CN110524922A - A kind of preparation method of thermally conductive silicone rubber composite material - Google Patents
A kind of preparation method of thermally conductive silicone rubber composite material Download PDFInfo
- Publication number
- CN110524922A CN110524922A CN201910681348.4A CN201910681348A CN110524922A CN 110524922 A CN110524922 A CN 110524922A CN 201910681348 A CN201910681348 A CN 201910681348A CN 110524922 A CN110524922 A CN 110524922A
- Authority
- CN
- China
- Prior art keywords
- composite material
- rubber
- thermally conductive
- silicone rubber
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
- B29C43/22—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of indefinite length
- B29C43/24—Calendering
- B29C43/245—Adjusting calender parameters, e.g. bank quantity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D7/00—Producing flat articles, e.g. films or sheets
- B29D7/01—Films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/08—Materials not undergoing a change of physical state when used
- C09K5/14—Solid materials, e.g. powdery or granular
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/28—Nitrogen-containing compounds
- C08K2003/282—Binary compounds of nitrogen with aluminium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/382—Boron-containing compounds and nitrogen
- C08K2003/385—Binary compounds of nitrogen with boron
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Thermal Sciences (AREA)
- Combustion & Propulsion (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Casting Or Compression Moulding Of Plastics Or The Like (AREA)
Abstract
The invention discloses a kind of preparation methods of thermally conductive silicone rubber composite material.Preparation method is first to be mixed with water and stratiform heat filling, and ultrasonic disperse adds vinyl silicone oil, and heating stirring evaporates moisture, obtains pre-dispersed object；Silicon rubber, reinforcing agent, pre-dispersed object, vulcanizing agent are mixed by rubber kneading machine, obtain rubber compound, rubber compound is rolled into flakiness using rubber calender, through hot-air presulfurization, then stretching and drawing, is thinned film, and occur to stretch orientation, thin film is rolled into cylindrical body, along being sliced perpendicular to cylinder axis direction, vulcanization is formed.For the present invention since heat filling is orientated along film stock thickness direction, film has high heat conductance.The thermal conductivity range of the silicon rubber composite material is 4~14W/ (mk), and thermal conductivity can be adjusted by the technological parameter and traction elongation for changing calender, and the preparation process simple process of composite material is environmentally protective.
Description
Technical field
The present invention relates to the preparation fields of thermally conductive silicone rubber composite material, and in particular to realizes stratiform by rubber calender
Different orientation degree of the heat filling in silicone rubber matrix, makes silicon rubber composite material acquisition high heat conductance and thermal conductivity is adjustable
Preparation method.
Background technique
As electronic component is towards miniaturization, integrated direction development, the demand to highly heat-conductive material is more more and more urgent.
Traditional metal base heat conducting material, although thermal conductivity is high, the disadvantage is that density is big, hardly possible processing, no elasticity.And heat-conducting polymer
Material has many advantages, such as that low-density, easy processing, shape are changeable.It include aluminium oxide, boron nitride, gold for high molecular heat filling
Belong to powder (copper powder, silver powder etc.), carbon-based filler (graphite, carbon nanotube etc.).Existing research shows that realize heat-conducting polymer material
The high heat conductance of material usually goes to realize using the method for increasing heat filling dosage, but this method often will cause material
Material mechanical property is remarkably decreased.
In addition, filler orientation can make heat-conducting polymer material obtain higher thermal conductivity.Such as Chinese invention patent
CN106867094A, which is reported, is pressed into thin slice to rubber composite material using open mill, is then overlapped thin slice, compared to
Conventional to be directly kneaded method, the thermal conductivity for preparing heat-conductive composite material in differently- oriented directivity increases.But for open mill plus
For work, sizing material crosses that the roller time is shorter, and roller speed, speed ratio, roll spacing and roller temperature are all difficult to adjust, and the orientation of heat filling is caused not fill
Point, degree of orientation is difficult to control, thus the thermal conductivity of Heat Conduction Material is also obviously improved space.
Summary of the invention
It is an object of the invention to overcome the shortcomings of prior art, a kind of rolled by rubber calender is provided and is prepared
The method of high-heat-conductingsilicon silicon rubber compound material, by changing calendering technology condition, so that silicon rubber composite material is in thickness direction
It is upper to realize different degrees of filler orientation, to obtain higher thermal conductivity, and thermal conductivity is adjustable in a big way.
Purpose to realize the present invention, The technical solution adopted by the invention is as follows:
A kind of preparation method of thermally conductive silicone rubber composite material, comprising the following steps:
(1) stratiform heat filling and water being mixed, ultrasonic disperse removes heat filling, vinyl silicone oil is then added,
It is mixed evenly, heating evaporation moisture, obtains the pre-dispersed object of vinyl silicone oil of stratiform heat filling；It is layered thermally conductive to fill out
Material is one of hexagonal boron nitride, aluminium nitride, lamellar graphite and graphene or a variety of mixtures；
(2) the pre-dispersed object of vinyl silicone oil of silicon rubber, reinforcing agent, heat filling is mixed in rubber kneading machine
It closes, vulcanizing agent is added, be kneaded uniformly, rubber compound is made；
(3) rubber compound is rolled to obtain thin film with rubber calender, heats presulfurization, traction stretches, and control is stretched
Long rate is 50%~100%, and winding obtains rubber cylinder；The roller temperature of the calendering is 50~80 DEG C, and speed ratio is 1.1~1.3,
Roll spacing between adjacent two roller is 0.5~2.0mm；
(4) rubber cylinder is cut into film along perpendicular to cylinder axis direction, controlled with a thickness of 1~10mm, it is low
Pressure vulcanization sizing；
In terms of mass fraction, the composition of raw materials of thermally conductive silicone rubber composite material is formed are as follows: 100 parts of silicon rubber, stratiform is thermally conductive
40~200 parts of filler, 10~50 parts of vinyl silicone oil, 10~40 parts of reinforcing agent, 1~5 part of vulcanizing agent.
To further realize the object of the invention, it is preferable that the silicon rubber is dimethyl silicone rubber, methyl ethylene silicon
One of rubber and methyl phenyl vinyl silicone rubber or a variety of mixtures.
Preferably, the power of the ultrasound is 300~600W, and ultrasonic time is 2~4h.
Preferably, the reinforcing agent is one of precipitated silica and gas-phase silica or a variety of mixtures.
Preferably, the vulcanizing agent is 2,5- dimethyl -2,5- di-t-butyl hexane peroxide, peroxidating diisopropyl
One of benzene, dibenzoyl peroxide or a variety of mixtures.
Preferably, the viscosity of the vinyl silicone oil is 100~500mPas.
Preferably, the rubber calender uses 3 rollers or 4 roll calendars, and roller arrangement is using I type, S type or Γ type row
Column mode.
Preferably, in step (3), the heating presulfurization is to carry out thin film in 180~200 DEG C of hot drying tunnel
Heating, heating time are 1~3min.
Preferably, in step (4), the sulfide stress of the thin film of the incision is 0.5~2.0MPa, and heating temperature is
160~190 DEG C, vulcanization time is 5~20min.
Preferably, in step (1), the stratiform heat filling and water are according to mass ratio 1:2~1:4；The mixing
The mixing speed stirred evenly is 100~300r/min, and mixing time is 30~60min；The heating evaporation moisture adds
Hot temperature is 100~150 DEG C.
Film presulfurization after calendering, to guarantee that traction drawing process film does not rupture.
Cardinal principle of the invention is the rolling effect using calender, and the silicon rubber of addition stratiform heat filling is allowed to mix
At the rolling mill roller gap by becoming narrow gradually, along rolling direction apparent orientation behavior occurs object for filler, i.e., along
Rolling direction generates aligning for layered fillers, and roll spacing is smaller, and the degree of orientation of filler is higher.And to the thin glue of calendering
Piece carries out traction stretching, and silicon rubber strand can be allowed to occur to stretch orientation, and film is further thinned, and is also beneficial to heat filling
Generate higher degree of orientation.After the thin slice of calendering is rolled into cylindrical body, heat filling will be along the axis side of cylindrical body
Multiple thermal conducting paths are formed to (i.e. perpendicular to rolling direction), thus it is higher along the thermal conductivity in cylinder axis direction.It will justify
Cylinder is along the film of 1~10mm is cut into perpendicular to axis direction, primarily to meeting answering for the thermally-conductive sheet of different-thickness
With needs.
Filler orientation mode is realized for existing conventional open mill, since the speed ratio of mill mixer roller, roller temperature etc. are all difficult
With adjustment, thus the degree of orientation of heat filling is unable to control and adjusts, and the thermal conductivity of mixture is lower and is difficult to, this
Outside, the mechanical property of silicon rubber film is also poor.Compared with the existing method for realizing heat filling orientation using rubber mixing mill,
The present invention carries out rolling orientation to silastic mixture using calender can by adjusting the roll spacing of calender, speed ratio, roller temperature
To adjust the degree of orientation of heat filling in silastic mixture in a big way, thus not increasing heat filling dosage
On the basis of, obtain the silicon rubber sheet material of high heat conductance and strong mechanical performance.
Compared with the existing technology, evident advantages of the present invention are:
(1) rubber mixing mill is replaced using rubber calender, can continuously adjusts the techniques such as roll spacing, speed ratio and roller temperature ginseng
Number, can be multiple with the heat-conducting silicon rubber for obtaining different orientation degree with the arrangement mode of the number of appropriate adjustment roller and roller
Condensation material can be in larger range only by calendering technology parameter is changed in the case where not changing heat filling dosage
The thermal conductivity of interior adjustment silicon rubber composite material；
(2) after ultrasound removing, specific surface area dramatically increases stratiform heat filling, and the vinyl silicon of heat filling is made
After the pre-dispersed object of oil, the dispersion in silicone rubber matrix is more uniform, and the thermal conductivity of silicon rubber composite material is caused significantly to mention
It is high；
(3) whole preparation process is without using any organic solvent, and VOC free discharge, environmentally protective, process flow is simple,
It is easily achieved continuous production.
Specific embodiment
In order to keep purposes, technical schemes and advantages of the present invention clearer, below by specific embodiment pair
Method of the invention is illustrated, this explanation is for explaining only the invention, not as a limitation of the invention.
The tensile strength of silicon rubber film is measured according to GB/T 528-2009.The thermal conductivity of silicon rubber film uses
The laser method of shining is measured (referring to national standard GB/T 22588-2008), shown in result such as formula (1):
λ=α × Cp×ρ (1)
In formula:
λ --- thermal coefficient, unit are W/ (mK)；
α --- thermal diffusion coefficient, unit m2/s；
Cp--- specific heat capacity, unit are J/ (kgK)；
ρ --- density, unit kg/m3。
Embodiment 1:
In terms of mass fraction, a kind of composition of raw materials of thermally conductive silicone rubber composite material is as follows:
100 parts of methyl vinyl silicone rubber
100 parts of hexagonal boron nitride
25 parts of vinyl silicone oil
25 parts of precipitated silica
2 parts of di-t-butyl hexane peroxide of 2,5- dimethyl -2,5-
A kind of preparation method of thermally conductive silicone rubber composite material, steps are as follows:
(1) hexagonal boron nitride and water are mixed according to mass ratio 1:3, ultrasonic disperse, power 600W, ultrasonic time 4h,
Hexagonal boron nitride is removed, the vinyl silicone oil that viscosity is 300mPas is then added, heating is mixed, mixing speed
For 300r/min, mixing time 60min, heating temperature is 150 DEG C, makes moisture evaporating completely, obtains the second of hexagonal boron nitride
The pre-dispersed object of alkenyl silicone oil；
(2) by methyl vinyl silicone rubber, precipitated silica, hexagonal boron nitride the pre-dispersed object of vinyl silicone oil in rubber
It is mixed in kneader, 2,5- dimethyl -2,5- di-t-butyl hexane peroxide is then added, be uniformly mixed, mixing is made
Glue；
(3) rubber compound is rolled with three roller I type calenders, 50 DEG C of roller temperature, roll spacing 2.0mm, speed ratio 1.1 obtains glue
Piece, through overheat drying tunnel heating, temperature is 180 DEG C, and time 2min is allowed to presulfurization, and then traction stretches, and elongation is
50%, winding obtains rubber cylinder；
(4) by rubber cylinder along perpendicular to cylinder axis direction cut, obtain with a thickness of 2mm film, then into
The vulcanization of row low pressure, curing temperature are 160 DEG C, sulfide stress 0.5MPa, vulcanization time 20min.
Thermal conductivity is 4.1W/ (mK), tensile strength 5.1MPa to gained silicon rubber composite material in a thickness direction.
Embodiment 2:
In terms of mass fraction, a kind of composition of raw materials of thermally conductive silicone rubber composite material is as follows:
100 parts of methyl vinyl silicone rubber
100 parts of hexagonal boron nitride
25 parts of vinyl silicone oil
25 parts of precipitated silica
2 parts of di-t-butyl hexane peroxide of 2,5- dimethyl -2,5-
A kind of preparation method of thermally conductive silicone rubber composite material, steps are as follows:
(1) hexagonal boron nitride and water are mixed according to mass ratio 1:3, ultrasonic disperse, power 600W, ultrasonic time 4h,
Hexagonal boron nitride is removed, the vinyl silicone oil that viscosity is 100mPas is then added, heating is mixed, mixing speed
For 300r/min, mixing time 60min, heating temperature is 150 DEG C, makes moisture evaporating completely, obtains the second of hexagonal boron nitride
The pre-dispersed object of alkenyl silicone oil；
(2) by methyl vinyl silicone rubber, precipitated silica, hexagonal boron nitride the pre-dispersed object of vinyl silicone oil in rubber
It is mixed in kneader, vulcanizing agent 2 is then added, 5- dimethyl -2,5- di-t-butyl hexane peroxide is uniformly mixed, system
At rubber compound；
(3) rubber compound is rolled with four-roller Γ type calender, 80 DEG C of roller temperature, roll spacing 0.5mm, speed ratio 1.3 obtains glue
Piece, through overheat drying tunnel heating, temperature is 180 DEG C, and heating time 2min is allowed to presulfurization, and then traction stretches, and elongation is
50%, winding obtains rubber cylinder；
(4) by rubber cylinder along perpendicular to cylinder axis direction cut, obtain with a thickness of 2mm film, then into
The vulcanization of row low pressure, curing temperature are 160 DEG C, sulfide stress 0.5MPa, vulcanization time 20min.
Thermal conductivity is 6.5W/ (mK), tensile strength 5.3MPa to gained silicon rubber composite material in a thickness direction.
Embodiment 3:
In terms of mass fraction, a kind of composition of raw materials of thermally conductive silicone rubber composite material is as follows:
100 parts of methyl vinyl silicone rubber
200 parts of hexagonal boron nitride
30 parts of gas-phase silica
50 parts of vinyl silicone oil
5 parts of di-t-butyl hexane peroxide of 2,5- dimethyl -2,5-
A kind of preparation method of thermally conductive silicone rubber composite material, steps are as follows:
(1) hexagonal boron nitride and water are mixed according to mass ratio 1:4, ultrasonic disperse, power 600W, ultrasonic time 3h,
Hexagonal boron nitride is removed, the vinyl silicone oil that viscosity is 100mPas is then added, is mixed, mixing speed is
300r/min, mixing time 40min, heating temperature are 130 DEG C, make moisture evaporating completely, obtain the ethylene of hexagonal boron nitride
The pre-dispersed object of base silicone oil；
(2) the pre-dispersed object of vinyl silicone oil of methyl vinyl silicone rubber, gas-phase silica, boron nitride is mediated in rubber
It carries out uniformly mixed in machine, is eventually adding 2,5- dimethyl -2,5- di-t-butyl hexane peroxide, rubber compound is made；
(3) rubber compound is rolled with four-roller I type calender, 80 DEG C of roller temperature, roll spacing 1.0mm, speed ratio 1.3 obtains glue
Piece, through overheat drying tunnel heating, temperature is 200 DEG C, heating time 1min, is allowed to presulfurization sizing, and then traction stretches, elongation
Rate is 100%, and winding obtains rubber cylinder；
(4) rubber cylinder is cut along perpendicular to cylinder axis direction, obtains the film with a thickness of 3mm, then
Low pressure vulcanization is carried out, curing temperature is 180 DEG C, sulfide stress 1.0MPa, vulcanization time 10min.
The thermal conductivity of gained silicon rubber composite material in a thickness direction is 10.6W/ (mK), and tensile strength is
4.2MPa。
Embodiment 4:
In terms of mass fraction, a kind of composition of raw materials of thermally conductive silicone rubber composite material is as follows:
100 parts of methyl vinyl silicone rubber
180 parts of lamellar graphite
20 parts of gas-phase silica
30 parts of vinyl silicone oil
1.5 parts of cumyl peroxide
A kind of preparation method of thermally conductive silicone rubber composite material, steps are as follows:
(1) lamellar graphite and water are mixed according to mass ratio 1:3, ultrasonic disperse, power 500W, ultrasonic time 3h make
Then lamellar graphite removing adds the vinyl silicone oil that viscosity is 500mPas, is mixed, mixing speed 300r/
Min, mixing time 50min, heating temperature are 150 DEG C, make moisture evaporating completely, the vinyl silicone oil for obtaining lamellar graphite is pre-
Dispersion；
(2) the pre-dispersed object of vinyl silicone oil of methyl vinyl silicone rubber, gas-phase silica, lamellar graphite is pinched in rubber
It is mixed in conjunction machine, vulcanizing agent cumyl peroxide is then added, be uniformly mixed, rubber compound is made；
(3) rubber compound is rolled with four-roller I type calender, 80 DEG C of roller temperature, roll spacing 1.2mm, speed ratio 1.3 obtains thin
Film, through overheat drying tunnel heating, temperature is 180 DEG C, heating time 2min, is allowed to presulfurization sizing, and then traction stretches, and stretches
Long rate is 100%, and winding obtains rubber cylinder；
(4) rubber cylinder is cut along perpendicular to cylinder axis direction, obtains the film with a thickness of 3mm, then
Low pressure vulcanization is carried out, curing temperature is 200 DEG C, sulfide stress 0.5MPa, vulcanization time 5min.
The thermal conductivity of gained silicon rubber composite material in a thickness direction is 8.1W/ (mK), tensile strength 4.5MPa.
Embodiment 5:
In terms of mass fraction, a kind of composition of raw materials of thermally conductive silicone rubber composite material is as follows:
100 parts of methyl phenyl vinyl silicone rubber
40 parts of graphene
20 parts of gas-phase silica
10 parts of vinyl silicone oil
1 part of cumyl peroxide
A kind of preparation method of thermally conductive silicone rubber composite material, steps are as follows:
(1) graphene and water are mixed according to mass ratio 1:4, ultrasonic disperse, power 600W, ultrasonic time 2h make stone
Black alkene removing, then adds the vinyl silicone oil that viscosity is 100mPas, is mixed, mixing speed 200r/min is stirred
Mixing the time is 30min, and heating temperature is 150 DEG C, makes moisture evaporating completely, obtains the pre-dispersed object of vinyl silicone oil of graphene；
(2) by methyl phenyl vinyl silicone rubber, gas-phase silica, graphene the pre-dispersed object of vinyl silicone oil in rubber
It is mixed in kneader, vulcanizing agent cumyl peroxide is then added, be kneaded uniformly, rubber compound is made；
(3) rubber compound is rolled with four-roller I type calender, 60 DEG C of roller temperature, roll spacing 1.0mm, speed ratio 1.3 obtains glue
Piece, through overheat drying tunnel heating, temperature is 200 DEG C, heating time 1min, is allowed to presulfurization sizing, and then traction stretches, elongation
Rate is 100%, and winding obtains rubber cylinder；
(4) rubber cylinder is cut along perpendicular to cylinder axis direction, obtains the film with a thickness of 2mm, then
Low pressure vulcanization is carried out, curing temperature is 180 DEG C, sulfide stress 1.0MPa, vulcanization time 10min.
The thermal conductivity of gained silicon rubber composite material in a thickness direction is 7.9W/ (mK), tensile strength 5.7MPa.
Embodiment 6:
In terms of mass fraction, a kind of composition of raw materials of thermally conductive silicone rubber composite material is as follows:
100 parts of methyl phenyl vinyl silicone rubber
80 parts of graphene
10 parts of gas-phase silica
20 parts of vinyl silicone oil
5 parts of cumyl peroxide
A kind of preparation method of thermally conductive silicone rubber composite material, steps are as follows:
(1) graphene and water are mixed according to mass ratio 1:3, ultrasonic disperse, power 600W, ultrasonic time 4h make stone
Black alkene removing, then adds the vinyl silicone oil that viscosity is 100mPas, is mixed, mixing speed 300r/min is stirred
Mixing the time is 60min, and heating temperature is 150 DEG C, makes moisture evaporating completely, obtains the pre-dispersed object of vinyl silicone oil of graphene；
(2) by methyl phenyl vinyl silicone rubber, gas-phase silica, graphene the pre-dispersed object of vinyl silicone oil in rubber
It is mixed in kneader, vulcanizing agent cumyl peroxide is then added, be uniformly mixed, rubber compound is made；
(3) rubber compound is rolled with four-roller S type calender, 80 DEG C of roller temperature, roll spacing 1.0mm, speed ratio 1.2 obtains glue
Piece, through overheat drying tunnel heating, temperature is 200 DEG C, heating time 1min, is allowed to presulfurization sizing, and then traction stretches, elongation
Rate is 100%, and winding obtains rubber cylinder；
(4) rubber cylinder is cut along perpendicular to cylinder axis direction, obtains the film with a thickness of 2mm, then
Low pressure vulcanization is carried out, curing temperature is 190 DEG C, sulfide stress 1.0MPa, vulcanization time 5min.
The thermal conductivity of gained silicon rubber composite material in a thickness direction is 13.7W/ (mK), and tensile strength is
5.9MPa。
Embodiment 7:
In terms of mass fraction, a kind of composition of raw materials of thermally conductive silicone rubber composite material is as follows:
100 parts of methyl phenyl vinyl silicone rubber
150 parts of aluminium nitride
20 parts of gas-phase silica
30 parts of vinyl silicone oil
3 parts of cumyl peroxide
A kind of preparation method of thermally conductive silicone rubber composite material, steps are as follows:
(1) aluminium nitride and water are mixed according to mass ratio 1:3, ultrasonic disperse, power 600W, ultrasonic time 4h make nitrogen
Change aluminium removing, then adds the vinyl silicone oil that viscosity is 500mPas, be mixed, mixing speed 200r/min is stirred
Mixing the time is 60min, and heating temperature is 150 DEG C, makes moisture evaporating completely, obtains the pre-dispersed object of vinyl silicone oil of aluminium nitride；
(2) the pre-dispersed object of vinyl silicone oil of methyl vinyl silicone rubber, gas-phase silica, aluminium nitride is mediated in rubber
It carries out uniformly mixed in machine, is eventually adding vulcanizing agent cumyl peroxide, rubber compound is made；
(3) rubber compound is rolled with four-roller Γ type calender, 60 DEG C of roller temperature, roll spacing 1.0mm, speed ratio 1.2 obtains thin
Film, through overheat drying tunnel heating, temperature is 200 DEG C, time 1min, is allowed to presulfurization sizing, then traction stretches, elongation
It is 100%, winding obtains rubber cylinder；
(4) rubber cylinder is cut along perpendicular to cylinder axis direction, obtains the film of 2mm, then carries out low
Pressure vulcanization, curing temperature are 190 DEG C, sulfide stress 1.5MPa, vulcanization time 5min.
The thermal conductivity of gained silicon rubber composite material in a thickness direction is 7.5W/ (mK), tensile strength 4.0MPa.
Comparative example:
In terms of mass fraction, a kind of composition of raw materials of thermally conductive silicone rubber composite material is as follows:
100 parts of methyl vinyl silicone rubber
200 parts of hexagonal boron nitride
30 parts of gas-phase silica
40 parts of vinyl silicone oil
5 parts of di-t-butyl hexane peroxide of 2,5- dimethyl -2,5-
A kind of preparation method of thermally conductive silicone rubber composite material, steps are as follows: by methyl vinyl silicone rubber, gas phase hard charcoal
Black, hexagonal boron nitride, vinyl silicone oil carry out uniformly mixed in rubber kneading machine, are eventually adding vulcanizing agent 2,5- dimethyl-
2,5- di-t-butyl hexane peroxides, are made rubber compound；With open mill slice, 50 DEG C of roller temperature, roll spacing 1.0mm, speed ratio 1.3,
Then press cure is carried out, curing temperature is 170 DEG C, sulfide stress 13.0MPa, vulcanization time 15min.
The thermal conductivity of gained silicon rubber composite material in a thickness direction is 2.7W/ (mK), tensile strength 2.1MPa.
Compared with comparative example, in embodiment 1-7, the silicon rubber composite material prepared using rubber calender, most
Lower thermal conductivity is 4.1W/ (mK), improves 52% than the thermal conductivity in comparative example, and silicon rubber vulcanization film is minimum
Tensile strength (4.0MPa) is higher by 90% than the tensile strength in comparative example, shows calendering technology method compared to open mill slice
Method, the thermal conductivity and mechanical property of the silicon rubber composite material of preparation are remarkably improved, and are not increasing heat filling dosage
Under the premise of, the thermal conductivity of silicon rubber composite material can be adjusted in a big way with the change of calendering technology parameter,
Roller temperature increases in a certain range, and speed ratio increases, and roll spacing is reduced, and the thermal conductivity of silicon rubber composite material correspondinglys increase, in addition, logical
After crossing film presulfurization, traction is stretched, and makes rubber molecular chain also occur to stretch orientation, to further increase the heat of composite material
Conductance.Thus compared with prior art, regulation method is entirely different, and silicon rubber composite material of the present invention can be used as the invention
The flexible Heat Conduction Material for meeting high heat conductance and high tensile simultaneously, for equipment and devices such as electronics, electric appliance, communication, mobile phones
The thermally conductive encapsulation of part.
It will be understood by those of skill in the art that not departing from this present invention is not limited to the content disclosed in embodiment
In the range for inventing essence, certain transformation or modification can be made to the present invention, it is any without departing from Spirit Essence of the invention with
Made changes, modifications, substitutions, combinations, simplifications under principle should be equivalent alternative, all in protection model of the invention
In enclosing.
Claims (10)
1. a kind of preparation method of thermally conductive silicone rubber composite material, it is characterised in that the following steps are included:
(1) stratiform heat filling and water are mixed, ultrasonic disperse removes heat filling, then adds vinyl silicone oil, mixes
It stirs evenly, heating evaporation moisture, obtains the pre-dispersed object of vinyl silicone oil of stratiform heat filling；Layered heat filling is
One of hexagonal boron nitride, aluminium nitride, lamellar graphite and graphene or a variety of mixtures；
(2) the pre-dispersed object of vinyl silicone oil of silicon rubber, reinforcing agent, heat filling is mixed in rubber kneading machine, is added
Enter vulcanizing agent, is kneaded uniformly, rubber compound is made；
(3) rubber compound is rolled to obtain thin film with rubber calender, heats presulfurization, traction stretches, control of percentage elongation
It is 50%~100%, winding obtains rubber cylinder；The roller temperature of the calendering is 50~80 DEG C, and speed ratio is 1.1~1.3, adjacent
Roll spacing between two rollers is 0.5~2.0mm；
(4) rubber cylinder is cut into film along perpendicular to cylinder axis direction, controlled with a thickness of 1~10mm, low pressure sulphur
Change sizing；
In terms of mass fraction, the composition of raw materials of thermally conductive silicone rubber composite material is formed are as follows: and 100 parts of silicon rubber, stratiform heat filling
40~200 parts, 10~50 parts of vinyl silicone oil, 10~40 parts of reinforcing agent, 1~5 part of vulcanizing agent.
2. the preparation method of thermally conductive silicone rubber composite material according to claim 1, it is characterised in that: the silicon rubber is
One of dimethyl silicone rubber, methyl vinyl silicone rubber and methyl phenyl vinyl silicone rubber or a variety of mixtures.
3. the preparation method of thermally conductive silicone rubber composite material according to claim 1, it is characterised in that: the function of the ultrasound
Rate is 300~600W, and ultrasonic time is 2~4h.
4. the preparation method of thermally conductive silicone rubber composite material according to claim 1, it is characterised in that: the reinforcing agent is
One of precipitated silica and gas-phase silica or a variety of mixtures.
5. the preparation method of thermally conductive silicone rubber composite material according to claim 1, it is characterised in that: the vulcanizing agent is
One of 2,5- dimethyl -2,5- di-t-butyl hexane peroxide, cumyl peroxide, dibenzoyl peroxide are a variety of
Mixture.
6. the preparation method of thermally conductive silicone rubber composite material according to claim 1, it is characterised in that: the vinyl silicon
The viscosity of oil is 100~500mPas.
7. the preparation method of thermally conductive silicone rubber composite material according to claim 1, it is characterised in that: the rubber calendering
Machine uses 3 rollers or 4 roll calendars, and roller arrangement uses I type, S type or Γ type arrangement mode.
8. the preparation method of thermally conductive silicone rubber composite material according to claim 1, it is characterised in that: described in step (3)
Heating presulfurization be to heat thin film in 180~200 DEG C of hot drying tunnel, heating time be 1~3min.
9. the preparation method of thermally conductive silicone rubber composite material according to claim 1, it is characterised in that: described in step (4)
The sulfide stress of the thin film cut is 0.5~2.0MPa, and heating temperature is 160~190 DEG C, and vulcanization time is 5~20min.
10. the preparation method of thermally conductive silicone rubber composite material according to claim 1, it is characterised in that: in step (1), institute
The stratiform heat filling and water stated are according to mass ratio 1:2~1:4；The mixing speed being mixed evenly be 100~
300r/min, mixing time are 30~60min；The heating temperature of the heating evaporation moisture is 100~150 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910681348.4A CN110524922B (en) | 2019-07-26 | 2019-07-26 | Preparation method of heat-conducting silicone rubber composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910681348.4A CN110524922B (en) | 2019-07-26 | 2019-07-26 | Preparation method of heat-conducting silicone rubber composite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110524922A true CN110524922A (en) | 2019-12-03 |
| CN110524922B CN110524922B (en) | 2020-12-11 |
Family
ID=68661821
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910681348.4A Active CN110524922B (en) | 2019-07-26 | 2019-07-26 | Preparation method of heat-conducting silicone rubber composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110524922B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112143465A (en) * | 2020-09-15 | 2020-12-29 | 上海阿莱德实业股份有限公司 | High-performance heat-conducting interface material and preparation method thereof |
| CN112552690A (en) * | 2020-12-10 | 2021-03-26 | 苏州鸿凌达电子科技有限公司 | Silica gel sheet with low dielectric constant and high heat conductivity coefficient |
| CN112659578A (en) * | 2020-12-10 | 2021-04-16 | 苏州鸿凌达电子科技有限公司 | Preparation method of silica gel sheet with low dielectric constant and high heat conductivity coefficient |
| CN113045831A (en) * | 2021-03-15 | 2021-06-29 | 广东信力科技股份有限公司 | Preparation method of high-thermal-conductivity composite rubber material |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101768365A (en) * | 2008-12-29 | 2010-07-07 | 翁文桂 | Polymer composite material with oriented padding and preparation method thereof |
| CN102070904A (en) * | 2010-12-02 | 2011-05-25 | 天津大学 | Silicone rubber composite material and preparation method thereof |
| CN106867094A (en) * | 2017-03-23 | 2017-06-20 | 四川行泰新材料科技有限公司 | A kind of heat-conductivity polymer composite and its preparation method using mill |
| CN108395702A (en) * | 2017-02-08 | 2018-08-14 | 阙燕娣 | A kind of production method of heat-conducting silica gel sheet |
| JPWO2018180997A1 (en) * | 2017-03-31 | 2019-04-11 | バンドー化学株式会社 | Thermally conductive sheet |
-
2019
- 2019-07-26 CN CN201910681348.4A patent/CN110524922B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101768365A (en) * | 2008-12-29 | 2010-07-07 | 翁文桂 | Polymer composite material with oriented padding and preparation method thereof |
| CN102070904A (en) * | 2010-12-02 | 2011-05-25 | 天津大学 | Silicone rubber composite material and preparation method thereof |
| CN108395702A (en) * | 2017-02-08 | 2018-08-14 | 阙燕娣 | A kind of production method of heat-conducting silica gel sheet |
| CN106867094A (en) * | 2017-03-23 | 2017-06-20 | 四川行泰新材料科技有限公司 | A kind of heat-conductivity polymer composite and its preparation method using mill |
| JPWO2018180997A1 (en) * | 2017-03-31 | 2019-04-11 | バンドー化学株式会社 | Thermally conductive sheet |
Non-Patent Citations (3)
| Title |
|---|
| 周文英: "《导热高分子材料》", 30 April 2014, 北京国防工业出版社 * |
| 周文英: "《聚合物基导热复合材料》", 30 September 2017, 北京国防工业出版社 * |
| 王思娇: "高导热硅橡胶材料研究进展", 《绝缘材料》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112143465A (en) * | 2020-09-15 | 2020-12-29 | 上海阿莱德实业股份有限公司 | High-performance heat-conducting interface material and preparation method thereof |
| CN112552690A (en) * | 2020-12-10 | 2021-03-26 | 苏州鸿凌达电子科技有限公司 | Silica gel sheet with low dielectric constant and high heat conductivity coefficient |
| CN112659578A (en) * | 2020-12-10 | 2021-04-16 | 苏州鸿凌达电子科技有限公司 | Preparation method of silica gel sheet with low dielectric constant and high heat conductivity coefficient |
| CN112552690B (en) * | 2020-12-10 | 2022-04-22 | 苏州鸿凌达电子科技有限公司 | Silica gel sheet with low dielectric constant and high heat conductivity coefficient |
| CN113045831A (en) * | 2021-03-15 | 2021-06-29 | 广东信力科技股份有限公司 | Preparation method of high-thermal-conductivity composite rubber material |
| CN113045831B (en) * | 2021-03-15 | 2023-01-31 | 广东信力科技股份有限公司 | Preparation method of high-thermal-conductivity composite rubber material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110524922B (en) | 2020-12-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110524922A (en) | A kind of preparation method of thermally conductive silicone rubber composite material | |
| CN106867094A (en) | A kind of heat-conductivity polymer composite and its preparation method using mill | |
| CN105331112B (en) | A kind of graphene silicon rubber composite foam material and preparation method thereof | |
| JP5541401B2 (en) | Manufacturing method of heat conductive sheet | |
| CN103333494B (en) | A kind of Thermal-conductive insulation silicone rubber thermal interface material and preparation method thereof | |
| CN103448254B (en) | A kind of thermostable biaxially oriented polypropylene capactive film and manufacture method thereof | |
| CN104262971B (en) | A kind of high heat conduction heat vulcanized silicone rubber composite and preparation method thereof | |
| CN103627179A (en) | Graphene-containing silicone rubber composite material with high thermal conductivity and preparation method thereof | |
| CN103772782A (en) | Self-limited flexible PTC (positive temperature coefficient) exothermic material and PTC core material prepared from same and preparation method of PTC core material | |
| JP2003112915A (en) | Graphitized carbon powder and heat conductive composite material composition | |
| CN107619496B (en) | Foamed polymer composite material with bimodal closed-cell structure and preparation method thereof | |
| CN108943921A (en) | A kind of multilayer insulation thermal interfacial material and preparation method thereof | |
| CN110791102A (en) | Silicone rubber pad with high heat conductivity coefficient and preparation method thereof | |
| CN109206908B (en) | High-thermal-conductivity graphite/plastic composite material and preparation method thereof | |
| CN103594214A (en) | Composite PTC (positive temperature coefficient) material for normal temperature heat control | |
| Song et al. | Frequency-adjustable electromagnetic interference shielding performance of sandwich-structured conductive polymer composites by selective foaming and tunable filler dispersion | |
| CN108192352A (en) | It is a kind of that there is thermally conductive sheet for being orientated the carbon nanotube that is staggered and preparation method thereof | |
| CN110218430A (en) | A kind of high thermal conductivity high molecular polymer graphene composite material and preparation method thereof | |
| CN104497585A (en) | High-thermal-conductivity silicone rubber and preparation method thereof | |
| CN107841145A (en) | A kind of transformer thermal conductive insulation silicon rubber composite material | |
| CN106928690A (en) | A kind of modified polyphenyl ether material of high heat conduction and preparation method thereof | |
| Yue et al. | Enhanced reproducibility of positive temperature coefficient effect of TPO/HDPE blends via elastic crosslinking | |
| CN105219092A (en) | A kind of high filling flexible heat-conducting silicon rubber and preparation method thereof | |
| CN106366402A (en) | Method for preparing high-heat-conductivity boron nitride reinforced polymer based composite material | |
| CN110079035B (en) | Rubber/low-melting-point alloy/nano-carbon composite material with three-dimensional conductive network and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |