CN108976802A - A kind of preparation method of heat conductive insulating silicone grease - Google Patents
A kind of preparation method of heat conductive insulating silicone grease Download PDFInfo
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Abstract
The invention discloses a kind of preparation methods of heat conductive insulating silicone grease, belong to thermal interfacial material technical field.According to parts by weight, it successively weighs: 70~80 parts of silicone oil, 10~12 parts of epoxidized soybean oils, 5~8 parts of catalyst, 10~18 parts of pretreatment conduction powders and 15~25 parts of modified carbon nano-tubes；Silicone oil and epoxidized soybean oil are mixed in blender, and catalyst is added into blender, pre-process conduction powder and modified carbon nano-tube, in temperature be 45~65 DEG C, after revolving speed is stirred 30~60min under conditions of being 300~400r/min, heat conductive insulating silicone grease is obtained.The heat conductive insulating silicone grease of technical solution of the present invention preparation has the characteristics that excellent heating conduction and insulation performance, has broad prospects in the development of thermal interfacial material industry.
Description
Technical field
The invention discloses a kind of preparation methods of heat conductive insulating silicone grease, belong to thermal interfacial material technical field.
Background technique
Heat conductive insulating silicone grease is combined using the metal oxide of thermal conductivity and excellent insulation performance and organosilicon oxygen,
Product has brilliant heat-conductive characteristic, and good electrical insulating property is coated on various electronic products, the hair in electrical equipment extensively
Contact surface between hot body and cooling facilities plays heat transfer and the performances such as moisture-proof, dust-proof, anticorrosion, shockproof.It is thermally conductive exhausted
Edge silicone grease is by high temperature resistant silicone oil, high heat conductive insulating filler and to add function additive etc..Aim to thermally conductive, heat resistance require compared with
The high heat conductive insulating cream of the heat dissipation and insulation and research and development of high Switching Power Supply, temperature controller and power amplifier tube and cooling fin, reduces
Solid interface thermal contact resistance, improvement interfacial heat exchange, -60~+300 DEG C of Applicable temperature range.
Heating surface and out-of-flatness between electronic component and heat sink or radiator, seem smooth chip surface and are
The spreader surface of nest temperature chip cooling has the tiny hole being much invisible to the naked eye recessed and fine impurities in fact.When the table of the two
When face contact, gully or gap between surface are all air.And the capacity of heat transmission of air is very poor, thermal resistance is larger, required to fill out
Filling other materials reduces thermal resistance, improves the performance of radiator.Then, heat-conducting medium just comes into being, and thermally conductive Gui rouge is for we
The most common heat-conducting medium on ordinary days is mainly used for filling the gap between two contact surfaces, to increase pyrotoxin and cooling fin
Contact area.
As LED manufacture and packaging technology are constantly progressive, the power of LED is increasing.Great power LED input power one
As in 1W or more, chip area 1mm × 1mm, heat flow density is in 100W/cm2More than, cooling requirements are very high.Heat is from chip
External environment is passed to, if to pass through dry interface, the warpage in gap, substrate between interface can all influence the heat dissipation of key part, shape
At interface resistance.Common boundary material has heat-conducting glue, heat-conducting silicone grease and thermally conductive film.Heat-conducting pad uses simply, but because of it
Thickness is larger, thermal resistance is bigger than normal, may not apply to the very high occasion of cooling requirements.Heat-conducting silicone grease be filled in accessory and radiator it
Between, drain intermediate air, can sufficiently moisten contact surface, form a low-down thermal resistance interface, conducive to help CPU, greatly
Power LED etc. generates heat rich and influential family rapidly " bringing down a fever ".Heat conductive silica gel and heat-conducting silicone grease are the filled media of intermediate heat, appearance also phase
Seemingly, difference is: heat conductive silica gel is a kind of casting glue, and main component is silica, has extraordinary viscosity, can under room temperature
With solidification；And heat-conducting silicone grease cannot solidify, without viscosity.So heat conductive silica gel is used primarily in no fastener or fixed device
Radiator in, and silicone grease is mainly to be used in the fixed heat dissipation equipment of fastener.
And the problem that traditional heat conductive insulating silicone grease is bad there is also insulation performance and heating conduction, cause in use without
Method reaches ideal effect, and therefore, how improving conventional thermal conductive insulation silicone grease insulation performance and heating conduction can not further increase
The shortcomings that, developing the heat conductive insulating silicone grease with good comprehensive performance in the hope of exploration is problem to be solved.
Summary of the invention
The present invention solves the technical problem of: it can not for conventional thermal conductive insulation silicone grease insulation performance and heating conduction
The shortcomings that further increasing provides a kind of preparation method of heat conductive insulating silicone grease.
In order to solve the above-mentioned technical problem, the technical scheme adopted by the invention is that:
A kind of preparation method of magnetosensitive rubber, specific preparation step are as follows:
A kind of preparation method of heat conductive insulating silicone grease, specific preparation step are as follows:
(1) carbon nanotube is mixed with dehydrated alcohol 1:300~1:320 in mass ratio, after ultrasonic disperse, adjusts pH to 8~10,
And be stirred to react, carbon nanotube mixture is obtained, the pH of carbon nanotube mixture is adjusted to neutrality, filters, wash, drying obtains pre-
Handle carbon nanotube；
(2) pretreatment carbon nanotube is mixed with ethanol water 1:300~1:320 in mass ratio, and pretreatment carbon is added and receives
The ammonium hydroxide that 2~4 times of mitron quality, ultrasonic disperse instill while ultrasonic disperse and pre-process 4~6 times of carbon nanotube mass
Ethyl orthosilicate mixture after being stirred, obtains pretreatment carbon nanotube mixture；It will pretreatment carbon nanotube mixture and silicon
Alkane is coupled agent composition 300:1~300:4 in mass ratio mixing, after being stirred, filters, and washing obtains pre- modified carbon nano-tube；
(3) pre- modified carbon nano-tube is mixed with water 1:200~1:400 in mass ratio, adjusts pH to 4.0~4.8, and be added pre-
The hydroxy silicon oil that 0.4~0.5 times of modified carbon nano-tube quality after being stirred, is aged, filters, washs, dry, obtains carbon modified
Nanometer blank；
(4) modified carbon nano tube blank is mixed with water 1:100~1:200 in mass ratio, and modified carbon nano tube blank is added
The amino silane that 0.3~0.5 times of quality, after being stirred, cooling, and pH value 6.5~6.8 is adjusted, and it filters, it is dry, obtain modification
Carbon nanotube；
(5) according to parts by weight, it successively weighs: 70~80 parts of silicone oil, 10~12 parts of epoxidized soybean oils, 5~8 parts of catalyst, 10
~18 parts of pretreatment conduction powders and 15~25 parts of modified carbon nano-tubes；Silicone oil is mixed with epoxidized soybean oil, and catalysis is added
Agent pre-processes conduction powder and modified carbon nano-tube, after being stirred, obtains heat conductive insulating silicone grease.
The average caliber of step (1) described carbon nanotube is 10~30nm, and length is 0.5~100 μm.
Step (2) ethanol water is that 4:1 is mixed by volume with water by dehydrated alcohol, obtains ethanol water.
Step (2) the ethyl orthosilicate mixture is can be than 1:8~1 by quality by ethyl orthosilicate and dehydrated alcohol:
10 mixing, obtain ethyl orthosilicate mixture.
Step (2) the silane coupled agent composition is to mix dehydrated alcohol and acetic acid 1:1 in mass ratio, and nothing is added
The Silane coupling reagent KH-570 that 0.4~0.6 times of water-ethanol quality, is stirred, and obtains silane coupled agent composition.
Step (5) catalyst is any one in nano magnesia or nano zine oxide.
Step (5) the pretreatment conduction powder is to mix nano-silicon nitride and nano aluminum nitride 1:1~2:1 in mass ratio
It closes, and 4~6 times of nano-silicon nitride quality of ethyl alcohol and 0.3~0.4 times of nano-silicon nitride quality of silane coupling agent KH- is added
570, after adjusting pH to 9.8~10.0, it is stirred, ultrasonic disperse, it is dry, obtain pretreatment conduction powder.
The beneficial effects of the present invention are:
(1) modified carbon nano-tube is added during preparing heat conductive insulating silicone grease in the present invention, firstly, carbon nanotube is by changing
Property rear surface be grafted with silica, be added product in after, silica can be uniformly distributed under the action of silane coupling agent
In product, so that modified carbon nano-tube be made to be uniformly distributed in product, and then improve the heating conduction of product, also, by
In the presence of silica, the reunion of carbon nanotube can be prevented, and then further increases the thermal conductivity of product, secondly, modified
After modification, silica surface hydroxyl and hydroxy silicon oil dehydrating condensation are formed newly the silica being grafted in carbon nanotube
Combination is built, so that the hydrophobicity of silica be made to improve, dispersibility is improved in silicone oil, and then improves the thermal conductivity of product；
(2) epoxidized soybean oil and catalyst is added in the present invention during preparing heat conductive insulating silicone grease, on the one hand, carbon modified is received
Hydroxy silicon oil amination in subsequent processing in mitron, can form under the effect of the catalyst crosslinking with epoxidized soybean oil, from
And certain cross-linked network can be formed in the product, and then improve the thermal conductivity of product, also, since carbon nanotube forms net
It after network structure, can not directly be contacted between carbon nanotube, its electric conductivity can be reduced, and then make product with preferable thermal conductivity
Meanwhile the insulating properties of product is improved, on the other hand, under the action of catalyst, epoxidized soybean oil is formed in modified carbon nano-tube
Catalyst and conduction powder can be fixed in product by cross-linked network, prevent the reunion of catalyst and conduction powder, and then make to produce
The thermal conductivity of product further increases.
Specific embodiment
Nano-silicon nitride and nano aluminum nitride 1:1~2:1 in mass ratio are mixed in beaker, and is added and receives into beaker
Rice 4~6 times of quality of ethyl alcohol of silicon nitride and 0.3~0.4 times of nano-silicon nitride quality of Silane coupling reagent KH-570, with quality point
Number is adjusted in pH beaker after the pH to 9.8~10.0 of material for 5~10% sodium hydroxide solution, is 55~65 DEG C in temperature, is turned
After speed is stirred 3~4h under conditions of being 300~400r/min, and the ultrasonic disperse under conditions of frequency is 50~55kHz
After 15~20min, then by material in beaker be 120~130 DEG C in temperature under conditions of after dry 3~4h, must pre-process thermally conductive
Powder；Carbon nanotube is mixed with dehydrated alcohol 1:300~1:320 in mass ratio, is surpassed under conditions of frequency is 50~55kHz
After sound disperses 20~30min, the potassium hydroxide solution for being 15~18% with mass fraction adjusts carbon nanotube and mixes with dehydrated alcohol
The pH to 8~10 of object, and in temperature be 85~90 DEG C, revolving speed be 300~400r/min under conditions of be stirred to react 8~9h after,
Carbon nanotube mixture is obtained, the pH for adjusting carbon nanotube mixture with the hydrochloric acid that mass fraction is 5~8% is filtered, obtained to neutrality
Filter cake after filter cake is washed with water 5~10 times, after being dried in vacuo 4~5h under conditions of being 70~80 DEG C in temperature, must pre-process
Carbon nanotube；Pretreatment carbon nanotube and ethanol water 1:300~1:320 in mass ratio are mixed in conical flask, and to
In conical flask be added pre-process 2~4 times of carbon nanotube mass mass fraction be 25~28% ammonium hydroxide, in frequency be 45~55kHz
Under conditions of after 60~70min of ultrasonic disperse, under conditions of ultrasonic disperse under conditions of 5~12mL/min into conical flask
The ethyl orthosilicate mixture for instilling 4~6 times of carbon nanotube mass of pretreatment after being added dropwise, is 50~60 DEG C in temperature, turns
After speed is stirred 15~18h under conditions of being 300~400r/min, pretreatment carbon nanotube mixture is obtained；Carbon will be pre-processed
Nanotube mixture is mixed with silane coupled agent composition 300:1~300:4 in mass ratio, in temperature be 45~55 DEG C, revolving speed
After being stirred 6~7h under conditions of 300~350r/min, filters, obtain pre- modified carbon nano tube blank, pre- carbon modified is received
After mitron blank is washed with water 5~8 times, pre- modified carbon nano-tube is obtained；By pre- modified carbon nano-tube and water 1:200 in mass ratio~
1:400 is mixed in flask, and the acetic acid for being 12~25% with mass fraction adjusts the pH to 4.0~4.8 of material in flask, and
The hydroxy silicon oil of 0.4~0.5 times of pre- modified carbon nano-tube quality is added into flask, in temperature be 45~65 DEG C, revolving speed 300
After being stirred 30~40min under conditions of~400r/min, by material in flask after being aged 1~3h under room temperature, mistake
Filter, obtains filter residue, after filter residue is washed with water 8~12 times, under conditions of being 60~70 DEG C in temperature after dry 30~40min, obtains
Modified carbon nano tube blank；Modified carbon nano tube blank and water 1:100~1:200 in mass ratio are mixed in three-necked flask,
And into three-necked flask be added 0.3~0.5 times of modified carbon nano tube blank quality amino silane, in temperature be 80~90 DEG C,
After revolving speed is stirred 4~5h under conditions of being 260~320r/min, temperature of charge in three-necked flask is cooled to 40~45
DEG C, and the acetic acid for being 12~20% with mass fraction is adjusted in three-necked flask after the pH value 6.5~6.8 of material, filtering obtains pre- place
Modified carbon nano-tube is managed, after being dried in vacuo 1~2h under conditions of being 60~70 DEG C in temperature by pretreatment modification carbon nanotube, is obtained
Modified carbon nano-tube；According to parts by weight, it successively weighs: 70~80 parts of silicone oil, 10~12 parts of epoxidized soybean oils, 5~8 parts of catalysis
Agent, 10~18 parts of pretreatment conduction powders and 15~25 parts of modified carbon nano-tubes；Silicone oil and epoxidized soybean oil are mixed in stirring
In machine, and catalyst is added into blender, pre-processes conduction powder and modified carbon nano-tube, is 45~65 DEG C in temperature, turns
After speed is stirred 30~60min under conditions of being 300~400r/min, heat conductive insulating silicone grease is obtained.The carbon nanotube is put down
Equal caliber is 10~30nm, and length is 0.5~100 μm.The ethanol water is that 4:1 is mixed by volume with water by dehydrated alcohol
It closes, obtains ethanol water.The ethyl orthosilicate mixture is can be than 1:8~1 by quality by ethyl orthosilicate and dehydrated alcohol:
10 mixing, obtain ethyl orthosilicate mixture.The silane coupled agent composition is to mix dehydrated alcohol and acetic acid 1:1 in mass ratio
It closes, and 0.4~0.6 times of dehydrated alcohol quality of Silane coupling reagent KH-570 is added, be stirred, obtain silane coupling agent mixing
Object.The catalyst is any one in nano magnesia or nano zine oxide.
Example 1
Nano-silicon nitride and nano aluminum nitride 2:1 in mass ratio are mixed in beaker, and nano-silicon nitride is added into beaker
The ethyl alcohol and 0.4 times of nano-silicon nitride quality of Silane coupling reagent KH-570 that 6 times of quality, the hydroxide for being 10% with mass fraction
Sodium solution is adjusted in pH beaker after the pH to 10.0 of material, is 65 DEG C in temperature, revolving speed stirs mixed under conditions of being 400r/min
After closing 4h, and under conditions of frequency is 55kHz after ultrasonic disperse 20min, then the item for being 130 DEG C in temperature by material in beaker
Under part after dry 4h, pretreatment conduction powder is obtained；Carbon nanotube is mixed with dehydrated alcohol 1:320 in mass ratio, is in frequency
Under conditions of 55kHz after ultrasonic disperse 30min, with mass fraction be 18% potassium hydroxide solution adjust carbon nanotube with it is anhydrous
The pH to 10 of alcohol mixture, and be 90 DEG C in temperature, after revolving speed is stirred to react 9h under conditions of being 400r/min, obtain carbon nanometer
Pipe mixture, the pH for adjusting carbon nanotube mixture with the hydrochloric acid that mass fraction is 8% filter to neutrality, filter cake are obtained, by filter cake
After being washed with water 10 times, after being dried in vacuo 5h under conditions of being 80 DEG C in temperature, pretreatment carbon nanotube is obtained；Pretreatment carbon is received
Mitron and ethanol water 1:320 in mass ratio are mixed in conical flask, and pretreatment carbon nanotube matter is added into conical flask
The mass fraction of 4 times of amount is 28% ammonium hydroxide, under conditions of frequency is 55kHz after ultrasonic disperse 70min, in the item of ultrasonic disperse
To instill the ethyl orthosilicate mixture for pre-processing 6 times of carbon nanotube mass under conditions of 12mL/min into conical flask under part,
After being added dropwise, it is 60 DEG C in temperature, after revolving speed is stirred 18h under conditions of being 400r/min, obtains pretreatment carbon nanotube
Mixture；Will pretreatment carbon nanotube mixture mixed with silane coupled agent composition 300:4 in mass ratio, in temperature be 55
DEG C, after revolving speed is stirred 7h under conditions of being 350r/min, filters, obtain pre- modified carbon nano tube blank, pre- carbon modified is received
After mitron blank is washed with water 8 times, pre- modified carbon nano-tube is obtained；Pre- modified carbon nano-tube is mixed with water 1:400 in mass ratio
In flask, and the acetic acid for being 25% with mass fraction adjusts the pH to 4.8 of material in flask, and pre- modification is added into flask
The hydroxy silicon oil that 0.5 times of carbon nanotube mass is 65 DEG C in temperature, and revolving speed is stirred 40min under conditions of being 400r/min
Afterwards, by material in flask after being aged 3h under room temperature, filtering obtains filter residue, after filter residue is washed with water 12 times, is in temperature
Under conditions of 70 DEG C after dry 40min, modified carbon nano tube blank is obtained；By modified carbon nano tube blank and water in mass ratio 1:
200 are mixed in three-necked flask, and the amino silane of 0.5 times of modified carbon nano tube blank quality is added into three-necked flask, in
Temperature is 90 DEG C, and after revolving speed is stirred 5h under conditions of being 320r/min, temperature of charge in three-necked flask is cooled to 45 DEG C,
And adjusted in three-necked flask after the pH value 6.8 of material with mass fraction for 20% acetic acid, filtering obtains pretreatment modification carbon nanometer
Pipe obtains modified carbon nano-tube after being dried in vacuo 2h under conditions of being 70 DEG C in temperature by pretreatment modification carbon nanotube；By weight
Number meter, successively weighs: 80 parts of silicone oil, 12 parts of epoxidized soybean oils, 8 parts of catalyst, and 18 parts of pretreatment conduction powders and 25 parts change
Property carbon nanotube；Silicone oil and epoxidized soybean oil are mixed in blender, and catalyst is added into blender, is pre-processed thermally conductive
Powder and modified carbon nano-tube are 65 DEG C in temperature, after revolving speed is stirred 60min under conditions of being 400r/min, obtain thermally conductive
Insulate silicone grease.The average caliber of the carbon nanotube is 30nm, and length is 100 μm.The ethanol water is by dehydrated alcohol
4:1 is mixed by volume with water, obtains ethanol water.The ethyl orthosilicate mixture is by ethyl orthosilicate and dehydrated alcohol
It can be mixed than 1:10 by quality, obtain ethyl orthosilicate mixture.The silane coupled agent composition is by dehydrated alcohol and acetic acid
The mixing of 1:1 in mass ratio, and 0.6 times of dehydrated alcohol quality of Silane coupling reagent KH-570 is added, it is stirred, obtains silane coupled
Agent composition.The catalyst is nano magnesia.
Example 2
Nano-silicon nitride and nano aluminum nitride 2:1 in mass ratio are mixed in beaker, and nano-silicon nitride is added into beaker
The ethyl alcohol and 0.4 times of nano-silicon nitride quality of Silane coupling reagent KH-570 that 6 times of quality, the hydroxide for being 10% with mass fraction
Sodium solution is adjusted in pH beaker after the pH to 10.0 of material, is 65 DEG C in temperature, revolving speed stirs mixed under conditions of being 400r/min
After closing 4h, and under conditions of frequency is 55kHz after ultrasonic disperse 20min, then the item for being 130 DEG C in temperature by material in beaker
Under part after dry 4h, pretreatment conduction powder is obtained；Carbon nanotube is mixed with dehydrated alcohol 1:320 in mass ratio, is in frequency
Under conditions of 55kHz after ultrasonic disperse 30min, with mass fraction be 18% potassium hydroxide solution adjust carbon nanotube with it is anhydrous
The pH to 10 of alcohol mixture, and be 90 DEG C in temperature, after revolving speed is stirred to react 9h under conditions of being 400r/min, obtain carbon nanometer
Pipe mixture, the pH for adjusting carbon nanotube mixture with the hydrochloric acid that mass fraction is 8% filter to neutrality, filter cake are obtained, by filter cake
After being washed with water 10 times, after being dried in vacuo 5h under conditions of being 80 DEG C in temperature, pretreatment carbon nanotube is obtained；Pretreatment carbon is received
Mitron and ethanol water 1:320 in mass ratio are mixed in conical flask, and pretreatment carbon nanotube matter is added into conical flask
The mass fraction of 4 times of amount is 28% ammonium hydroxide, under conditions of frequency is 55kHz after ultrasonic disperse 70min, in the item of ultrasonic disperse
To instill the ethyl orthosilicate mixture for pre-processing 6 times of carbon nanotube mass under conditions of 12mL/min into conical flask under part,
After being added dropwise, it is 60 DEG C in temperature, after revolving speed is stirred 18h under conditions of being 400r/min, obtains pretreatment carbon nanotube
Mixture；Will pretreatment carbon nanotube mixture mixed with silane coupled agent composition 300:4 in mass ratio, in temperature be 55
DEG C, after revolving speed is stirred 7h under conditions of being 350r/min, filters, obtain pre- modified carbon nano tube blank, pre- carbon modified is received
After mitron blank is washed with water 8 times, pre- modified carbon nano-tube is obtained；Pre- modified carbon nano-tube is mixed with water 1:400 in mass ratio
In flask, and the acetic acid for being 25% with mass fraction adjusts the pH to 4.8 of material in flask, and pre- modification is added into flask
The hydroxy silicon oil that 0.5 times of carbon nanotube mass is 65 DEG C in temperature, and revolving speed is stirred 40min under conditions of being 400r/min
Afterwards, by material in flask after being aged 3h under room temperature, filtering obtains filter residue, after filter residue is washed with water 12 times, is in temperature
Under conditions of 70 DEG C after dry 40min, modified carbon nano-tube is obtained；According to parts by weight, it successively weighs: 80 parts of silicone oil, 12 parts of rings
Oxygen soybean oil, 8 parts of catalyst, 18 parts of pretreatment conduction powders and 25 parts of modified carbon nano-tubes；Silicone oil and epoxidized soybean oil are mixed
Together in blender, and catalyst is added into blender, pre-processes conduction powder and modified carbon nano-tube, in temperature be 65
DEG C, after revolving speed is stirred 60min under conditions of being 400r/min, obtain heat conductive insulating silicone grease.The average pipe of the carbon nanotube
Diameter is 30nm, and length is 100 μm.The ethanol water is that 4:1 is mixed by volume with water by dehydrated alcohol, and it is water-soluble to obtain ethyl alcohol
Liquid.The ethyl orthosilicate mixture is that can mix ethyl orthosilicate than 1:10 by quality with dehydrated alcohol, obtains positive silicic acid second
Ester admixture.The silane coupled agent composition is to mix dehydrated alcohol and acetic acid 1:1 in mass ratio, and dehydrated alcohol is added
The Silane coupling reagent KH-570 that 0.6 times of quality, is stirred, and obtains silane coupled agent composition.The catalyst is nano oxidized
Magnesium.
Example 3
Nano-silicon nitride and nano aluminum nitride 2:1 in mass ratio are mixed in beaker, and nano-silicon nitride is added into beaker
The ethyl alcohol and 0.4 times of nano-silicon nitride quality of Silane coupling reagent KH-570 that 6 times of quality, the hydroxide for being 10% with mass fraction
Sodium solution is adjusted in pH beaker after the pH to 10.0 of material, is 65 DEG C in temperature, revolving speed stirs mixed under conditions of being 400r/min
After closing 4h, and under conditions of frequency is 55kHz after ultrasonic disperse 20min, then the item for being 130 DEG C in temperature by material in beaker
Under part after dry 4h, pretreatment conduction powder is obtained；Carbon nanotube is mixed with dehydrated alcohol 1:320 in mass ratio, is in frequency
Under conditions of 55kHz after ultrasonic disperse 30min, with mass fraction be 18% potassium hydroxide solution adjust carbon nanotube with it is anhydrous
The pH to 10 of alcohol mixture, and be 90 DEG C in temperature, after revolving speed is stirred to react 9h under conditions of being 400r/min, obtain carbon nanometer
Pipe mixture, the pH for adjusting carbon nanotube mixture with the hydrochloric acid that mass fraction is 8% filter to neutrality, filter cake are obtained, by filter cake
After being washed with water 10 times, after being dried in vacuo 5h under conditions of being 80 DEG C in temperature, pretreatment carbon nanotube is obtained；Pretreatment carbon is received
Mitron and ethanol water 1:320 in mass ratio are mixed in conical flask, and pretreatment carbon nanotube matter is added into conical flask
The mass fraction of 4 times of amount is 28% ammonium hydroxide, under conditions of frequency is 55kHz after ultrasonic disperse 70min, in the item of ultrasonic disperse
To instill the ethyl orthosilicate mixture for pre-processing 6 times of carbon nanotube mass under conditions of 12mL/min into conical flask under part,
After being added dropwise, it is 60 DEG C in temperature, after revolving speed is stirred 18h under conditions of being 400r/min, obtains pretreatment carbon nanotube
Mixture；Will pretreatment carbon nanotube mixture mixed with silane coupled agent composition 300:4 in mass ratio, in temperature be 55
DEG C, after revolving speed is stirred 7h under conditions of being 350r/min, filters, obtain pre- modified carbon nano tube blank, pre- carbon modified is received
After mitron blank is washed with water 8 times, pre- modified carbon nano-tube is obtained；Pre- modified carbon nano-tube is mixed with water 1:400 in mass ratio
In flask, and the acetic acid for being 25% with mass fraction adjusts the pH to 4.8 of material in flask, and pre- modification is added into flask
The hydroxy silicon oil that 0.5 times of carbon nanotube mass is 65 DEG C in temperature, and revolving speed is stirred 40min under conditions of being 400r/min
Afterwards, by material in flask after being aged 3h under room temperature, filtering obtains filter residue, after filter residue is washed with water 12 times, is in temperature
Under conditions of 70 DEG C after dry 40min, modified carbon nano tube blank is obtained；By modified carbon nano tube blank and water in mass ratio 1:
200 are mixed in three-necked flask, and the amino silane of 0.5 times of modified carbon nano tube blank quality is added into three-necked flask, in
Temperature is 90 DEG C, and after revolving speed is stirred 5h under conditions of being 320r/min, temperature of charge in three-necked flask is cooled to 45 DEG C,
And adjusted in three-necked flask after the pH value 6.8 of material with mass fraction for 20% acetic acid, filtering obtains pretreatment modification carbon nanometer
Pipe obtains modified carbon nano-tube after being dried in vacuo 2h under conditions of being 70 DEG C in temperature by pretreatment modification carbon nanotube；By weight
Number meter, successively weighs: 80 parts of silicone oil, 8 parts of catalyst, 18 parts of pretreatment conduction powders and 25 parts of modified carbon nano-tubes；By silicon
Catalyst is added into blender in blender for oil, pre-processes conduction powder and modified carbon nano-tube, in temperature be 65
DEG C, after revolving speed is stirred 60min under conditions of being 400r/min, obtain heat conductive insulating silicone grease.The average pipe of the carbon nanotube
Diameter is 30nm, and length is 100 μm.The ethanol water is that 4:1 is mixed by volume with water by dehydrated alcohol, and it is water-soluble to obtain ethyl alcohol
Liquid.The ethyl orthosilicate mixture is that can mix ethyl orthosilicate than 1:10 by quality with dehydrated alcohol, obtains positive silicic acid second
Ester admixture.The silane coupled agent composition is to mix dehydrated alcohol and acetic acid 1:1 in mass ratio, and dehydrated alcohol is added
The Silane coupling reagent KH-570 that 0.6 times of quality, is stirred, and obtains silane coupled agent composition.The catalyst is nano oxidized
Magnesium.
Example 4
Nano-silicon nitride and nano aluminum nitride 2:1 in mass ratio are mixed in beaker, and nano-silicon nitride is added into beaker
The ethyl alcohol and 0.4 times of nano-silicon nitride quality of Silane coupling reagent KH-570 that 6 times of quality, the hydroxide for being 10% with mass fraction
Sodium solution is adjusted in pH beaker after the pH to 10.0 of material, is 65 DEG C in temperature, revolving speed stirs mixed under conditions of being 400r/min
After closing 4h, and under conditions of frequency is 55kHz after ultrasonic disperse 20min, then the item for being 130 DEG C in temperature by material in beaker
Under part after dry 4h, pretreatment conduction powder is obtained；Carbon nanotube is mixed with dehydrated alcohol 1:320 in mass ratio, is in frequency
Under conditions of 55kHz after ultrasonic disperse 30min, with mass fraction be 18% potassium hydroxide solution adjust carbon nanotube with it is anhydrous
The pH to 10 of alcohol mixture, and be 90 DEG C in temperature, after revolving speed is stirred to react 9h under conditions of being 400r/min, obtain carbon nanometer
Pipe mixture, the pH for adjusting carbon nanotube mixture with the hydrochloric acid that mass fraction is 8% filter to neutrality, filter cake are obtained, by filter cake
After being washed with water 10 times, after being dried in vacuo 5h under conditions of being 80 DEG C in temperature, pretreatment carbon nanotube is obtained；Pretreatment carbon is received
Mitron and ethanol water 1:320 in mass ratio are mixed in conical flask, and pretreatment carbon nanotube matter is added into conical flask
The mass fraction of 4 times of amount is 28% ammonium hydroxide, under conditions of frequency is 55kHz after ultrasonic disperse 70min, in the item of ultrasonic disperse
To instill the ethyl orthosilicate mixture for pre-processing 6 times of carbon nanotube mass under conditions of 12mL/min into conical flask under part,
After being added dropwise, it is 60 DEG C in temperature, after revolving speed is stirred 18h under conditions of being 400r/min, obtains pretreatment carbon nanotube
Mixture；Will pretreatment carbon nanotube mixture mixed with silane coupled agent composition 300:4 in mass ratio, in temperature be 55
DEG C, after revolving speed is stirred 7h under conditions of being 350r/min, filters, obtain pre- modified carbon nano tube blank, pre- carbon modified is received
After mitron blank is washed with water 8 times, pre- modified carbon nano-tube is obtained；Pre- modified carbon nano-tube is mixed with water 1:400 in mass ratio
In flask, and the acetic acid for being 25% with mass fraction adjusts the pH to 4.8 of material in flask, and pre- modification is added into flask
The hydroxy silicon oil that 0.5 times of carbon nanotube mass is 65 DEG C in temperature, and revolving speed is stirred 40min under conditions of being 400r/min
Afterwards, by material in flask after being aged 3h under room temperature, filtering obtains filter residue, after filter residue is washed with water 12 times, is in temperature
Under conditions of 70 DEG C after dry 40min, modified carbon nano tube blank is obtained；By modified carbon nano tube blank and water in mass ratio 1:
200 are mixed in three-necked flask, and the amino silane of 0.5 times of modified carbon nano tube blank quality is added into three-necked flask, in
Temperature is 90 DEG C, and after revolving speed is stirred 5h under conditions of being 320r/min, temperature of charge in three-necked flask is cooled to 45 DEG C,
And adjusted in three-necked flask after the pH value 6.8 of material with mass fraction for 20% acetic acid, filtering obtains pretreatment modification carbon nanometer
Pipe obtains modified carbon nano-tube after being dried in vacuo 2h under conditions of being 70 DEG C in temperature by pretreatment modification carbon nanotube；By weight
Number meter, successively weighs: 80 parts of silicone oil, 12 parts of epoxidized soybean oils, 18 parts of pretreatment conduction powders and 25 parts of modified carbon nano-tubes；
Silicone oil and epoxidized soybean oil are mixed in blender, conduction powder and modified carbon nano-tube are pre-processed, is 65 DEG C in temperature, turns
After speed is stirred 60min under conditions of being 400r/min, heat conductive insulating silicone grease is obtained.The average caliber of the carbon nanotube is
30nm, length are 100 μm.The ethanol water is that 4:1 is mixed by volume with water by dehydrated alcohol, obtains ethanol water.
The ethyl orthosilicate mixture is that can mix ethyl orthosilicate than 1:10 by quality with dehydrated alcohol, and it is mixed to obtain ethyl orthosilicate
Close object.The silane coupled agent composition is to mix dehydrated alcohol and acetic acid 1:1 in mass ratio, and dehydrated alcohol quality is added
0.6 times of Silane coupling reagent KH-570, is stirred, and obtains silane coupled agent composition.
Comparative example: the heat conductive insulating silicone grease of Shanghai tech materials production Co., Ltd production.
Example 1 to the resulting heat conductive insulating silicone grease of example 4 and comparative example product are subjected to performance detection, specific detection method
It is as follows:
Thermal conductivity: according to 10294 standard of GB/T, (transient hot wire technique) detection test specimen is measured using thermal constant analyzer.
Volume resistivity: according to 1410 standard of GB/T, detection test specimen is measured using megger.
Specific testing result is as shown in table 1:
1 heat-conducting insulating silicon rouge performance test results of table
| Detection project | Example 1 | Example 2 | Example 3 | Example 4 | Comparative example |
| Thermal conductivity/Wm-1K-1 | 3.98 | 3.65 | 2.77 | 2.03 | 1.16 |
| Volume resistivity/Ω cm | 9.13×1016 | 8.90×1016 | 6.27×1016 | 3.84×1016 | 1.89×1016 |
By 1 testing result of table it is found that the heat conductive insulating silicone grease of technical solution of the present invention preparation is with excellent heating conduction and absolutely
The characteristics of edge performance, has broad prospects in the development of thermal interfacial material industry.
Claims (7)
1. a kind of preparation method of heat conductive insulating silicone grease, which is characterized in that specific preparation step are as follows:
(1) carbon nanotube is mixed with dehydrated alcohol 1:300~1:320 in mass ratio, after ultrasonic disperse, adjusts pH to 8~10,
And be stirred to react, carbon nanotube mixture is obtained, the pH of carbon nanotube mixture is adjusted to neutrality, filters, wash, drying obtains pre-
Handle carbon nanotube；
(2) pretreatment carbon nanotube is mixed with ethanol water 1:300~1:320 in mass ratio, and pretreatment carbon is added and receives
The ammonium hydroxide that 2~4 times of mitron quality, ultrasonic disperse instill while ultrasonic disperse and pre-process 4~6 times of carbon nanotube mass
Ethyl orthosilicate mixture after being stirred, obtains pretreatment carbon nanotube mixture；It will pretreatment carbon nanotube mixture and silicon
Alkane is coupled agent composition 300:1~300:4 in mass ratio mixing, after being stirred, filters, and washing obtains pre- modified carbon nano-tube；
(3) pre- modified carbon nano-tube is mixed with water 1:200~1:400 in mass ratio, adjusts pH to 4.0~4.8, and be added pre-
The hydroxy silicon oil that 0.4~0.5 times of modified carbon nano-tube quality after being stirred, is aged, filters, washs, dry, obtains carbon modified
Nanometer blank；
(4) modified carbon nano tube blank is mixed with water 1:100~1:200 in mass ratio, and modified carbon nano tube blank is added
The amino silane that 0.3~0.5 times of quality, after being stirred, cooling, and pH value 6.5~6.8 is adjusted, and it filters, it is dry, obtain modification
Carbon nanotube；
(5) according to parts by weight, it successively weighs: 70~80 parts of silicone oil, 10~12 parts of epoxidized soybean oils, 5~8 parts of catalyst, 10
~18 parts of pretreatment conduction powders and 15~25 parts of modified carbon nano-tubes；Silicone oil is mixed with epoxidized soybean oil, and catalysis is added
Agent pre-processes conduction powder and modified carbon nano-tube, after being stirred, obtains heat conductive insulating silicone grease.
2. a kind of preparation method of heat conductive insulating silicone grease according to claim 1, it is characterised in that: step (1) described carbon
The average caliber of nanotube is 10~30nm, and length is 0.5~100 μm.
3. a kind of preparation method of heat conductive insulating silicone grease according to claim 1, it is characterised in that: step (2) described second
Alcohol solution is that 4:1 is mixed by volume with water by dehydrated alcohol, obtains ethanol water.
4. a kind of preparation method of heat conductive insulating silicone grease according to claim 1, it is characterised in that: step (2) is described just
Silester mixture is that can mix ethyl orthosilicate than 1:8~1:10 by quality with dehydrated alcohol, and it is mixed to obtain ethyl orthosilicate
Close object.
5. a kind of preparation method of heat conductive insulating silicone grease according to claim 1, it is characterised in that: step (2) described silicon
It is to mix dehydrated alcohol and acetic acid 1:1 in mass ratio, and be added 0.4~0.6 times of dehydrated alcohol quality that alkane, which is coupled agent composition,
Silane coupling reagent KH-570, be stirred, obtain silane coupled agent composition.
6. a kind of preparation method of heat conductive insulating silicone grease according to claim 1, it is characterised in that: step (5) is described to urge
Agent is any one in nano magnesia or nano zine oxide.
7. a kind of preparation method of heat conductive insulating silicone grease according to claim 1, it is characterised in that: step (5) is described pre-
Processing conduction powder is to mix nano-silicon nitride with nano aluminum nitride 1:1~2:1 in mass ratio, and it is siliceous that nano silicon nitride is added
4~6 times of ethyl alcohol and 0.3~0.4 times of nano-silicon nitride quality of Silane coupling reagent KH-570 are measured, pH to 9.8~10.0 is adjusted
Afterwards, it is stirred, ultrasonic disperse, it is dry, obtain pretreatment conduction powder.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1052893A (en) * | 1990-11-12 | 1991-07-10 | 天津大学 | Enhanced moisture-resistant agent for resin bonded sand |
| US20070149834A1 (en) * | 2005-12-27 | 2007-06-28 | Shin-Etsu Chemical Co., Ltd. | Heat conductive silicone grease compositions |
| JP2009096961A (en) * | 2007-10-19 | 2009-05-07 | Shin Etsu Chem Co Ltd | Heat-conductive silicone grease composition excellent in reworkability |
| CN101597418A (en) * | 2009-06-18 | 2009-12-09 | 华中科技大学 | A kind of electric insulation heat-conducting resin composite material and preparation method thereof |
| CN102583403A (en) * | 2012-03-06 | 2012-07-18 | 山东理工大学 | Preparation method of super-hydrophobic nanoscale white carbon black membrane and super-hydrophobic nanoscale white carbon black powder |
| CN103709757A (en) * | 2013-12-30 | 2014-04-09 | 无锡中石油润滑脂有限责任公司 | Insulating and heat-conducting silicone grease and preparation method thereof |
-
2018
- 2018-07-11 CN CN201810755728.3A patent/CN108976802B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1052893A (en) * | 1990-11-12 | 1991-07-10 | 天津大学 | Enhanced moisture-resistant agent for resin bonded sand |
| US20070149834A1 (en) * | 2005-12-27 | 2007-06-28 | Shin-Etsu Chemical Co., Ltd. | Heat conductive silicone grease compositions |
| JP2009096961A (en) * | 2007-10-19 | 2009-05-07 | Shin Etsu Chem Co Ltd | Heat-conductive silicone grease composition excellent in reworkability |
| CN101597418A (en) * | 2009-06-18 | 2009-12-09 | 华中科技大学 | A kind of electric insulation heat-conducting resin composite material and preparation method thereof |
| CN102583403A (en) * | 2012-03-06 | 2012-07-18 | 山东理工大学 | Preparation method of super-hydrophobic nanoscale white carbon black membrane and super-hydrophobic nanoscale white carbon black powder |
| CN103709757A (en) * | 2013-12-30 | 2014-04-09 | 无锡中石油润滑脂有限责任公司 | Insulating and heat-conducting silicone grease and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| MOHAMED A. ABDELWAHAB等: ""Epoxidized pine oil-siloxane: Crosslinking kinetic study and thermomechanical properties"", 《JOURNAL OF APPLIED POLYMER SCIENCE》 * |
| 张群: ""环氧大豆油改性白炭黑对天然橡胶性能的影响"", 《橡胶工业》 * |
| 贺曼罗: "《环氧树脂胶粘剂》", 30 April 2004, 中国石化出版社 * |
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