CN106380630B - A kind of preparation method and applications of chemical bond mould assembly heat conductive insulating compounded mix - Google Patents
A kind of preparation method and applications of chemical bond mould assembly heat conductive insulating compounded mix Download PDFInfo
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Abstract
A kind of preparation method and applications of chemical bond mould assembly heat conductive insulating compounded mix, belong to heat conductive insulating compounded mix technical field.The purpose of the present invention is exactly the insulating properties in conjunction with carbon material preferable thermal conductivity and heat conduction inorganic nano-particle, and heat conduction inorganic nano-particle is loaded to carbon material surface by chemical bonding methods.The compounded mix of preparation has higher heat conductivility, but inorganic nano-particle has obstructed the conductive capability of carbon material simultaneously.Inorganic nano-particle also enhances the surface roughness of carbon material, improves its interface cohesion with polymer resin matrix.The compounded mix is mixed into fluoropolymer resin, obtained composite material has the characteristics that good heat conductivility and insulation performance under low sizing loading, can be applied to the industry field for requiring heat conduction and insulation, such as electronic package material.
Description
Technical field
Heat conduction inorganic nano-particle is modified into carbon material as the preparation of heat conductive insulating compounded mix the present invention relates to a kind of
Technology, and itself and mixed with polymers are prepared into resin base heat conductive insulating composite material, electronic package material field is can be applied to,
Belong to heat conductive insulating compounded mix technical field.
Background technology
High molecular material because its have the characteristics that it is resistant to chemical etching, it is easily molded processing, anti-fatigue performance it is excellent, it is light by
The extensive concern of people.But since high molecular material is mostly the non-conductor of heat, limit its application in terms of heat conduction.It is special
It is not in recent years, with the fast development of great-power electronic, electric product, to occur more and more since product fever causes
The problems such as product efficacy reduction, reduced service life, the requirement to electronic package material heat conductivility is also higher and higher.Thus open
Send out the novel high polymer material with Thermal conductivity, it has also become the important development direction of present Heat Conduction Material.
Heat filling common at this stage includes mainly metal packing, carbon-based material and metal oxide, nitride metal
The carbon-based materials such as object filler, wherein carbon black, carbon fiber, carbon nanotube or graphene are a kind of important heat fillings, in addition to tool
Have outside excellent heat conductivility, also tends to have the advantages that some other uniquenesses.Such as the antifriction lubrication effect of graphite, carbon fiber
High-modulus and high intensity etc., be widely used in the preparation of filled-type thermally conductive high molecular material.But since carbon-based material is logical
It often also has good conductive property, applies and limited to when material requires higher to electrical insulation capability and heat conductivility,
Such as LED encapsulation material.Therefore carbon-based Heat Conduction Material is modified, leading for material can be improved under relatively low loading
Hot and insulating properties is of great significance for the development of heat conductive insulating high molecular material.
Invention content
The invention discloses a kind of preparation method and application of chemical bond mould assembly heat conductive insulating compounded mix, the heat conductive insulatings
Filler is that heat conduction inorganic nano-particle is coated on carbon material surface by covalent bond, in conjunction with the good thermal conductivity of carbon material and is led
The hot good insulating properties of inorganic nano-particle realizes the efficient heat conductivility of compounded mix and insulation performance, is filled into resin base
The good heat conductive insulating function of composite material is assigned after body.
The present invention provides a kind of technologies of preparing of chemical bond mould assembly heat conductive insulating compounded mix.First respectively with ammonia
The coupling agent 1 of base and the coupling agent 2 with epoxy group are drawn with heat conduction inorganic nano-particle surface by reacting respectively in carbon material
Enter reactive group amino and epoxy group；Then the carbon material for introducing reactive group is mixed with heat conduction inorganic nano-particle, is utilized
The carbon-based heat conductive insulating compounded mix for reacting acquisition area load heat conduction inorganic nano-particle of amino and epoxy group；Finally by this
Kind chemical bond mould assembly heat conductive insulating compounded mix prepares the heat conductive insulating composite material haveing excellent performance with resin alloy.
Wherein, the chemical bond is the epoxy group by the amino and heat conduction inorganic nano-particle surface of carbon material surface
Group is obtained by the reaction, reaction equation such as Fig. 1.
The present invention can be by changing surface reaction time, heat conduction inorganic nano-particle mass fraction and hybrid reaction temperature
(time) controls the load factor of carbon material surface heat conduction inorganic nano-particle, and then passes through load factor and this chemical bond mould assembly
The loading of heat conductive insulating compounded mix controls the thermal conductivity and insulating properties of composite material.
The present invention provides a kind of preparation methods of chemical bond mould assembly heat conductive insulating compounded mix, as a kind of preferred modification
Means are prepared using following steps：
Step A1：Carbon material is put into acidification such as 1~8h in acid, hydroxyl is generated in carbon material surface, then uses deionization
Water washing is to neutrality, by the carbon material drying for standby after acidification；
Step A2：It is reacted with coupling agent 1 with the carbon material after acidification, amino is introduced on its surface；It is right with coupling agent 2
Heat conduction inorganic nano-particle carries out surface reaction treatment so that epoxy group on its surface grafting；Wherein the coupling agent 1 is excellent
It is selected as gamma-aminopropyl-triethoxy-silane, phenylaminomethyl trimethoxy silane or other coupling agents with amino；Described
Coupling agent 2 is preferably γ-glycidyl ether oxygen propyl trimethoxy silicane or other coupling agents with epoxy group.
Step A3：The carbon material of surface amination is mixed with the heat conduction inorganic nano-particle of surface grafting epoxy group point
It is dispersed in toluene and is chemically reacted, carry out cooling down after reaction, filter, dry, it is multiple to obtain chemical bond mould assembly heat conductive insulating
Close filler.
The wherein described carbon material can be graininess, threadiness, sheet, and appearance and size ranging from 0.001~5mm is led
The particle size range of hot inorganic nano-particle is 200~2000 mesh.
Carbon material is preferably at least one of carbon black, carbon fiber, carbon nanotube or graphene；The heat conduction inorganic nano
Particle is preferably at least one of aluminium oxide, zinc oxide, magnesia, boron nitride, silicon carbide.
Further preferably, rapid A2, when carbon material surface is functionalized, with volume ratio for 5:The mixing of 1 second alcohol and water is molten
For liquid as solvent, the mass percent concentration of coupling agent 1 is 0.1~5%, and the mass percent concentration of carbon material is 1~10%,
60~120 DEG C of 1~6h of reaction under nitrogen protection.
Further preferably, rapid A2, heat conduction inorganic nano-particle carry out surface reaction treatment when, heat conduction inorganic nano-particle with
Mass fraction is that 1~20wt% is mixed with toluene, the coupling agent 2 that mass percent concentration is 0.1~5% is added, 60~120
2~12h is reacted at DEG C, and functionalized heat conduction inorganic nano-particle is made.
Further preferably, the inorganic nano-particle of epoxy group on 2~20 mass fraction surface graftings is distributed to 50~200
In mass fraction toluene solvant, supersonic oscillations dispersion；Then the carbon material carbon material of surface amination is added；It is preferred that reaction temperature
Degree is 60~120 DEG C, and the reaction time is 2~12h, then filters, washs, the dry carbon for obtaining surface coated inorganic nano-particle
Material.
Further preferred step A3, using toluene as the reaction process of solvent in prepared carbon material surface inorganic nano-particle
Sub- grafting rate is 1%~20%.
The application of gained chemical bond mould assembly heat conductive insulating compounded mix of the invention, it is compound to be applied to polymer matrix heat conductive insulating
In material, wherein the resin matrix of the heat conductive insulating composite material is polyethylene, nylon, polystyrene, polypropylene, gathers
At least one of carbonic ester, epoxy resin or polyurethane.
Scheme compared to existing technology, innovation of the invention are as follows：
The first, the two kinds of heat fillings (carbon material and heat conduction inorganic nano material) selected in technical scheme of the present invention are
Pass through chemical bonded refractory using coupling agent infall logos to be combined together, forms stable heat conductive insulating compound system.It is this multiple
Zoarium system has carbon material and the good heat conductivility of heat conduction inorganic nano-particle, and it is good absolutely to have both inorganic nano-particle
Edge feature.
The second, in technical scheme of the present invention, it is mutual that the addition of heat conduction inorganic nano-particle can improve carbon material
Overlap joint probability, to further increase the heat conductivility of compounded mix；The excellent insulating properties of inorganic nano-particle also may be used simultaneously
To obstruct the electric conductivity of carbon material, assign this compounded mix good insulation function.
In third, technical scheme of the present invention, there is couplings on this chemical bond mould assembly heat conductive insulating compounded mix surface
Agent so that compounded mix dispersibility in resin matrix is more preferable, the polymer matrix heat conductive insulating prepared using this compounded mix
Composite material can reach good thermal conductivity under lower loading.
Description of the drawings
Fig. 1 is that the amino of carbon material surface reacts schematic diagram with the epoxy group on heat conduction inorganic nano-particle surface；
Fig. 2,1 differential responses temperature of embodiment are grafted magnesia compounded mix grafting rate figure to carbon fiber surface；
a,d-60℃；b,e-80℃；c,f-100℃；d,g-120℃.
Specific implementation mode
With reference to embodiment, the invention will be further described, but the present invention is not limited to following embodiments.
Embodiment 1：
(1) chopped carbon fiber surface modification：Carbon fiber is placed in concentrated acid first after handling 6h and is cleaned with deionized water, and
Vacuum drying；Then configuration concentration is the ethanol/water mixed solution (volume ratio 5 of 3% gamma-aminopropyl-triethoxy-silane：1),
Reflux 3h is reacted with the chopped carbon fiber of 5% concentration for 100 DEG C under nitrogen protection, is cleaned after reaction with ethyl alcohol, vacuum is dried
It is dry, obtain the chopped carbon fiber on amido modified surface.
(2) magnesia particle surface modification：The 2g magnesia particles dried are mixed with 96g toluene, in room temperature ultrasound point
Scattered 30min obtains suspension, γ-glycidyl ether oxygen propyl trimethoxy silicane of 2g is then added, and at a temperature of 60 DEG C
React 10h.It filters, wash while hot after reaction, vacuum drying, obtaining the magnesia particle of epoxy group modification.
(3) chopped carbon fiber surface grafting magnesia particle：MgO particles epoxy group modified 10g is ultrasonic in toluene
Disperse 30min, the carbon fiber of the amido modified mistakes of 2g is then added, reflux 10h postcoolings are clear with absolute ethyl alcohol to room temperature at 60 DEG C
Rear vacuum drying is washed, obtains the carbon fiber of surface grafting magnesia particle, grafting rate 12.8%, the grafting obtained under different temperatures
Rate is shown in Fig. 2.
(4) preparation of heat conductive insulating nylon 6 composite material：By the carbon fiber of the surface grafting magnesia particle of 5g steps (3)
Dimension, 94g nylon 6 resins and 1g auxiliary agents (on the processing aid of thermal coefficient, surface resistivity without influence, such as antiager) utilize
High speed mixer is blended, and heat conduction is obtained after then feeding the mixture into double screw extruder melting extrusion, pelletizing, drying, molding
The nylon 6 composite material of insulation.
Modified carbon fiber loading influences part table 1 to the thermal coefficient of nylon 6 composite material and surface resistivity.
Embodiment 2：
(1) carbon nano tube surface is modified：Carbon nanotube is placed in concentrated acid first after handling 1h and is cleaned with deionized water, and
Vacuum drying；Then configuration concentration is the ethanol/water mixed solution (volume ratio 5 of 2% gamma-aminopropyl-triethoxy-silane：1),
Reflux 1h is reacted with the carbon nanotube of 1% concentration for 120 DEG C under nitrogen protection, is cleaned after reaction with ethyl alcohol, vacuum drying,
Obtain amido modified carbon nanotube.
(2) zinc oxide particles surface modification：Room temperature ultrasonic disperse after the 4g zinc oxide particles dried are mixed with 93g toluene
30min obtains suspension, and γ-glycidyl ether oxygen propyl trimethoxy silicon of 3g is then added, and is reacted at a temperature of 100 DEG C
6h.It filters, wash while hot after reaction, vacuum drying, obtaining epoxy group modified zinc oxide particles.
(3) carbon nano tube surface is grafted zinc oxide particles：Zinc oxide particles epoxy group modified 4g are ultrasonic in toluene
Disperse 30min, the amido modified carbon nanotubes of 2g are then added, absolute ethyl alcohol is used in combination to room temperature in reflux 4h postcoolings at 100 DEG C
Cleaning, vacuum drying obtain the carbon nanotube of surface grafting zinc oxide particles, grafting rate 5.8%.
(4) preparation of heat conductive insulating PP composite material：By the carbon of the surface grafting magnesia particle of 9.5g steps (3)
15min is blended using high speed mixer in nanotube, 94g acrylic resins and 1g auxiliary agents, then feeds the mixture into twin-screw and squeezes
The PP composite material of heat conduction, insulation is obtained after going out machine melting extrusion, pelletizing, drying, molding.
Embodiment 3：
(1) graphene surface is modified：Graphene is placed in concentrated acid first after handling 0.5h and is cleaned with deionized water, and is true
Sky drying；Then configuration concentration is the ethanol/water mixed solution (volume ratio of 4% phenylaminomethyl trimethoxysilane coupling agent
5：1), reflux 5h is reacted with the graphene of 2% concentration for 80 DEG C under nitrogen protection, cleaned after reaction with ethyl alcohol, vacuum is dried
It is dry, obtain amido modified graphene.
(2) aluminium oxide particles surface modification：The 3g aluminium oxide particles dried are mixed into (rear room temperature ultrasound point with 93g toluene
Scattered 30min obtains suspension, γ-glycidyl ether oxygen propyl trimethoxy silicane of 4g is then added, and at a temperature of 90 DEG C
React 8h.It filters, wash while hot after reaction, vacuum drying, obtaining epoxy group modified aluminium oxide particles.
(3) graphene surface is grafted aluminium oxide particles：By the epoxy group modified Al of 3g2O3Particle ultrasonic disperse in toluene
Then the amido modified graphenes of 5g are added in 30min, to room temperature washes of absolute alcohol is used in combination, very in reflux 8h postcoolings at 90 DEG C
Sky drying, obtains the graphene of surface grafting aluminium oxide particles, grafting rate 3.1%.
(4) preparation of heat conductive insulating composite polyethylene material：By the surface grafting aluminium oxide particles of 16.8g steps (3)
15min is blended using high speed mixer in graphene, 94g polyvinyl resins and 1g auxiliary agents, then feeds the mixture into twin-screw and squeezes
The composite polyethylene material of heat conductive insulating is obtained after going out machine melting extrusion, pelletizing, drying, molding.
Embodiment 4：
(1) carbon blacksurface is modified：Carbon black is placed in concentrated acid first after handling 3h and is cleaned with deionized water, and vacuum is dried
Dry, then configuration concentration is the ethanol/water mixed solution (volume ratio 5 of 1% gamma-aminopropyl-triethoxy-silane：1), and by charcoal
Black 70 DEG C of reaction reflux 5h under nitrogen protection, are cleaned, vacuum drying with ethyl alcohol, obtain amido modified charcoal after reaction
It is black.
(2) boron nitride particles surface modification：Room temperature ultrasonic disperse after the 8g boron nitride particles dried are mixed with 88g toluene
30min obtains suspension, γ-glycidyl ether oxygen propyl trimethoxy silicane of 4g is then added, and anti-at a temperature of 110 DEG C
Answer 4h.It filters, wash while hot after reaction, vacuum drying, obtaining epoxy group modified boron nitride particles.
(3) carbon blacksurface is grafted boron nitride particles：By boron nitride particles epoxy group modified 12g in toluene ultrasonic disperse
30min, then addition 2g is amido modified crosses carbon black, and to room temperature washes of absolute alcohol is used in combination, very in reflux 4h postcoolings at 110 DEG C
Sky drying, obtains the carbon black of surface grafting boron nitride particles, grafting rate 15.3%.
(4) preparation of heat conductive insulating epoxy resin composite material：By the surface grafting boron nitride particles of 23.8g steps (3)
Carbon black, 94g epoxy resin and 1g auxiliary agents be uniformly mixed, and then will obtain the epoxy of heat conductive insulating after mixture solidification, molding
Resin composite materials.
Table 1,1 modified carbon fiber loading of embodiment influence the thermal coefficient of nylon 6 composite material and surface resistivity
Claims (10)
1. a kind of preparation method of chemical bond mould assembly heat conductive insulating compounded mix, which is characterized in that first respectively with amino
Coupling agent 1 and coupling agent 2 with epoxy group introduced respectively with heat conduction inorganic nano-particle surface by reacting in carbon material
Reactive group amino and epoxy group；Then the carbon material for introducing reactive group is mixed with heat conduction inorganic nano-particle, utilizes ammonia
The carbon-based heat conductive insulating compounded mix for reacting acquisition area load heat conduction inorganic nano-particle of base and epoxy group；
The wherein described coupling agent 1 be gamma-aminopropyl-triethoxy-silane, phenylaminomethyl trimethoxy silane or other carry
The coupling agent of amino；The coupling agent 2 is γ-glycidyl ether oxygen propyl trimethoxy silicane or other carry epoxy group
Coupling agent；The heat conduction inorganic nano-particle is at least one in aluminium oxide, zinc oxide, magnesia, boron nitride, silicon carbide
Kind.
2. a kind of preparation method of chemical bond mould assembly heat conductive insulating compounded mix described in accordance with the claim 1, which is characterized in that
Carbon material is graininess, threadiness or sheet, appearance and size ranging from 0.001~5mm.
3. a kind of preparation method of chemical bond mould assembly heat conductive insulating compounded mix described in accordance with the claim 1, which is characterized in that
Carbon material is at least one of carbon black, carbon fiber, carbon nanotube or graphene.
4. a kind of preparation method of chemical bond mould assembly heat conductive insulating compounded mix described in accordance with the claim 1, which is characterized in that
Specifically include following steps：
Step A1：Carbon material is put into acid and is acidified, hydroxyl is generated in carbon material surface, is then washed with deionized into
Property, by the carbon material drying for standby after acidification；
Step A2：It is reacted with coupling agent 1 with the carbon material after acidification, amino is introduced on its surface；With coupling agent 2 to heat conduction
Inorganic nano-particle carries out surface reaction treatment so that epoxy group on its surface grafting；
Step A3：The carbon material of surface amination is mixed with the heat conduction inorganic nano-particle of surface grafting epoxy group and is dispersed in
It is chemically reacted in toluene, carries out cooling down after reaction, filter, dry, obtain that chemical bond mould assembly heat conductive insulating is compound to be filled out
Material.
5. a kind of preparation method of chemical bond mould assembly heat conductive insulating compounded mix according to claim 4, which is characterized in that
Step A2, when carbon material surface is functionalized, with volume ratio for 5:The mixed solution of 1 second alcohol and water is as solvent, coupling agent 1
Mass percent concentration be 0.1~5%, the mass percent concentration of carbon material is 1~10%, under nitrogen protection 60~
120 DEG C of 1~6h of reaction.
6. a kind of preparation method of chemical bond mould assembly heat conductive insulating compounded mix according to claim 4, which is characterized in that
Step A2, heat conduction inorganic nano-particle carry out surface reaction treatment when, heat conduction inorganic nano-particle with mass fraction be 1~
20wt% is mixed with toluene, be added mass percent concentration be 0.1~5% coupling agent 2, at 60~120 DEG C react 2~
Functionalized heat conduction inorganic nano-particle is made in 12h.
7. a kind of preparation method of chemical bond mould assembly heat conductive insulating compounded mix according to claim 4, which is characterized in that
The inorganic nano-particle of epoxy group on 2~20 mass fraction surface graftings is distributed in 50~200 mass fraction toluene solvants,
Supersonic oscillations are disperseed；Then the carbon material of surface amination is added；Reaction temperature be 60~120 DEG C, the reaction time be 2~
Then 12h is filtered, is washed, the dry carbon material for obtaining surface coated inorganic nano-particle.
8. a kind of preparation method of chemical bond mould assembly heat conductive insulating compounded mix according to claim 4, which is characterized in that
Step A3, using toluene as the reaction process of solvent in prepared carbon material surface inorganic nano-particle grafting rate be 1%~
20%.
9. the chemical bond mould assembly heat conductive insulating compounded mix being prepared according to any one of claim 1-8 preparation methods.
10. the chemical bond mould assembly heat conductive insulating compounded mix being prepared according to any one of claim 1-8 preparation methods is answered
With applied in polymer matrix heat conductive insulating composite material, wherein the resin matrix of the heat conductive insulating composite material is poly-
At least one of ethylene, nylon, polystyrene, polypropylene, makrolon, epoxy resin or polyurethane.
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