnetic agitation is preferably 10
~30min, more preferably 15~25min.The stirring rate that the present invention mixes the magnetic agitation is not particularly limited, and is selected
Stirring rate well known to those skilled in the art.In the present invention, the quality of the hexagonal boron nitride and silane coupling agent
Than being preferably 15~25:1, more preferably 20:1；In the present invention, the temperature being stirred is preferably 20~80 DEG C, more
Preferably 25~50 DEG C；The time being stirred is preferably 1~2h, more preferably 1.5h.The present invention is to being stirred
Stirring rate is not particularly limited, and selects stirring rate well known to those skilled in the art.In the present invention, the filtering
Preferably filter.The present invention is not particularly limited the method for suction filtration, selects suction filtration method well known to those skilled in the art i.e.
It can.In the present invention, the detergent of the washing is preferably ethyl alcohol.The present invention is not particularly limited the method for washing, selects
Washing methods well known to those skilled in the art.The present invention removes extra silane coupling agent by washing.In the present invention
In, the drying is preferably dried in vacuo, and the vacuum drying temperature is preferably 100~110 DEG C, when described vacuum drying
Between preferably 10~12h.The present invention is not particularly limited vacuum drying vacuum degree, selects well known to those skilled in the art
Vacuum degree.The present invention is made to nitrogenize boron surface in conjunction with coupling agent, is greatly improved by the first coupling agent surface modification treatment
Its hydrophily combines filler well with matrix so as to improve the dispersibility and cohesive force of filler in the base, improves compound
The mechanical performance and thermal property of material.
After obtaining modified hexagonal boron nitride, the present invention mixes the modified hexagonal boron nitride with nanogold particle solution,
Gained mixed liquor is dry, obtain hexagonal boron nitride/gold nano grain compound.
In the present invention, the partial size of nanogold particle is preferably 1~20nm in the nano-Au solution, more preferably 5~
15nm；The mass concentration of the nanogold particle is preferably 0.1%~0.3%, and more preferably 0.15%~0.25%；It is described to receive
Solvent in rice gold solution is preferably toluene.In the present invention, it is received in the modified hexagonal boron nitride and nanogold particle solution
The mass ratio of meter Jin is preferably 50~150:1, more preferably 60~100:1.
In terms of mass percentage, the raw material of heat conductive insulating epoxy resin composite material of the present invention includes a cube nitridation
Boron micro mist 1~2%, more preferably 5~15%, most preferably 10%.
In the present invention, the preparation method of the modified cubic boron nitride micro mist preferably includes following steps
Cubic boron nitride micro mist is successively carried out to the second annealing and the second silane coupling agent surface modification treatment, is obtained
Modified cubic boron nitride micro mist.
In the present invention, the partial size of the cubic boron nitride micro mist is preferably 1~100 μm, and more preferably 10~80 μm, most
Preferably 30~50 μm.The present invention is not particularly limited a cube source for nitridation micro mist, selects those skilled in the art known
Preparation method be prepared.Such as high temperature and high pressure synthesis or hydrothermal synthesis method.
In the present invention, the temperature of second annealing is preferably 500~1000 DEG C, and more preferably 750 DEG C；It is described
The time of second annealing is preferably 1~2h, more preferably 1.5h.Specifically, the present invention heats cubic boron nitride micro mist
It is cooling after keeping the temperature the time for reaching the second annealing to the second annealing temperature.The present invention does not have heating and cooling rate
Particular determination selects heating well known to those skilled in the art and cooling rate.In the present invention, second annealing
Processing is similar with the effect of the first annealing, and details are not described herein.
In the present invention, the specific steps of the second silane coupling agent surface modification treatment are preferred are as follows: will be silane coupled
Agent, ethyl alcohol and hydromagnetic power are stirred, and obtain silane coupling agent hydrolyzate；After the silane coupling agent hydrolyzate and fire processing
Gained cubic boron nitride micro mist is stirred, and gained mixed liquor is successively filtered, washs and is dried, and obtains modified cube nitrogen
Change boron micro mist.
In the present invention, the silane coupling agent is preferably KH-550；The mass ratio of the silane coupling agent, second alcohol and water
Preferably 1:130~150:10~20, more preferably 1:135~145:15~17；The time of the magnetic agitation is preferably 10
~50min, more preferably 25~35min.The stirring rate that the present invention mixes the magnetic agitation is not particularly limited, and is selected
Stirring rate well known to those skilled in the art.In the present invention, the cubic boron nitride micro mist and silane coupling agent
Mass ratio is preferably 15~25:1, more preferably 20:1；In the present invention, the temperature being stirred is preferably 20~80
DEG C, more preferably 30~70 DEG C；The time being stirred is preferably 1~2h, more preferably 1.5h.The present invention is mixed to stirring
The stirring rate of conjunction is not particularly limited, and selects stirring rate well known to those skilled in the art.In the present invention, described
Filtering preferably filters.The present invention is not particularly limited the method for suction filtration, selects suction filtration side well known to those skilled in the art
Method.In the present invention, the detergent of the washing is preferably ethyl alcohol.The present invention is not particularly limited the method for washing,
Select washing methods well known to those skilled in the art.The present invention removes extra silane coupling agent by washing.At this
In invention, the drying is preferably dried in vacuo, and the vacuum drying temperature is preferably 100~110 DEG C, the vacuum drying
Time be preferably 10~12h.The present invention is not particularly limited vacuum drying vacuum degree, selects those skilled in the art ripe
The vacuum degree known.In the present invention, the effect of the second silane coupling agent surface modification treatment and first silane coupled
The effect of agent surface modification treatment is identical, and details are not described herein.
In terms of mass percentage, the raw material of heat conductive insulating epoxy resin composite material of the present invention includes epoxy resin
30~49%, more preferably 35~45%, most preferably 40%.
In the present invention, the epoxy resin is preferably E-44 bisphenol A type epoxy resin；The epoxy of the epoxy resin is worked as
Value is preferably 0.41~0.48mol/100g.
In terms of mass percentage, the raw material of heat conductive insulating epoxy resin composite material of the present invention includes curing agent 30
~49%, more preferably 35~45%, most preferably 40%.
In the present invention, the curing agent is preferably 650 polyamide curing agents；The amine value of the curing agent is preferably 180
~200mgKOH/g, more preferably 185~190mgKOH/g.
The present invention also provides the preparation methods of above-mentioned heat conductive insulating epoxy resin composite material, comprising the following steps:
By the epoxy resin, hexagonal boron nitride/gold nano grain compound, modified cubic boron nitride micro mist and curing agent
Vacuum defoamation, precuring and solidification are successively carried out after mixing, obtain heat conductive insulating epoxy resin composite material.
In the present invention, the epoxy resin is added preferably in the form of epoxy resin ethanol solution.In the present invention, institute
Stating the amount ratio of epoxy resin and ethyl alcohol in epoxy resin ethanol solution is preferably 10g:6mL.In the present invention, the mixing side
Method is specially that epoxy resin ethanol solution and hexagonal boron nitride/gold nano grain compound are carried out ultrasonic mixing, obtains ultrasound
Mixed liquor；The ultrasonic mixing liquid is mixed with curing agent again.In the present invention, the ultrasonic time of the ultrasonic mixing be 10~
30min, more preferably 15~20min.The present invention is not particularly limited the frequency of the ultrasound, selects those skilled in the art
Well known frequency.
In the present invention, the time of the vacuum defoamation is preferably 10~40min, more preferably 20~30min.The present invention
The other parameters of vacuum defoamation are not particularly limited, parameter well known to those skilled in the art is selected.
In the present invention, the temperature of the precuring is preferably 20~30 DEG C, and more preferably 25 DEG C.
In the present invention, the cured temperature is preferably 90~100 DEG C, and more preferably 80 DEG C；The cured time
Preferably 1~4h, more preferably 2~3h.
It in the present invention, further preferably include being cooled to room temperature after the solidification.The present invention is not special to cooling rate
It limits, selects cooling rate well known to those skilled in the art.Such as natural cooling.
For a better understanding of the present invention, below with reference to the embodiment content that the present invention is furture elucidated, but it is of the invention
Content is not limited solely to the following examples.
Embodiment 1
The preparation of hexagonal boron nitride/gold nano grain compound:
Weighing diameter is about 5 μm, thickness is about 50nm hexagonal boron nitride nanometer sheet powder 0.75g, is heated at 1000 DEG C
2h；Obtain-alkane coupling agent hydrating solution；Hexagonal boron nitride nanometer sheet powder after annealing is added above-mentioned silane coupled
In agent hydrating solution, 2h is stirred at 60 DEG C, is filtered, and washes of absolute alcohol washes away extra silane coupling agent, 100 DEG C of vacuum
Dry 12h obtains modified hexagonal boron nitride nanometer sheet；
1) it by modified hexagonal boron nitride nanometer sheet obtained in step 1), is added in 3.75mL gold nano grain solution,
Wherein gold nano grain size is 9nm, and concentration 0.2% is slowly stirred for 24 hours, and then 100 DEG C of heat drying 12h, obtain hexagonal
Boron nitride/gold nano grain compound.
Gained hexagonal boron nitride/gold nano grain compound transmission electron microscope (TEM) figure and the nitridation of original hexagonal
The photo of boron powder, hexagonal boron nitride and gold nano grain solution mixture, wherein left figure is the nitridation of original hexagonal in the upper right corner
Boron powder, right figure are hexagonal boron nitride and gold nano grain solution mixture, and as shown in Figure 1, gold nano grain is attached to nitridation
The edge of boron nanometer sheet (in Fig. 1 shown in circle)；Fig. 2 is that hexagonal boron nitride/gold nano grain compound high-resolution is saturating
Electron microscope (HRTEM) figure is penetrated, the lattice fringe of gold nano grain, interplanar distance are 0.21nm as shown in Figure 2, corresponding
(111) crystal face.
The preparation of modified cubic boron nitride micro mist:
The cubic boron nitride micro mist that 2.25g partial size is about 44 μm is weighed, then 750 DEG C of heating 1h；Obtained sample is abundant
Grinding is stand-by；0.15g silane resin acceptor kh-550,21.6g dehydrated alcohol and 2.4g aqueous solution are mixed, silane coupling agent is obtained
Hydrating solution；Cubic boron nitride nanometer sheet powder after annealing is added in above-mentioned silane coupling agent hydrating solution, 60
2h is stirred at DEG C, is filtered, washes of absolute alcohol, extra silane coupling agent is washed away, and 100 DEG C of vacuum drying 12h obtain modified six
Angle boron nitride nanosheet.
The preparation of heat conductive insulating epoxy resin composite material: dehydrated alcohol 3ml being added into 5g epoxy resin, is uniformly mixed
Afterwards, obtain epoxy resin ethanol solution, by 0.75g hexagonal boron nitride nanometer sheet/gold nano grain compound obtained above,
2.25g modified cubic boron nitride micro mist obtained above is added in epoxy resin ethanol solution, is ultrasonically treated 30min；It weighs
650 polyamide curing agent of 5g is added in the mixture of boron nitride and epoxy resin, is uniformly mixed, then vacuum defoamation 30min,
It pours into mold, first 20 DEG C of precuring 3h, then 80 DEG C of 4h that are heating and curing, cooled to room temperature finally demould, and obtain thermally conductive
Insulating epoxy composite material, thermal conductivity are 0.35W/ (mk), compare no added epoxy resin and improve 81.2%.From
0v starts to apply voltage to sample, is pressurized to 220V always, measures almost nil by the electric current of sample, prepared is thermally conductive multiple
Condensation material insulating properties is good.
Embodiment 2:
The preparation of hexagonal boron nitride/gold nano grain compound:
1) weighing diameter is about 5 μm, thickness is about 50nm hexagonal boron nitride nanometer sheet powder 1g, is heated at 1000 DEG C
1h；Obtained sample is fully ground for use；By 0.067g silane resin acceptor kh-550,9.65g dehydrated alcohol and 1.07g aqueous solution
Mixing, obtains silane coupling agent hydrating solution；It is even that above-mentioned silane is added in hexagonal boron nitride nanometer sheet powder after annealing
Join in agent hydrating solution, 2h is stirred at 70 DEG C, filter, washes of absolute alcohol, wash away extra silane coupling agent, 110 DEG C true
The dry 10h of sky, obtains modified hexagonal boron nitride nanometer sheet；
2) it by modified hexagonal boron nitride nanometer sheet obtained in step 1), is added in 5mL gold nano grain solution, wherein
Gold nano grain size is 20nm, and concentration 0.18% is slowly stirred 20h, and then 110 DEG C of heat drying 10h, obtain hexagonal nitrogen
Change boron/gold nano grain compound.
The preparation of modified cubic boron nitride micro mist:
The cubic boron nitride micro mist that 1g partial size is about 44 μm is weighed, then 750 DEG C of heating 1h；Obtained sample is fully ground
For use；0.067g silane resin acceptor kh-550,9.65 dehydrated alcohols and 1.07 aqueous solutions are mixed, silane coupling agent hydrolysis is obtained
Solution；Cubic boron nitride nanometer sheet powder after annealing is added in above-mentioned silane coupling agent hydrating solution, at 70 DEG C
2h is stirred, is filtered, washes of absolute alcohol, extra silane coupling agent is washed away, 110 DEG C of vacuum drying 10h obtain modified hexagonal nitrogen
Change boron nanometer sheet.
The preparation of heat conductive insulating epoxy resin composite material: dehydrated alcohol 3ml being added into 5g epoxy resin, is uniformly mixed
Afterwards, the ethanol solution for obtaining epoxy resin, by 1g hexagonal boron nitride nanometer sheet/gold nano grain composite material obtained above with
1g cubic boron nitride micro mist obtained above is added in the ethanol solution of epoxy resin, is ultrasonically treated 20min；Weigh 5g 650
Polyamide curing agent is added in the mixture of boron nitride and epoxy resin, is uniformly mixed, then vacuum defoamation 30min, pours into mould
In tool, the first precuring 3h at 30 DEG C, then 100 DEG C of solidification 3h, cooled to room temperature are finally demoulded, and obtain gold nano
Grain/boron nitride heat-conducting insulation material.Its thermal conductivity be 0.66W/ (mk), compare no added epoxy resin improve 237%. from
0v starts to apply voltage to sample, is pressurized to 220v always, measures almost nil by the electric current of sample, prepared is thermally conductive multiple
Condensation material insulating properties is good.Section scanning electron microscope (SEM) figure of gained heat conductive insulating composite material as shown in figure 3, by
Known to Fig. 3 in gold nano grain/boron nitride heat-conducting insulation material, filler is close with substrate contact, is conducive to the transmitting of heat.
Embodiment 3:
The preparation of hexagonal boron nitride/gold nano grain compound:
1) weighing diameter is about 8 μm, thickness is about 50nm hexagonal boron nitride nanometer sheet powder 0.5g, at 1000 DEG C plus
Hot 1h；Obtained sample is fully ground for use；By 0.033g silane resin acceptor kh-550,4.75g dehydrated alcohol and 0.528g water
Solution mixing, obtains silane coupling agent hydrating solution；Above-mentioned silicon is added in hexagonal boron nitride nanometer sheet powder after annealing
In alkane coupling agent hydrating solution, 2h is stirred at 70 DEG C, is filtered, washes of absolute alcohol washes away extra silane coupling agent, and 110
DEG C vacuum drying 12h, obtains modified hexagonal boron nitride nanometer sheet；
2) it by modified hexagonal boron nitride nanometer sheet obtained in step 1), is added in 2.5mL gold nano grain solution,
Middle gold nano grain size is 20nm, and concentration 0.25% is slowly stirred 20h, and then 110 DEG C of heat drying 12h, obtain hexagonal
Boron nitride/gold nano grain compound.
The preparation of modified cubic boron nitride micro mist:
The cubic boron nitride micro mist that 1.5g partial size is about 100 μm is weighed, then 1000 DEG C of heating 1h；Obtained sample is abundant
Grinding is stand-by；0.1g silane resin acceptor kh-550,14.4g dehydrated alcohol and 1.6g aqueous solution are mixed, silane coupling agent is obtained
Hydrating solution；Cubic boron nitride nanometer sheet powder after annealing is added in above-mentioned silane coupling agent hydrating solution, 30
3h is stirred at DEG C, is filtered, washes of absolute alcohol, extra silane coupling agent is washed away, and 100 DEG C of vacuum drying 12h obtain modified six
Angle boron nitride nanosheet.
The preparation of heat conductive insulating epoxy resin composite material: dehydrated alcohol 3ml being added into 3g epoxy resin, is uniformly mixed
Afterwards, the ethanol solution for obtaining epoxy resin, by 0.5g hexagonal boron nitride nanometer sheet/gold nano grain composite material obtained above
It is added in the ethanol solution of epoxy resin with 1.5g cubic boron nitride micro mist obtained above, is ultrasonically treated 35min；Weigh 3g
650 polyamide curing agents are added in the mixture of boron nitride and epoxy resin, are uniformly mixed, then vacuum defoamation 30min,
Enter in mold, first the precuring 3h at 30 DEG C, then 80 DEG C of solidification 3h, cooled to room temperature finally demould, and obtain gold nano
Particle/boron nitride heat-conducting insulation material.Its thermal conductivity is 0.55W/ (mk), compares no added epoxy resin and improves 182%.
Voltage is applied to the sample, it is measured almost nil by electric current in the range of 0~220v, it was demonstrated that prepared is thermally conductive compound
Insulation resistance is good.
The present invention is simple and environmentally-friendly about the preparation method of heat conductive insulating epoxy resin composite material, convenient for operation, by hexagonal
Boron nitride/gold nano grain compound and modified cubic boron nitride micro mist are as heat filling, the nitridation of different sizes and shapes
Boron heat filling forms thermal conduction path in the epoxy, and wherein gold nano grain is nitrogenized in cubic boron nitride micro mist and hexagonal
Heat conducting bridge beam action has been played between boron, has effectively reduced internal thermal resistance, further improves the thermal conductivity of composite material, and
The heat-conductive composite material insulating properties of preparation is good.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of heat conductive insulating epoxy resin composite material, which is characterized in that be prepared by the raw material for including following percentage composition
It arrives:
Hexagonal boron nitride/2~20wt.% of gold nano grain compound；
Modified 1~20wt.% of cubic boron nitride micro mist；
30~49wt.% of epoxy resin；
30~49wt.% of curing agent.
2. heat conductive insulating epoxy resin composite material according to claim 1, which is characterized in that the hexagonal boron nitride/
The preparation method of gold nano grain compound the following steps are included:
Hexagonal boron nitride is successively carried out to the first annealing and the first silane coupling agent surface modification treatment, obtains modified hexagonal
Boron nitride；The hexagonal boron nitride is hexagonal boron nitride nanometer sheet and/or hexagonal boron nitride micro mist；
The modified hexagonal boron nitride is mixed with nanogold particle solution, gained mixed liquor is dry, obtain hexagonal boron nitride/
Gold nano grain compound.
3. heat conductive insulating epoxy resin composite material according to claim 2, which is characterized in that the hexagonal boron nitride is received
The diameter of rice piece is 0.5~10 μm, with a thickness of 1~100nm；The diameter of the hexagonal boron nitride micro mist is 1~45 μm, with a thickness of
1~5 μm.
4. heat conductive insulating epoxy resin composite material according to claim 2, which is characterized in that first annealing
Temperature be 900~1100 DEG C, the time be 1~2h.
5. heat conductive insulating epoxy resin composite material according to claim 2, which is characterized in that in the nano-Au solution
The partial size of nanogold particle is 1~20nm；The mass concentration of the nanogold particle is 0.1~0.3%.
6. heat conductive insulating epoxy resin composite material according to claim 2, which is characterized in that the modified hexagonal nitridation
The mass ratio of nanogold is 50~150:1 in boron and nanogold particle solution.
7. heat conductive insulating epoxy resin composite material according to claim 1, which is characterized in that the modification cube nitridation
The preparation method of boron micro mist the following steps are included:
Cubic boron nitride micro mist is successively carried out to the second annealing and the second silane coupling agent surface modification treatment, is modified
Cubic boron nitride micro mist.
8. heat conductive insulating epoxy resin composite material according to claim 7, which is characterized in that the cubic boron nitride is micro-
The partial size of powder is 1~100 μm.
9. heat conductive insulating epoxy resin composite material according to claim 1, which is characterized in that the curing agent is 650
Polyamide curing agent, the amine value of the curing agent are 180~200mgKOH/g.
10. the preparation method of heat conductive insulating epoxy resin composite material according to any one of claims 1 to 9, which is characterized in that
The following steps are included:
The epoxy resin, hexagonal boron nitride/gold nano grain compound, modified cubic boron nitride micro mist and curing agent are mixed
Vacuum defoamation, precuring and solidification are successively carried out afterwards, obtain heat conductive insulating epoxy resin composite material.
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