CN109971180A - A kind of high-temperature resistant heat-conducting silicone grease and preparation method thereof - Google Patents
A kind of high-temperature resistant heat-conducting silicone grease and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of high-temperature resistant heat-conducting silicone greases and preparation method thereof, belong to the technical field of silicone grease.Silicone grease raw material prepared by the present invention; with certain reinforcing effect, the silicone grease after solidification has the lower coefficient of cubical expansion and better cold-hot number of shocks, and firmness change is small in ageing process; and the phenomenon that making it not generate cracking, differentiation, form preferable siliceous protective layer；The filler additive of preparation improves and improves with the compatibility of silicone grease matrix, the interaction between nano particle reduced, so that heat transfer efficiency is enhanced；The active crosslinker of preparation reduces the viscosity that silicone grease is influenced on the hydrolysis of silicone grease, while the resistance to temperature stability of silicone grease is improved using ketoxime base, so that silicone grease forms preferable cold-resistant Thermal protection, and prevents the injury to silicone grease matrix.The present invention solves current heat-conducting silicone grease and occurs the problem of the phenomenon that silicone oil is separated with heat filling, silicone grease coating meeting fragmentation, heating conduction is deteriorated after multiple cold cycling.
Description
Technical field
The present invention relates to the technical field of silicone grease, in particular to a kind of high-temperature resistant heat-conducting silicone grease and preparation method thereof.
Background technique
With the development of science and technology, the densification of integrated circuit and micromation degree are higher and higher, the operation of electronic component
Speed is continuously improved, and power density is continuously increased, and when work can release amount of heat, if cannot be transferred out in time
It goes, it is easy to localized hyperthermia is caused, device lifetime is caused to reduce, or even loses effect, thus to the heat dissipation of electronic device to pass
It is important.And there are imperceptible rough the air gap, air thermal conductivities between microelectronic material surface and radiator
Only 0.024W/ (mK) is the non-conductor of heat, and the thermal contact resistance that will lead between electronic component and radiator is very big, sternly
The conduction of heat is hindered again, ultimately causes the inefficiency of radiator.Heat-conducting silicone grease, referred to as " silicone grease ", be commonly called as heat-conducting cream or
Thermal grease is in high efficiency and heat radiation product paste, is mixed with matrix silicone oil by process for treating surface etc. by heat filling
At high heat conductive insulating organosilicon material, can -50 ~ 230 DEG C at a temperature of for a long time keep use when fat state.To have
Machine silicone is primary raw material, adds heat-resisting, excellent thermal conductivity material, and manufactured heat-conducting type organosilicon smectic compound is used
In the thermally conductive of the electronic components such as power amplifier, transistor, electron tube, CPU and heat dissipation, to guarantee electronic instrument and meter
Deng electric property stabilization.Not only there is excellent electrical insulating property, but also have excellent thermal conductivity, while having low oily (to become from degree
To in zero), high-low temperature resistant, water-fast, ozone, weather-resistant.Heat-conducting silicone grease is also referred to as thermal interfacial material, heat dissipation with it is thermally conductive
In, even very bright and clean two planes in surface have gap appearance in the Shi Douhui that contacts with each other, the sky in these gaps
Gas is the non-conductor of heat, can hinder conduction of the heat to cooling fin.And heat-conducting silicone grease is exactly that one kind can fill these gaps,
Make the more smooth rapid material of the conduction of heat.It can be coated on various electronic products, the heater in electrical equipment extensively
Contact surface between (power tube, silicon-controlled, electric heating heap etc.) and cooling facilities (cooling fin, heat sink strip, shell etc.) plays heat transfer matchmaker
Jie effect and the performances such as moisture-proof, dust-proof, anticorrosion, shockproof, be suitable for microwave communication, microwave transport equipment, microwave power source special,
The surface of the various microwave devices such as regulated power supply coats or whole encapsulating.Heat-conducting silicone grease provides the electronic component for generating heat
Splendid heat-conducting effect.Heat-conducting silicone grease can be used for such as: transistor, CPU assembling, thermistor, temperature sensor, automotive electronics zero
During component, refrigerator of vehicle, power module, printer are first-class.Heat-conducting silicone grease is filled between heater and radiator, can effectively be filled out
The spatial joint clearance of full contact surface, abundant wetting contact surface reduces the work of electronic component to substantially reduce contact resistance
Temperature improves reliability and extends the service life.However, most of heat-conducting silicone greases currently on the market are in order to pursue single high thermal conductivity
Rate is usually filled a large amount of heat filling mechanical mixture in matrix silicone oil and is prepared, this is easy so that silicone grease viscosity mistake
Height, influences the mobility of silicone grease, finally influences practical heat dissipation effect when it is used to encapsulate.And it is filled out using low viscosity matrix silicone oil
The silicone grease of heat filling preparation is filled, mobility is excessive, then is easy trickling, is easy to appear pollution circuit board in use, draws
Play the failures such as short circuit.In addition, in the long-term use, passing through because the compatibility of heat filling and silicone oil is poor in silicone grease
After multiple cold cycling, often there is the phenomenon that silicone oil is separated with heat filling, causes silicone grease coating to dry out, differentiation, fragmentation, lead
Hot property variation etc..When simultaneously in face of the instantaneous high-power heat production of heating device, silicone grease heat conduction and heat radiation not in time, easily leads to heat
Accumulation rapidly, temperature increase, and influence the properties of electronic device.
Summary of the invention
The technical problems to be solved by the invention: occur after multiple cold cycling for current heat-conducting silicone grease silicone oil with
The phenomenon that heat filling separates, silicone grease coating can fragmentation, the problem of heating conduction is deteriorated, provide a kind of high-temperature resistant heat-conducting silicone grease and
Preparation method.
In order to solve the above technical problems, the present invention is using technical solution as described below:
A kind of high-temperature resistant heat-conducting silicone grease, including silicone grease raw material, filler additive, active crosslinker.
The silicone grease raw material the preparation method comprises the following steps: take dimethoxydiphenylsilane 3 ~ 7:5 in mass ratio ~ 10 be added third
Ketone, the sodium hydroxide solution that acetone quality 5 ~ 10% is added are stirred, and are stood, and precipitating rotary evaporation is taken, and it is surplus to collect rotary evaporation
Excess takes rotary evaporation residue 1 ~ 3:5 in mass ratio ~ 8 that toluene is added and is stirred, the clay of toluene quality 5 ~ 10% is added
Raw material is stirred, and filtering takes filtrate 2 ~ 5:10 in mass ratio ~ 15 that normal heptane is added, and stands 1 ~ 3h, and filtering takes filtration cakes torrefaction,
Up to silicone grease raw material.
The raw clay are as follows: take diatomite 5 ~ 8:1 in mass ratio ~ 4 be added kaolin mixing to get.
The filler additive the preparation method comprises the following steps: take heat filling 2 ~ 5:10 in mass ratio ~ 15 be added N- methylpyrrole
Alkanone is stirred, and obtains mixture, takes mixture 10 ~ 20:2 in mass ratio ~ 5 that 3,5- diaminobenzoic acid is added, and mixing is added
The pyridine of amount of substance 10 ~ 20% adds the triphenyl phosphite of mixture quality 1 ~ 3%, is passed through nitrogen protection, is stirred,
It is cooled to room temperature, filters, take filter cake to wash through n,N-Dimethylformamide, methanol, be dried in vacuo to get filler additive.
The heat filling are as follows: take graphene nanometer sheet, hexagonal boron nitride, ball-aluminium oxide, silicon carbide whisker, nitridation
Aluminium, antimony powder, any one in carbon fiber or it is any it is several by any mass ratio mix to get.
The active crosslinker the preparation method comprises the following steps:
(1) it takes diacetylmonoxime 2 ~ 5:5 in mass ratio ~ 10 that n-hexane is added, is passed through nitrogen protection, is stirred, then diacetylmonoxime is added dropwise
The Chloromethyltrichlorosilane of quality 30 ~ 40% is stirred, and is stood, and is taken supernatant 10 ~ 20:1 in mass ratio ~ 3 that triethylamine is added and is stirred
Mixing is mixed, is filtered, is taken filtrate decompression to distill, obtain vacuum distillation object；
(2) it takes a n-butylamine 3 ~ 5:40 in mass ratio ~ 50 that acetonitrile is added, is passed through nitrogen protection, is stirred, then a positive fourth is added dropwise
1 ~ 3 times of amine quality of vacuum distillation object is stirred, and filtering takes filtrate decompression to distill to get active crosslinker.
The preparation method includes the following steps:
A. it takes octamethylcy-clotetrasiloxane 3 ~ 7:1 in mass ratio ~ 3 that silicone grease raw material is added, adds silicone grease material quality 4 ~ 8%
Hexamethyldisiloxane is stirred, and obtains stirring mixture, takes stirring mixture 200 ~ 500:1 in mass ratio ~ 3 that hydroxide is added
Potassium is stirred, and is cooled to room temperature, and cooled material is obtained, and takes cooled material 1 ~ 3:2 in mass ratio ~ 5 that hexahydrotoluene is added, and cooling is added
The acetic acid of amount of substance 1 ~ 3% is stirred, and must stir mixture a；
B. it takes stirring mixture a 200 ~ 300:1 in mass ratio ~ 3 that sodium bicarbonate is added to be stirred, is evaporated under reduced pressure, steaming must be depressurized
Object a is evaporated, according to the mass fraction, takes 200 ~ 300 parts of vacuum distillation object a, 20 ~ 50 parts of filler additives, 10 ~ 15 parts of activity crosslinkings
Agent, 1 ~ 3 part of emulsifying dispersant are stirred to get high-temperature resistant heat-conducting silicone grease.
Emulsifying dispersant in the step B are as follows: take peregal O-3 2 ~ 5:1 in mass ratio ~ 4:1 ~ 3 be added paregal O -7,
OP-10 mixing to get.
The present invention is compared with other methods, and advantageous effects are:
(1) silicone grease raw material prepared by the present invention is that the raw materials such as sodium hydroxide solution, purifying are added through dimethoxydiphenylsilane
The cyclotetrasiloxane containing phenyl is obtained, then it is raw material that methyl-silicone oil, which is added, as raw material using it, prepares methyl phenyl silicone oil as silicon
The raw material of rouge, in cross-linking process with make structure itself formed cross-linked structure, formed high-crosslinking-degree skeleton, have
Certain reinforcing effect, improves hardness, and utilizes the silicone oil type phenyl introduced, due to hydrogen containing siloxane molecular weight compared with
Greatly, the silicone grease after solidification has the lower coefficient of cubical expansion and better cold-hot number of shocks, and hardness becomes in ageing process
Change small, and the phenomenon that make it not generate cracking, differentiation, forms preferable siliceous protective layer；
(2) filler additive prepared by the present invention is with graphene nanometer sheet, hexagonal boron nitride, ball-aluminium oxide etc. for raw material,
With 3,5- diaminobenzoic acid for monomer, in heat filling surface grafting Hyperbranched Aromatic Polyamides polymer, due to hyperbranched knot
Structure is wound it tightly with filler, improves the conjugation of itself and silicone grease matrix, and the separation for reducing heat filling is precipitated,
And by reducing heat filling surface free energy, improves and improved with the compatibility of silicone grease matrix, reduced between nano particle
Interaction to improve the dispersibility of nano particle, while can form covalent bond with silicone grease using the amino introduced, this
Two-phase interface thermal resistance can be effectively reduced in strong interaction, so that heat transfer efficiency is enhanced；
(3) active crosslinker prepared by the present invention is to generate the silicon containing ketoxime base with diacetylmonoxime, Chloromethyltrichlorosilane reaction
Alkane, then nucleophilic substitution is carried out with a n-butylamine, and crosslinking agent is made to contain a large amount of connection active site, with silicone grease base
Body carries out being cross-linked to form tridimensional network, and hinders diffusion of moisture in air inside silicone grease, reduces to silicone grease
The viscosity of silicone grease is hydrolyzed and influenced, while improving the resistance to temperature stability of silicone grease using ketoxime base, in cold cycling repeatedly,
Oxime key forms self-crosslinking reparation, and silicone grease is made to form preferable cold-resistant Thermal protection, and prevents the injury to silicone grease matrix；
(4) present invention first reduces firmness change and the coefficient of cubical expansion in cold-resistant thermal shock with silicone grease raw material, reduces extraneous ring
Border prevents cracking, differentiation to the injury in the structure of silicone grease, then is wound with filler additive and heat filling, reduces phase
Separation is precipitated, and improves the dispersion performance of heat filling, reduces the thermal resistance between filler and silicone grease, enhances heat transfer efficiency, finally
Active crosslinker is added, forms the cross-linked structure with self-healing properties, tolerance is strong under cooling thermal impact, forms length to silicone grease
The protective value of effect.
Specific embodiment
Raw clay are as follows: take diatomite 5 ~ 8:1 in mass ratio ~ 4 be added kaolin mixing to get.
Silicone grease raw material the preparation method comprises the following steps: take dimethoxydiphenylsilane 3 ~ 7:5 in mass ratio ~ 10 be added acetone, add
The sodium hydroxide solution for entering the mass fraction 0.5% of acetone quality 5 ~ 10% is warming up to 50 ~ 60% and is stirred 1 ~ 3h, stand 30 ~
60min takes precipitating rotary evaporation, collects rotary evaporation residue, takes rotary evaporation residue 1 ~ 3:5 in mass ratio ~ 8 that first is added
Benzene is stirred 20 ~ 40min, and the raw clay of toluene quality 5 ~ 10% is added, is stirred 30 ~ 60min, filters, takes filtrate
Normal heptane is added in 2 ~ 5:10 in mass ratio ~ 15, stands 1 ~ 3h, and filtering takes filtration cakes torrefaction to get silicone grease raw material.
Heat filling are as follows: take graphene nanometer sheet, hexagonal boron nitride, ball-aluminium oxide, silicon carbide whisker, aluminium nitride, antimony
Any one in powder, carbon fiber or it is any it is several by any mass ratio mix to get.
Filler additive the preparation method comprises the following steps: take heat filling 2 ~ 5:10 in mass ratio ~ 15 be added N-Methyl pyrrolidone,
It is stirred 20 ~ 30min in 20 ~ 40 DEG C, obtains mixture, takes mixture 10 ~ 20:2 in mass ratio ~ 5 that 3,5- diaminobenzene is added
Formic acid is added the pyridine of mixture quality 10 ~ 20%, adds the triphenyl phosphite of mixture quality 1 ~ 3%, is passed through nitrogen guarantor
Shield, is warming up to 90 ~ 100 DEG C and is stirred 2 ~ 4h, be cooled to room temperature, and filters, filter cake is taken to wash through n,N-Dimethylformamide, methanol
It washs, is dried in vacuo to get filler additive.
Active crosslinker the preparation method comprises the following steps:
(1) it takes diacetylmonoxime 2 ~ 5:5 in mass ratio ~ 10 that n-hexane is added, is passed through nitrogen protection, it is stirred 20 in 20 ~ 25 DEG C ~
30min, then the Chloromethyltrichlorosilane of diacetylmonoxime quality 30 ~ 40% is added dropwise is stirred 2 ~ 4h in 20 ~ 25 DEG C, stand 20 ~
30min takes supernatant 10 ~ 20:1 in mass ratio ~ 3 that triethylamine is added, is stirred 20 ~ 30min, filters, filtrate decompression is taken to steam
It evaporates, obtains vacuum distillation object；
(2) it takes a n-butylamine 3 ~ 5:40 in mass ratio ~ 50 that acetonitrile is added, is passed through nitrogen protection, it is stirred 20 in 20 ~ 25 DEG C ~
40min, then the vacuum distillation object of 1 ~ 3 times of a n-butylamine quality is added dropwise, it is stirred 4 ~ 7h in 30 ~ 35 DEG C, filters, filtrate is taken to subtract
Pressure distillation is to get active crosslinker.
Emulsifying dispersant are as follows: take peregal O-3 2 ~ 5:1 in mass ratio ~ 4:1 ~ 3 that paregal O -7, OP-10 mixing is added, i.e.,
?.
A kind of preparation method of high-temperature resistant heat-conducting silicone grease, includes the following steps:
A. it takes octamethylcy-clotetrasiloxane 3 ~ 7:1 in mass ratio ~ 3 that silicone grease raw material is added, adds silicone grease material quality 4 ~ 8%
Hexamethyldisiloxane is stirred 30 ~ 50min, obtains stirring mixture, takes stirring mixture 200 ~ 500:1 ~ 3 in mass ratio
Potassium hydroxide is added, is warming up to 150 ~ 160 DEG C and is stirred 6 ~ 8h, be cooled to room temperature, obtain cooled material, take cooled material in mass ratio
Hexahydrotoluene is added in 1 ~ 3:2 ~ 5, and the acetic acid of cooled material quality 1 ~ 3% is added, is stirred 60 ~ 90min, obtains stirring mixture
a；
B. it takes stirring mixture a 200 ~ 300:1 in mass ratio ~ 3 that sodium bicarbonate is added, is stirred 20 ~ 30min, be evaporated under reduced pressure,
It must be evaporated under reduced pressure object a, according to the mass fraction, take 200 ~ 300 parts of vacuum distillation object a, 20 ~ 50 parts of filler additives, 10 ~ 15 parts of work
Property crosslinking agent, 1 ~ 3 part of emulsifying dispersant, are stirred 1 ~ 3h in 60 ~ 70 DEG C to get high-temperature resistant heat-conducting silicone grease.
Embodiment 1
Raw clay are as follows: take diatomite 5:1 in mass ratio be added kaolin mixing to get.
Silicone grease raw material the preparation method comprises the following steps: take dimethoxydiphenylsilane 3:5 in mass ratio be added acetone, be added acetone
The sodium hydroxide solution of the mass fraction 0.5% of quality 5% is warming up to 50% and is stirred 1h, stands 30min, and precipitating rotation is taken to steam
Hair collects rotary evaporation residue, takes rotary evaporation residue 1:5 in mass ratio that toluene is added, is stirred 20min, is added
The raw clay of toluene quality 5% is stirred 30min, and filtering takes filtrate 2:10 in mass ratio that normal heptane is added, and stands 1h,
Filtering, takes filtration cakes torrefaction to get silicone grease raw material.
Heat filling are as follows: take graphene nanometer sheet.
Filler additive the preparation method comprises the following steps: take heat filling 2:10 in mass ratio be added N-Methyl pyrrolidone, in 20
DEG C it is stirred 20min, obtains mixture, take mixture 10:2 in mass ratio that 3,5- diaminobenzoic acid is added, mixture is added
The pyridine of quality 10% adds the triphenyl phosphite of mixture quality 1%, is passed through nitrogen protection, and it is mixed to be warming up to 90 DEG C of stirrings
2h is closed, is cooled to room temperature, is filtered, filter cake is taken to wash through n,N-Dimethylformamide, methanol, vacuum drying is to get filler addition
Agent.
Active crosslinker the preparation method comprises the following steps:
(1) it takes diacetylmonoxime 2:5 in mass ratio that n-hexane is added, is passed through nitrogen protection, is stirred 20min in 20 DEG C, then be added dropwise
The Chloromethyltrichlorosilane of diacetylmonoxime quality 30% is stirred 2h in 20 DEG C, stands 20min, takes supernatant 10:1 in mass ratio
Triethylamine is added, is stirred 20min, filters, takes filtrate decompression to distill, obtain vacuum distillation object；
(2) it takes n-butylamine 3:40 in mass ratio that acetonitrile is added, is passed through nitrogen protection, is stirred 20min in 20 DEG C, then be added dropwise
The vacuum distillation object of one 1 times of n-butylamine quality, is stirred 4h in 30 DEG C, filtering, takes filtrate decompression to distill to get activity crosslinking
Agent.
Emulsifying dispersant are as follows: take peregal O-3 2:1:1 in mass ratio be added paregal O -7, OP-10 mixing to get.
A kind of preparation method of high-temperature resistant heat-conducting silicone grease, includes the following steps:
A. it takes octamethylcy-clotetrasiloxane 3:1 in mass ratio that silicone grease raw material is added, adds the hexamethyl of silicone grease material quality 4%
Disiloxane is stirred 30min, obtains stirring mixture, takes stirring mixture 200:1 in mass ratio that potassium hydroxide is added, rises
Temperature is stirred 6h to 150 DEG C, is cooled to room temperature, obtains cooled material, takes cooled material 1:2 in mass ratio that hexahydrotoluene is added, adds
The acetic acid for entering cooled material quality 1%, is stirred 60min, must stir mixture a；
B. it takes stirring mixture a 200:1 in mass ratio that sodium bicarbonate is added, is stirred 20min, be evaporated under reduced pressure, steaming must be depressurized
Object a is evaporated, according to the mass fraction, takes 200 parts of vacuum distillation object a, 20 parts of filler additives, 10 parts of active crosslinkers, 1 part of emulsification point
Powder is stirred 1h in 60 DEG C to get high-temperature resistant heat-conducting silicone grease.
Embodiment 2
Raw clay are as follows: take diatomite 8:4 in mass ratio be added kaolin mixing to get.
Silicone grease raw material the preparation method comprises the following steps: take dimethoxydiphenylsilane 7:10 in mass ratio be added acetone, be added third
The sodium hydroxide solution of the mass fraction 0.5% of ketone quality 10% is warming up to 60% and is stirred 3h, stand 60min, precipitating is taken to revolve
Turn evaporation, collect rotary evaporation residue, takes rotary evaporation residue 3:8 in mass ratio that toluene is added, be stirred 40min,
The raw clay of toluene quality 10% is added, is stirred 60min, filters, takes filtrate 5:15 in mass ratio that normal heptane is added, it is quiet
3h is set, filters, takes filtration cakes torrefaction to get silicone grease raw material.
Heat filling are as follows: take ball-aluminium oxide.
Filler additive the preparation method comprises the following steps: take heat filling 5:15 in mass ratio be added N-Methyl pyrrolidone, in 40
DEG C it is stirred 30min, obtains mixture, take mixture 20:5 in mass ratio that 3,5- diaminobenzoic acid is added, mixture is added
The pyridine of quality 20% adds the triphenyl phosphite of mixture quality 3%, is passed through nitrogen protection, and it is mixed to be warming up to 100 DEG C of stirrings
4h is closed, is cooled to room temperature, is filtered, filter cake is taken to wash through n,N-Dimethylformamide, methanol, vacuum drying is to get filler addition
Agent.
Active crosslinker the preparation method comprises the following steps:
(1) it takes diacetylmonoxime 5:10 in mass ratio that n-hexane is added, is passed through nitrogen protection, is stirred 30min in 25 DEG C, then be added dropwise
The Chloromethyltrichlorosilane of diacetylmonoxime quality 40% is stirred 4h in 25 DEG C, stands 30min, takes supernatant 20:3 in mass ratio
Triethylamine is added, is stirred 30min, filters, takes filtrate decompression to distill, obtain vacuum distillation object；
(2) it takes n-butylamine 5:50 in mass ratio that acetonitrile is added, is passed through nitrogen protection, is stirred 40min in 25 DEG C, then be added dropwise
The vacuum distillation object of one 3 times of n-butylamine quality, is stirred 7h in 35 DEG C, filtering, takes filtrate decompression to distill to get activity crosslinking
Agent.
Emulsifying dispersant are as follows: take peregal O-3 5:4:3 in mass ratio be added paregal O -7, OP-10 mixing to get.
A kind of preparation method of high-temperature resistant heat-conducting silicone grease, includes the following steps:
A. it takes octamethylcy-clotetrasiloxane 7:3 in mass ratio that silicone grease raw material is added, adds the hexamethyl of silicone grease material quality 8%
Disiloxane is stirred 50min, obtains stirring mixture, takes stirring mixture 500:3 in mass ratio that potassium hydroxide is added, rises
Temperature is stirred 8h to 160 DEG C, is cooled to room temperature, obtains cooled material, takes cooled material 3:5 in mass ratio that hexahydrotoluene is added, adds
The acetic acid for entering cooled material quality 3%, is stirred 90min, must stir mixture a；
B. it takes stirring mixture a 300:3 in mass ratio that sodium bicarbonate is added, is stirred 30min, be evaporated under reduced pressure, steaming must be depressurized
Object a is evaporated, according to the mass fraction, takes 300 parts of vacuum distillation object a, 50 parts of filler additives, 15 parts of active crosslinkers, 3 parts of emulsifications point
Powder is stirred 3h in 70 DEG C to get high-temperature resistant heat-conducting silicone grease.
Embodiment 3
Raw clay are as follows: take diatomite 7:3 in mass ratio be added kaolin mixing to get.
Silicone grease raw material the preparation method comprises the following steps: take dimethoxydiphenylsilane 5:7 in mass ratio be added acetone, be added acetone
The sodium hydroxide solution of the mass fraction 0.5% of quality 7% is warming up to 55% and is stirred 2h, stands 50min, and precipitating rotation is taken to steam
Hair collects rotary evaporation residue, takes rotary evaporation residue 2:7 in mass ratio that toluene is added, is stirred 30min, is added
The raw clay of toluene quality 7% is stirred 50min, and filtering takes filtrate 3:13 in mass ratio that normal heptane is added, and stands 2h,
Filtering, takes filtration cakes torrefaction to get silicone grease raw material.
Heat filling are as follows: take silicon carbide whisker.
Filler additive the preparation method comprises the following steps: take heat filling 3:13 in mass ratio be added N-Methyl pyrrolidone, in 30
DEG C it is stirred 25min, obtains mixture, take mixture 15:6 in mass ratio that 3,5- diaminobenzoic acid is added, mixture is added
The pyridine of quality 15% adds the triphenyl phosphite of mixture quality 2%, is passed through nitrogen protection, and it is mixed to be warming up to 95 DEG C of stirrings
3h is closed, is cooled to room temperature, is filtered, filter cake is taken to wash through n,N-Dimethylformamide, methanol, vacuum drying is to get filler addition
Agent.
Active crosslinker the preparation method comprises the following steps:
(1) it takes diacetylmonoxime 3:7 in mass ratio that n-hexane is added, is passed through nitrogen protection, is stirred 25min in 22 DEG C, then be added dropwise
The Chloromethyltrichlorosilane of diacetylmonoxime quality 35% is stirred 3h in 23 DEG C, stands 25min, takes supernatant 15:2 in mass ratio
Triethylamine is added, is stirred 25min, filters, takes filtrate decompression to distill, obtain vacuum distillation object；
(2) it takes n-butylamine 4:45 in mass ratio that acetonitrile is added, is passed through nitrogen protection, is stirred 30min in 23 DEG C, then be added dropwise
The vacuum distillation object of one 2 times of n-butylamine quality, is stirred 6h in 32 DEG C, filtering, takes filtrate decompression to distill to get activity crosslinking
Agent.
Emulsifying dispersant are as follows: take peregal O-3 3:2:2 in mass ratio be added paregal O -7, OP-10 mixing to get.
A kind of preparation method of high-temperature resistant heat-conducting silicone grease, includes the following steps:
A. it takes octamethylcy-clotetrasiloxane 5:2 in mass ratio that silicone grease raw material is added, adds the hexamethyl of silicone grease material quality 6%
Disiloxane is stirred 40min, obtains stirring mixture, takes stirring mixture 300:2 in mass ratio that potassium hydroxide is added, rises
Temperature is stirred 7h to 155 DEG C, is cooled to room temperature, obtains cooled material, takes cooled material 2:3 in mass ratio that hexahydrotoluene is added, adds
The acetic acid for entering cooled material quality 2%, is stirred 70min, must stir mixture a；
B. it takes stirring mixture a 250:2 in mass ratio that sodium bicarbonate is added, is stirred 25min, be evaporated under reduced pressure, steaming must be depressurized
Object a is evaporated, according to the mass fraction, takes 250 parts of vacuum distillation object a, 30 parts of filler additives, 12 parts of active crosslinkers, 2 parts of emulsifications point
Powder is stirred 2h in 65 DEG C to get high-temperature resistant heat-conducting silicone grease.
Comparative example 1: it is essentially identical with the preparation method of embodiment 2, it has only the difference is that lacking silicone grease raw material.
Comparative example 2: it is essentially identical with the preparation method of embodiment 2, it has only the difference is that lacking filler additive.
Comparative example 3: it is essentially identical with the preparation method of embodiment 2, it has only the difference is that lacking active crosslinker.
Comparative example 4: the high-temperature resistant heat-conducting silicone grease of company, Shenzhen production.
The high-temperature resistant heat-conducting silicone grease that above-described embodiment is prepared with comparative example is detected, viscosity presses GB/T 2794-1995
Requirement, using NDJ-7 rotary viscosity design determining；Thermal coefficient is measured by the requirement of GB/T 10294-2008；Volume electricity
Resistance rate is measured according to the requirement of GB/T 1410-2006；Latent heat of phase change value is surveyed using differential scanning calorimeter (DSC)
It is fixed.Measuring repeat number is 5 times, i.e. n=5, and result is the average value of 5 data in table, obtains that the results are shown in Table 1.
Table 1:
In summary, high-temperature resistant heat-conducting silicone grease effect of the invention is more preferable as can be seen from Table 1, is worth of widely use, the above institute
Preferred mode only of the invention is stated, is not intended to limit the invention, all within the spirits and principles of the present invention, made
What modification, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (8)
1. a kind of high-temperature resistant heat-conducting silicone grease, which is characterized in that including silicone grease raw material, filler additive, active crosslinker.
2. high-temperature resistant heat-conducting silicone grease according to claim 1, which is characterized in that the silicone grease raw material the preparation method comprises the following steps:
It takes dimethoxydiphenylsilane 3 ~ 7:5 in mass ratio ~ 10 that acetone is added, the sodium hydroxide solution of acetone quality 5 ~ 10% is added
It is stirred, stands, take precipitating rotary evaporation, collect rotary evaporation residue, take rotary evaporation residue 1 ~ 3:5 in mass ratio
~ 8 addition toluene is stirred, be added toluene quality 5 ~ 10% raw clay be stirred, filter, take filtrate in mass ratio 2 ~
Normal heptane is added in 5:10 ~ 15, stands 1 ~ 3h, and filtering takes filtration cakes torrefaction to get silicone grease raw material.
3. high-temperature resistant heat-conducting silicone grease according to claim 2, which is characterized in that the raw clay are as follows: take diatomite by
5 ~ 8:1 of mass ratio ~ 4 be added kaolin mixing to get.
4. high-temperature resistant heat-conducting silicone grease according to claim 1, which is characterized in that the preparation method of the filler additive
Are as follows: take heat filling 2 ~ 5:10 in mass ratio ~ 15 be added N-Methyl pyrrolidone be stirred, obtain mixture, take mixture by
3,5- diaminobenzoic acid is added in 10 ~ 20:2 of mass ratio ~ 5, and the pyridine of mixture quality 10 ~ 20% is added, adds compounding substances
The triphenyl phosphite of amount 1 ~ 3%, is passed through nitrogen protection, is stirred, be cooled to room temperature, and filters, takes filter cake through N, N- dimethyl
Formamide, methanol washing, are dried in vacuo to get filler additive.
5. high-temperature resistant heat-conducting silicone grease according to claim 4, which is characterized in that the heat filling are as follows: graphene is taken to receive
Rice piece, hexagonal boron nitride, ball-aluminium oxide, silicon carbide whisker, aluminium nitride, antimony powder, any one in carbon fiber or any several
By any mass ratio mix to get.
6. high-temperature resistant heat-conducting silicone grease according to claim 1, which is characterized in that the preparation method of the active crosslinker
Are as follows:
(1) it takes diacetylmonoxime 2 ~ 5:5 in mass ratio ~ 10 that n-hexane is added, is passed through nitrogen protection, is stirred, then diacetylmonoxime is added dropwise
The Chloromethyltrichlorosilane of quality 30 ~ 40% is stirred, and is stood, and is taken supernatant 10 ~ 20:1 in mass ratio ~ 3 that triethylamine is added and is stirred
Mixing is mixed, is filtered, is taken filtrate decompression to distill, obtain vacuum distillation object；
(2) it takes a n-butylamine 3 ~ 5:40 in mass ratio ~ 50 that acetonitrile is added, is passed through nitrogen protection, is stirred, then a positive fourth is added dropwise
1 ~ 3 times of amine quality of vacuum distillation object is stirred, and filtering takes filtrate decompression to distill to get active crosslinker.
7. a kind of preparation method of the high-temperature resistant heat-conducting silicone grease as described in claim 1 ~ 6 any one, which is characterized in that the system
Preparation Method includes the following steps:
A. it takes octamethylcy-clotetrasiloxane 3 ~ 7:1 in mass ratio ~ 3 that silicone grease raw material is added, adds silicone grease material quality 4 ~ 8%
Hexamethyldisiloxane is stirred, and obtains stirring mixture, takes stirring mixture 200 ~ 500:1 in mass ratio ~ 3 that hydroxide is added
Potassium is stirred, and is cooled to room temperature, and cooled material is obtained, and takes cooled material 1 ~ 3:2 in mass ratio ~ 5 that hexahydrotoluene is added, and cooling is added
The acetic acid of amount of substance 1 ~ 3% is stirred, and must stir mixture a；
B. it takes stirring mixture a 200 ~ 300:1 in mass ratio ~ 3 that sodium bicarbonate is added to be stirred, is evaporated under reduced pressure, steaming must be depressurized
Object a is evaporated, according to the mass fraction, takes 200 ~ 300 parts of vacuum distillation object a, 20 ~ 50 parts of filler additives, 10 ~ 15 parts of activity crosslinkings
Agent, 1 ~ 3 part of emulsifying dispersant are stirred to get high-temperature resistant heat-conducting silicone grease.
8. the preparation method of high-temperature resistant heat-conducting silicone grease according to claim 7, which is characterized in that emulsified in the step B
Dispersing agent are as follows: take peregal O-3 2 ~ 5:1 in mass ratio ~ 4:1 ~ 3 be added paregal O -7, OP-10 mixing to get.
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