CN109294236A - A kind of preparation method of the graphene-based heat conductive silica gel of high dispersive - Google Patents
A kind of preparation method of the graphene-based heat conductive silica gel of high dispersive Download PDFInfo
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Abstract
The present invention relates to a kind of preparation methods of the graphene-based heat conductive silica gel of high dispersive, comprising: (1) is added to the water graphite oxide, ultrasound removing forms graphene oxide aqueous suspensions；Aluminium salt is added in the graphene oxide aqueous suspensions, ultrasonic disperse, forms solution A；Precipitant solution is prepared, and dispersing agent is added, forms B solution；The solution A is mixed with B solution, is stirred, is obtained gray precipitate, then the gray precipitate is filtered, clean, dry, is calcined, obtain graphene/Al2O3Compounded mix；(2) coupling agent solution is prepared, the graphene/Al is added2O3Then compounded mix is stirred, filters, cleans, dries, obtain graphene/Al of coupling agent modification2O3Compounded mix；(3) graphene/Al for modifying the coupling agent2O3Compounded mix is mixed with silicone rubber matrix and auxiliary agent, is then vulcanized, and the graphene-based heat conductive silica gel of high dispersive is obtained.It can be improved dispersibility of the graphene as heat filling through the invention, improve its heating conduction.
Description
Technical field
The present invention relates to Heat Conduction Material field more particularly to a kind of preparation methods of the graphene-based heat conductive silica gel of high dispersive.
Background technique
As semiconductor, electronic component constantly develop toward micromation, lightness and efficient direction, hot puzzlement problem adds
Play, there is an urgent need to good cooling measures to solve.Heat conductive silica gel is as the elastic material between a kind of filling heat source and radiator
Material has expulsion air and accelerates the important function of heat dissipation, good heat dissipation, damping, chemical corrosion resistance and wider makes
With temperature (- 90~250 DEG C), elasticity and stability in use can be kept in the limit and harsh environment, be very suitable to LED illumination,
The elastic adhesive in the fields such as electromagnetic shielding, electronic information, communication apparatus, aerospace, automobile and household electrical appliance, positioning, heat dissipation,
Insulation and sealing use.
Heat conductive silica gel usually requires to be filled into polysiloxanes macromolecule matrix using the good filler of thermal conductivity, is formed equal
The system of even dispersion, to obtain high-termal conductivity, common filler is metal, metal oxide and nitride etc., and these are traditional
The thermal conductivity of filler has been unable to meet the requirement of present market opposite heat tube reason material, and excessive loading also will affect the machine of silica gel
Tool performance.
Graphene has single layer sp as a kind of novel heat-conducting filler2The carbon atom of hydridization accumulates the bi-dimensional cellular to be formed
Shape structure, thickness in monolayer are only 0.335nm, and specific surface area is up to 2630m2·g-1, it is most thin and most hard in the world receive
Rice material, has many advantages, such as carrier mobility, excellent thermal conductivity, high-specific surface area and the high-flexibility of superelevation, graphene
2.3% light is only absorbed, single-layer graphene thermal conductivity is up to 5300W/ (mK), therefore is filled into silica gel matrix using graphene
In, high conductivity material can be prepared, heating conduction is far superior to other fillers, has broad application prospects.
But graphene-based heat conductive silica gel problems faced is at present: 1, graphene is easy to reunite, in filling matrix
The formation that portion can influence thermal conducting path because of reuniting causes its with higher this is because graphene specific surface area is larger
Surface energy, winding and reunion are easy to happen in dispersion process, is difficult to form uniform dispersion, graphene with other materials
The number of plies is fewer, and heating conduction is better, therefore the dispersion problem of graphene in the base seriously affects graphene-based thermal conductive silicon
The heating conduction of glue.2, heat conductive silica gel is individually filled using graphene, it is interior there are certain gap between filler and basal body interface
During portion's heat transmission, interface interaction causes interface resistance, directly affects the thermal conductivity of system.3, unlike material, different rulers
Very little, the heat filling of different dimensions mutually mixes, and by the heat filling that the synergistic effect between heat filling is prepared, is conducive to
The thermal conductivity of heat conductive silica gel is promoted, but existing research can not play the association between graphene and other heat fillings completely
Same mechanism.4, in the aluminium oxide of different-shape, ball-aluminium oxide has optimal thermally conductive as heat conductive silica gel prepared by filler
Performance, the preparation method of ball-aluminium oxide are mainly had sol-gal process, drop ball, template etc., are prepared using sol-gal process
Ball-aluminium oxide, particle size range is wider, and spherical rate is high, and preferably, but it is serious to reunite after being sintered for dispersibility；Dripping ball is to molten
Glue-emulsion-gel method is in technologic further improvement, and the aluminium oxide purity is high of preparation, dispersibility is best, but size range
Narrow, usual partial size is larger；Template is suitable for preparing hollow ball, and to the more demanding of template, preparation process step is more,
Higher cost.
Summary of the invention
Based on this, the object of the present invention is to provide a kind of preparation methods of the graphene-based heat conductive silica gel of high dispersive, can
Dispersibility of the graphene as heat filling is improved, its heating conduction is improved.
The purpose of the present invention is what is be achieved through the following technical solutions: a kind of preparation of the graphene-based heat conductive silica gel of high dispersive
Method, comprising the following steps:
S1: graphite oxide is added to the water, and ultrasound removing forms graphene oxide aqueous suspensions；The oxidation is added in aluminium salt
In graphene aqueous suspensions, ultrasonic disperse forms solution A；Precipitant solution is prepared, and dispersing agent is added, forms B solution；By institute
It states solution A to mix with B solution, stirs, obtain gray precipitate, then the gray precipitate is filtered, clean, dry, is forged
It burns, obtains graphene/Al2O3Compounded mix；
S2: coupling agent solution is prepared, the graphene/Al is added2O3Compounded mix, be then stirred, filter, cleaning,
Drying obtains graphene/Al of coupling agent modification2O3Compounded mix；
S3: graphene/Al that the coupling agent is modified2O3Compounded mix is mixed with silicone rubber matrix and auxiliary agent, then sulphur
Change, obtains the graphene-based heat conductive silica gel of high dispersive.
Compared with the existing technology, beneficial effects of the present invention are as follows:
1, the present invention is using the preferable graphene oxide of dispersibility as raw material, surface oxygen-containing function rich in
,-OH and C-O-C is contained in plane, and contain C=O and-COOH at its lamella edge, there is good wellability and surface
Activity utilizes the active function groups of graphene oxide, fabricated in situ graphene oxide/Al2O3Compound, also by high temperature sintering
Original place reason, obtains the graphene-based material of favorable dispersibility, can effectively avoid graphene from asking as the dispersibility of heat filling
Topic, plays its heating conduction.Principle therein is as follows: surface of graphene oxide is negatively charged due to containing-OH abundant and-COOH,
With positively charged Al3+With the combination of stronger ionic bond, make Al3+Uniform load is in surface of graphene oxide；After precipitating reagent is added,
Al3+Make Al with coordinate bond active force2O3It is deposited on surface of graphene oxide；By high-temperature calcination, graphene oxide is reduced shape
At graphene, with Al2O3Between combined with electrostatic force, form the combination product with good dispersion and thermal conductivity.
2, graphene/Al obtained through the invention2O3In compounded mix, graphene is in Al2O3Bridging is formed between particle
Structure forms graphene/Al2O3The close-packed structure of compounded mix in a polymer matrix, can promote to form thermally conductive network chain
Structure reduces interface resistance, to improve the thermal conductivity of heat conductive silica gel.
3, graphene/Al obtained through the invention2O3In compounded mix, Al2O3Uniformly adhere on the surface of graphene, no
The heating conduction that can only utilize graphene excellent, improves Al2O3The defect not high as single filler thermal conductivity, while can
The Al utilized2O3Electrical insulating property prevents composite material from reaching electroosmotic flow threshold value, obtains preferable synergistic effect.
4, the present invention prepares ball-aluminium oxide powder using sluggish precipitation, low, simple process, operation with cost of material
Advantage easy, low for equipment requirements.
Further, in step S1, the graphene/Al2O3In compounded mix, graphene and Al2O3Mass ratio be 1:
(10~40).If the content of graphene is excessive, it is difficult to ensure the dispersibility of graphene in complex conductive fillers, if cannot protect
The dispersibility for demonstrate,proving graphene, the heat conductive silica gel that will lead to preparation form gap, substantially reduce thermal conductivity；And if the content of graphene
Excessively, then it is difficult to ensure the insulating properties of complex conductive fillers, because graphene has good electric conductivity, content is excessive, meeting
Reduce insulating properties；If graphene content is very few, it is difficult to improve the thermal conductivity of heat conductive silica gel.Graphene and Al2O3Best in quality
Than for 1:30.
Further, in step S1, the ratio of the concentration of precipitating reagent and the concentration of aluminium salt in the solution A in the B solution
For (2~6): 1.If the amount of precipitating reagent is excessive, easily there is insoluble phenomenon；If the amount of precipitating reagent is very few, be difficult to ensure aluminium from
Sub precipitating completely, it is possible to create other impurities.The precipitating reagent is preferably ammonium hydrogen carbonate, ammonium carbonate, urea or six methines four
Amine.The aluminium salt is preferably aluminum sulfate, alum or 12 hydrazine aluminum sulfate potassium.
Further, in step S1, in solution A and B solution mixed process, it is 5~9 that aqueous slkali control pH, which is added,
30~50h is stirred at 70~110 DEG C.The aqueous slkali is preferably ammonium hydroxide, sodium hydroxide solution or sodium carbonate liquor.
Further, in step S1, the calcination process are as follows: be first placed in 300~500 DEG C of 3~8h of pre-burning in argon atmosphere；
900~1500 DEG C of 2~5h of calcining in argon atmosphere are placed in after grinding again.
Further, in step S2, the process for preparation of the coupling agent solution are as follows: coupling agent is dissolved in ethyl alcohol, it is described
The volume fraction of coupling agent is 1~8%.The coupling agent is preferably silane coupling agent, specifically can be γ-(methacryl
Oxygen) propyl trimethoxy silicane, γ-(2,3- the third oxygen of epoxy) propyl trimethoxy silicane, γ-(methacryloxypropyl) propyl three
Any one in methoxy silane.
Further, in step S2, the graphene/Al2O3The mass ratio of compounded mix and coupling agent be 100:(1~
20).Coupling agent thermal conductivity is poor, acts on as coupling filler and macromolecule matrix, reduction interface resistance, if the amount mistake of coupling agent
More, accounting, which crosses conference, reduces thermal conductivity；If the amount of coupling agent is very few, the effective coupling being difficult to realize between filler and matrix,
Increase interface resistance.
Further, in step S2, the graphene/Al is added in coupling agent solution2O3Before compounded mix, first it is added
It is 3~5 that glacial acetic acid, which controls pH,.
Further, in step S3, graphene/Al of the coupling agent modification2O3It compounded mix, silicone rubber matrix and helps
The mass ratio of agent is (45~65): (51~27): (4~8).Excessive filler be easy to cause dispersion uneven, forms gap；It is very few
Filler be difficult to be effectively improved the thermal conductivity of heat conductive silica gel.The material obtained under said ratio has good thermal conductivity, when
Graphene/Al2O3When the mass ratio of compounded mix, silicone rubber matrix and auxiliary agent is 60:35:5, the thermal conductivity of material is best.It is described
Silicone rubber matrix is preferably methyl vinyl silicone rubber, dimethyl silicone rubber or methyl phenyl vinyl silicone rubber.The auxiliary agent
It can be constitution controller, reinforcing agent, vulcanizing agent or catalyst.The constitution controller is preferably hydroxy silicon oil, aminomethyl phenyl
Methoxyl group silicone oil or methylhydroxy silicone oil.The reinforcing agent is preferably gas-phase silica, kaolin, silica flour, calcium silicates, silicic acid
Zirconium, zinc oxide or iron oxide.The vulcanizing agent is preferably benzoyl peroxide, 2,4- dichlorobenzoperoxide, peroxidating two
Tert-butyl, 2,5- dimethyl -2,5- di-t-butyl hexane peroxide.The catalyst is preferably platinum catalyst or chloroplatinic acid
Aqueous isopropanol.
Further, step S3 specifically: the graphene/Al for modifying the coupling agent2O3Compounded mix, silicon rubber base
Body and auxiliary agent are added in high speed open mill, vacuum mix 3~6h, lead to it is 2~5 times thin, then using vulcameter 120~300
3~8h of post-cure at DEG C obtains the graphene-based heat conductive silica gel of high dispersive.
In order to better understand and implement, illustrates the present invention with reference to the accompanying drawings and examples.
Detailed description of the invention
Fig. 1 is graphene/Al in embodiment 12O3The SEM of compounded mix schemes.
Specific embodiment
The present invention provides a kind of preparation methods of the graphene-based heat conductive silica gel of high dispersive, comprising the following steps:
(1) graphite oxide is weighed, is add to deionized water, the mass fraction of graphite oxide is 0.01~10%, ultrasound
Removing forms graphene oxide aqueous suspensions；Then aluminium salt is weighed, is added in the graphene oxide aqueous suspensions, stone in product is controlled
Black alkene and Al2O3Mass ratio be 1:(10~40), 0.5~2h of ultrasonic disperse, formed solution A；Precipitating reagent is weighed, is configured to dense
Degree is the solution of 0.1~5mol/L, and the ratio of precipitant concentration and aluminium salt concentration is (2~6): 1, addition ethylene glycol polymer conduct
Dispersing agent, concentration are 0.1~10%, form B solution；Then the solution A is mixed with B solution, with stirring and is added one
Quantitative aqueous slkali, control pH value of solution are 5~9, and maintaining temperature is 70~110 DEG C, stir 30~50h, obtain gray precipitate；So
The gray precipitate is filtered afterwards, with deionized water and washes of absolute alcohol 3~6 times, after drying 300 in argon atmosphere
~500 DEG C of 3~8h of pre-burning are placed in 900~1500 DEG C of 2~5h of calcining in argon atmosphere again after grinding.Obtain graphene/Al2O3It is multiple
Close filler.
(2) coupling agent is measured, is dissolved in ethyl alcohol, the volume fraction of coupling agent is 1~8%；It is added with stirring glacial acetic acid
Controlling pH is 3~5, adds graphene/Al made from step (1)2O3Compounded mix controls graphene/Al2O3Compounded mix
Mass ratio with coupling agent is 100:(1~20)；Then 1~4h is stirred, filter and is cleaned with alcohol, 60~80 DEG C of drying obtain
Graphene/Al of coupling agent modification2O3Compounded mix.
(3) graphene/Al for modifying coupling agent made from step (2)2O3Compounded mix is pressed with silicone rubber matrix and auxiliary agent
According to (45~65): (51~27): the mass ratio of (4~8) is added in high speed open mill, and vacuum mixes 3~6h, is led to thin by 2~5
It is secondary, vulcameter 3~8h of post-cure at 120~300 DEG C is then used, the graphene-based heat conductive silica gel of high dispersive is obtained.
It is further illustrated below by way of specific embodiment.
Embodiment 1
A kind of preparation method of the graphene-based heat conductive silica gel of high dispersive of the present embodiment, comprising the following steps:
(1) 0.2g graphite oxide is weighed, is added in 500mL deionized water, it is outstanding that ultrasound removing forms graphene oxide water
Liquid；Then 25.66g aluminum sulfate is added, ultrasonic disperse 1h forms solution A；Then 23.72g ammonium hydrogen carbonate is weighed, is configured to dense
Degree is the solution of 0.6mol/L, and 5mL polyethylene glycol 400 is added, is sufficiently stirred, and forms B solution；Then solution A is slowly added dropwise
Into B solution, with stirring and being added a certain amount of aqueous slkali, regulation pH value of solution is 6.5, and maintaining temperature is 85 DEG C, and electromagnetism stirs
Mix 12h, reaction sufficiently obtains gray precipitate, with deionized water and washes of absolute alcohol 3 times, after drying 300 in argon atmosphere
DEG C pre-burning 3h, is placed in 1000 DEG C of calcining 2h in argon atmosphere again, obtains graphene/Al after grinding2O3Compounded mix.
(2) 5mL coupling agent is measured, is dissolved into 200mL ethyl alcohol, a certain amount of glacial acetic acid is added with stirring, controls solution
PH is 3, and graphene/Al made from the above-mentioned reaction of 30g is added2O3Compounded mix after electromagnetic agitation 1.5h, filters simultaneously clear with ethyl alcohol
It washes, 60 DEG C of drying obtain graphene/Al of coupling agent modification2O3Compounded mix.
(3) using graphene/Al of above-mentioned coupling agent modification2O3Compounded mix, methyl vinyl silicone rubber matrix and one
Quantitative auxiliary agent is 59:35:6 in mass ratio, is added in high speed open mill, vacuum mix 3h, lead to it is 2 times thin, then use sulphur
Change and vulcanize 3h at 180 DEG C of instrument, obtains the graphene-based heat conductive silica gel of high dispersive.
Embodiment 2
A kind of preparation method of the graphene-based heat conductive silica gel of high dispersive of the present embodiment, comprising the following steps:
(1) 0.5g graphite oxide is weighed, is added in 500mL deionized water, it is outstanding that ultrasound removing forms graphene oxide water
Liquid；Then 51.33g aluminum sulfate is added, ultrasonic disperse 2h forms solution A；Then 43.24g ammonium carbonate is weighed, concentration is configured to
For the solution of 0.9mol/L, 10mL polyethylene glycol 2000 is added, is sufficiently stirred, forms B solution；Then solution A is slowly added dropwise
Into B solution, with stirring and being added a certain amount of aqueous slkali, regulation pH value of solution is 7, and maintaining temperature is 90 DEG C, electromagnetic agitation
For 24 hours, reaction sufficiently obtains gray precipitate, with deionized water and washes of absolute alcohol 4 times, after drying 350 DEG C in argon atmosphere
Pre-burning 5h is placed in 1100 DEG C of calcining 3h in argon atmosphere again, obtains graphene/Al after grinding2O3Compounded mix.
(2) 10mL coupling agent is measured, is dissolved into 250mL ethyl alcohol, a certain amount of glacial acetic acid is added with stirring, controls solution
PH is 4, and graphene/Al made from the above-mentioned reaction of 60g is added2O3Compounded mix after electromagnetic agitation 2h, is filtered and is simultaneously cleaned with ethyl alcohol,
65 DEG C of drying, obtain graphene/Al of coupling agent modification2O3Compounded mix.
(3) using graphene/Al of above-mentioned coupling agent modification2O3Compounded mix, dimethyl silicone rubber matrix and a certain amount of
Auxiliary agent be in mass ratio 60:35:5, be added in high speed open mill, vacuum mix 4h, lead to it is 4 times thin, then use vulcameter
Vulcanize 5h at 190 DEG C, obtains the graphene-based heat conductive silica gel of high dispersive.
Embodiment 3
A kind of preparation method of the graphene-based heat conductive silica gel of high dispersive of the present embodiment, comprising the following steps:
(1) 0.7g graphite oxide is weighed, is added in 500mL deionized water, it is outstanding that ultrasound removing forms graphene oxide water
Liquid；Then 94.86g alum is added, ultrasonic disperse 3h forms solution A；Then 36.04g urea is weighed, concentration is configured to
For the solution of 1.2mol/L, 15mL Macrogol 6000 is added, is sufficiently stirred, forms B solution；Then solution A is slowly added dropwise
Into B solution, with stirring and being added a certain amount of aqueous slkali, regulation pH value of solution is 7.5, and maintaining temperature is 95 DEG C, and electromagnetism stirs
Mix 48h, reaction sufficiently obtains gray precipitate, with deionized water and washes of absolute alcohol 5 times, after drying 400 in argon atmosphere
DEG C pre-burning 8h, is placed in 1200 DEG C of calcining 4h in argon atmosphere again, obtains graphene/Al after grinding2O3Compounded mix.
(2) 15mL coupling agent is measured, is dissolved into 500mL ethyl alcohol, a certain amount of glacial acetic acid is added with stirring, controls solution
PH is 5, and graphene/Al made from the above-mentioned reaction of 80g is added2O3Compounded mix after electromagnetic agitation 3h, is filtered and is simultaneously cleaned with ethyl alcohol,
70 DEG C of drying, obtain graphene/Al of coupling agent modification2O3Compounded mix.
(3) using graphene/Al of above-mentioned coupling agent modification2O3Compounded mix, dimethyl silicone rubber matrix and a certain amount of
Auxiliary agent be in mass ratio 61:34:5, be added in high speed open mill, vacuum mix 6h, lead to it is 5 times thin, then use vulcameter
Vulcanize 6h at 200 DEG C, obtains the graphene-based heat conductive silica gel of high dispersive.
Comparative example 1
A kind of preparation method of the graphene-based heat conductive silica gel of high dispersive of this comparative example, comprising the following steps:
(1) 0.2g graphene is weighed, is added in 500mL deionized water, ultrasonic disperse forms graphene aqueous suspensions；Then
25.66g aluminum sulfate is added, ultrasonic disperse 1h forms solution A；Then 23.72g ammonium hydrogen carbonate is weighed, being configured to concentration is
The solution of 0.6mol/L is added 5mL polyethylene glycol 400, is sufficiently stirred, and forms B solution；Then it is molten solution A to be slowly dropped to B
In liquid, with stirring and being added a certain amount of aqueous slkali, regulation pH value of solution is 6.5, and maintaining temperature is 85 DEG C, electromagnetic agitation 12h,
Reaction sufficiently obtains gray precipitate, with deionized water and washes of absolute alcohol 3 times, 300 DEG C of pre-burnings in argon atmosphere after drying
3h is placed in 1000 DEG C of calcining 2h in argon atmosphere again, obtains graphene/Al after grinding2O3Compounded mix.
(2) 5mL coupling agent is measured, is dissolved into 200mL ethyl alcohol, a certain amount of glacial acetic acid is added with stirring, controls solution
PH is 3, and graphene/Al made from the above-mentioned reaction of 30g is added2O3Compounded mix after electromagnetic agitation 1.5h, filters simultaneously clear with ethyl alcohol
It washes, 60 DEG C of drying obtain graphene/Al of coupling agent modification2O3Compounded mix.
(3) using graphene/Al of above-mentioned coupling agent modification2O3Compounded mix, methyl vinyl silicone rubber matrix and one
Quantitative auxiliary agent is 59:35:6 in mass ratio, is added in high speed open mill, vacuum mix 3h, lead to it is 2 times thin, then use sulphur
Change and vulcanize 3h at 180 DEG C of instrument, obtains graphene-based heat conductive silica gel.
Comparative example 2
A kind of preparation method of the graphene-based heat conductive silica gel of high dispersive of this comparative example, comprising the following steps:
(1) 0.5g graphene is weighed, is added in 500mL deionized water, ultrasound removing forms graphene aqueous suspensions；Then
51.33g aluminum sulfate is added, ultrasonic disperse 2h forms solution A；Then 43.24g ammonium carbonate is weighed, being configured to concentration is
The solution of 0.9mol/L is added 10mL polyethylene glycol 2000, is sufficiently stirred, and forms B solution；Then solution A is slowly dropped to B
In solution, be simultaneously added a certain amount of aqueous slkali with stirring, regulation pH value of solution is 7, and maintaining temperature is 90 DEG C, electromagnetic agitation for 24 hours,
Reaction sufficiently obtains gray precipitate, with deionized water and washes of absolute alcohol 4 times, 350 DEG C of pre-burnings in argon atmosphere after drying
5h is placed in 1100 DEG C of calcining 3h in argon atmosphere again, obtains graphene/Al after grinding2O3Compounded mix.
(2) 10mL coupling agent is measured, is dissolved into 250mL ethyl alcohol, a certain amount of glacial acetic acid is added with stirring, controls solution
PH is 4, and graphene/Al made from the above-mentioned reaction of 60g is added2O3Compounded mix after electromagnetic agitation 2h, is filtered and is simultaneously cleaned with ethyl alcohol,
65 DEG C of drying, obtain graphene/Al of coupling agent modification2O3Compounded mix.
(3) using graphene/Al of above-mentioned coupling agent modification2O3Compounded mix, dimethyl silicone rubber matrix and a certain amount of
Auxiliary agent be in mass ratio 60:35:5, be added in high speed open mill, vacuum mix 4h, lead to it is 4 times thin, then use vulcameter
Vulcanize 5h at 190 DEG C, obtains graphene-based heat conductive silica gel.
Comparative example 3
A kind of preparation method of the graphene-based heat conductive silica gel of high dispersive of this comparative example, comprising the following steps:
(1) 0.7g graphene is weighed, while weighing 20.39g spherical shape Al2O3, after powder is dry-mixed, obtain graphene and Al2O3
Compounded mix.
(2) 5mL coupling agent is measured, is dissolved into 200mL ethyl alcohol, a certain amount of glacial acetic acid is added with stirring, controls solution
PH is 3, and graphene and Al made from the above-mentioned reaction of 30g is added2O3Compounded mix after electromagnetic agitation 1.5h, filters simultaneously clear with ethyl alcohol
It washes, 60 DEG C of drying obtain the graphene and Al of coupling agent modification2O3Compounded mix.
3. using the graphene and Al of the modification of above-mentioned coupling agent2O3Compounded mix, methyl vinyl silicone rubber matrix and one
Quantitative auxiliary agent is 59:35:6 in mass ratio, is added in high speed open mill, vacuum mix 3h, lead to it is 2 times thin, then use sulphur
Change and vulcanize 3h at 180 DEG C of instrument, obtains graphene-based heat conductive silica gel.
Performance test
Referring to Fig. 1, it is graphene/Al in embodiment 12O3The SEM of compounded mix schemes.It can be seen from the figure that stone
Black alkene lamella is relatively thin, and yarn shape is presented, and has polymolecularity；Al2O3For spherical nanoparticle, it is dispersed in graphene sheet layer
In；Graphene and Al2O3Particle fits closely, and the two mutually cooperates with, and forms evenly dispersed compounded mix.
Heat conductive silica gel made from Examples 1 to 3 and comparative example 1~3 is tested for the property, test method is using domestic
Outer common standard method of test, obtained result are as shown in table 1 below.
As can be seen from the table, the comprehensive performance of the embodiment of the present invention 1~3 is better than comparative example 1~3.Original of the invention
Material uses graphene oxide, and has synthesized spherical Al by sluggish precipitation2O3, using the active function groups of graphene oxide,
Fabricated in situ graphene oxide/Al2O3Compound obtains the graphene substrate of favorable dispersibility by high temperature sintering reduction treatment
Material, can effectively avoid dispersion problem of the graphene as heat filling, play its heating conduction.It is obtained through the invention
Graphene/Al2O3In compounded mix, graphene is in Al2O3Bridged linkage is formed between particle, forms graphene/Al2O3It is compound to fill out
The close-packed structure of material in a polymer matrix, can promote to form thermally conductive supply chain network structure, interface resistance be reduced, to improve
The thermal conductivity of heat conductive silica gel.And Al2O3Uniformly adhere on the surface of graphene, the heating conduction that graphene can not only be utilized excellent,
Improve Al2O3The defect not high as single filler thermal conductivity, while the Al that can be utilized2O3Electrical insulating property prevents composite material
Reach electroosmotic flow threshold value, obtains preferable synergistic effect.In addition, the present invention prepares spherical alumina aluminium powder using sluggish precipitation
Body has the advantages that low cost of material, simple process, easy to operate, low for equipment requirements.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention
Range.
Claims (10)
1. a kind of preparation method of the graphene-based heat conductive silica gel of high dispersive, it is characterised in that: the following steps are included:
S1: graphite oxide is added to the water, and ultrasound removing forms graphene oxide aqueous suspensions；The graphite oxide is added in aluminium salt
In alkene aqueous suspensions, ultrasonic disperse forms solution A；Precipitant solution is prepared, and dispersing agent is added, forms B solution；The A is molten
Liquid is mixed with B solution, and stirring obtains gray precipitate, is then filtered, cleans, dries, calcines to the gray precipitate, obtain
To graphene/Al2O3Compounded mix；
S2: coupling agent solution is prepared, the graphene/Al is added2O3Then compounded mix is stirred, filters, cleans, dries
It is dry, obtain graphene/Al of coupling agent modification2O3Compounded mix；
S3: graphene/Al that the coupling agent is modified2O3Compounded mix is mixed with silicone rubber matrix and auxiliary agent, is then vulcanized,
Obtain the graphene-based heat conductive silica gel of high dispersive.
2. the preparation method of the graphene-based heat conductive silica gel of high dispersive according to claim 1, it is characterised in that: step S1
In, the graphene/Al2O3In compounded mix, graphene and Al2O3Mass ratio be 1:(10~40).
3. the preparation method of the graphene-based heat conductive silica gel of high dispersive according to claim 1 or 2, it is characterised in that: step
In S1, the ratio of the concentration of precipitating reagent and the concentration of aluminium salt in the solution A is (2~6) in the B solution: 1.
4. the preparation method of the graphene-based heat conductive silica gel of high dispersive according to claim 3, it is characterised in that: step S1
In, in solution A and B solution mixed process, it is 5~9 that aqueous slkali control pH, which is added, and 30~50h is stirred at 70~110 DEG C.
5. the preparation method of the graphene-based heat conductive silica gel of high dispersive according to claim 4, it is characterised in that: step S1
In, the calcination process are as follows: be first placed in 300~500 DEG C of 3~8h of pre-burning in argon atmosphere；It is placed in argon atmosphere again after grinding
900~1500 DEG C of 2~5h of calcining.
6. the preparation method of the graphene-based heat conductive silica gel of high dispersive according to claim 1, it is characterised in that: step S2
In, the process for preparation of the coupling agent solution are as follows: coupling agent is dissolved in ethyl alcohol, the volume fraction of the coupling agent is 1~
8%.
7. the preparation method of the graphene-based heat conductive silica gel of high dispersive according to claim 6, it is characterised in that: step S2
In, the graphene/Al2O3The mass ratio of compounded mix and coupling agent is 100:(1~20).
8. the preparation method of the graphene-based heat conductive silica gel of high dispersive according to claim 7, it is characterised in that: step S2
In, the graphene/Al is added in coupling agent solution2O3Before compounded mix, it is 3~5 that glacial acetic acid control pH, which is first added,.
9. the preparation method of the graphene-based heat conductive silica gel of high dispersive according to claim 1, it is characterised in that: step S3
In, graphene/Al of the coupling agent modification2O3The mass ratio of compounded mix, silicone rubber matrix and auxiliary agent is (45~65): (51
~27): (4~8).
10. the preparation method of the graphene-based heat conductive silica gel of high dispersive according to claim 9, it is characterised in that: step S3
Specifically: the graphene/Al for modifying the coupling agent2O3Compounded mix, silicone rubber matrix and auxiliary agent are added to high speed open mill
In, vacuum mix 3~6h, lead to it is 2~5 times thin, then use vulcameter 3~8h of post-cure at 120~300 DEG C, obtain height
Dispersed graphite alkenyl heat conductive silica gel.
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