CN106867094A - A kind of heat-conductivity polymer composite and its preparation method using mill - Google Patents
A kind of heat-conductivity polymer composite and its preparation method using mill Download PDFInfo
- Publication number
- CN106867094A CN106867094A CN201710177143.3A CN201710177143A CN106867094A CN 106867094 A CN106867094 A CN 106867094A CN 201710177143 A CN201710177143 A CN 201710177143A CN 106867094 A CN106867094 A CN 106867094A
- Authority
- CN
- China
- Prior art keywords
- heat
- polymer
- mill
- polymer composite
- sheet material
- 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.)
- Pending
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 65
- 239000002131 composite material Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 61
- 238000011049 filling Methods 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims description 29
- 229920001971 elastomer Polymers 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 14
- 239000000806 elastomer Substances 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 239000005060 rubber Substances 0.000 claims description 10
- 229910052582 BN Inorganic materials 0.000 claims description 9
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 239000012190 activator Substances 0.000 claims description 8
- 230000006835 compression Effects 0.000 claims description 7
- 238000007906 compression Methods 0.000 claims description 7
- 238000001125 extrusion Methods 0.000 claims description 6
- 229910021389 graphene Inorganic materials 0.000 claims description 6
- 238000012545 processing Methods 0.000 claims description 5
- 229920002379 silicone rubber Polymers 0.000 claims description 5
- 239000002322 conducting polymer Substances 0.000 claims description 4
- 229920001940 conductive polymer Polymers 0.000 claims description 4
- 239000002135 nanosheet Substances 0.000 claims description 4
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 3
- 235000021355 Stearic acid Nutrition 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 239000005864 Sulphur Substances 0.000 claims description 3
- -1 accelerator Substances 0.000 claims description 3
- 239000004917 carbon fiber Substances 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 3
- 239000008117 stearic acid Substances 0.000 claims description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 2
- MHKLKWCYGIBEQF-UHFFFAOYSA-N 4-(1,3-benzothiazol-2-ylsulfanyl)morpholine Chemical compound C1COCCN1SC1=NC2=CC=CC=C2S1 MHKLKWCYGIBEQF-UHFFFAOYSA-N 0.000 claims description 2
- 239000005062 Polybutadiene Substances 0.000 claims description 2
- 229920005549 butyl rubber Polymers 0.000 claims description 2
- REQPQFUJGGOFQL-UHFFFAOYSA-N dimethylcarbamothioyl n,n-dimethylcarbamodithioate Chemical compound CN(C)C(=S)SC(=S)N(C)C REQPQFUJGGOFQL-UHFFFAOYSA-N 0.000 claims description 2
- 238000011017 operating method Methods 0.000 claims description 2
- 150000002978 peroxides Chemical class 0.000 claims description 2
- 229920001568 phenolic resin Polymers 0.000 claims description 2
- 239000005011 phenolic resin Substances 0.000 claims description 2
- 229920001084 poly(chloroprene) Polymers 0.000 claims description 2
- 229920002857 polybutadiene Polymers 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 229920003225 polyurethane elastomer Polymers 0.000 claims description 2
- 238000003672 processing method Methods 0.000 claims description 2
- 238000007493 shaping process Methods 0.000 claims description 2
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 239000004033 plastic Substances 0.000 claims 1
- 229920003023 plastic Polymers 0.000 claims 1
- 239000004575 stone Substances 0.000 claims 1
- 239000011701 zinc Substances 0.000 claims 1
- 229910052725 zinc Inorganic materials 0.000 claims 1
- 239000000945 filler Substances 0.000 abstract description 24
- 238000010008 shearing Methods 0.000 abstract description 8
- 244000043261 Hevea brasiliensis Species 0.000 description 6
- 229920003052 natural elastomer Polymers 0.000 description 6
- 229920001194 natural rubber Polymers 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 238000007731 hot pressing Methods 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229920002521 macromolecule Polymers 0.000 description 4
- LLYXJBROWQDVMI-UHFFFAOYSA-N 2-chloro-4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1Cl LLYXJBROWQDVMI-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 230000005684 electric field Effects 0.000 description 3
- HIHIPCDUFKZOSL-UHFFFAOYSA-N ethenyl(methyl)silicon Chemical compound C[Si]C=C HIHIPCDUFKZOSL-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000004945 silicone rubber Substances 0.000 description 3
- 230000000903 blocking effect Effects 0.000 description 2
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000007500 overflow downdraw method Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 230000004308 accommodation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/74—Mixing; Kneading using other mixers or combinations of mixers, e.g. of dissimilar mixers ; Plant
- B29B7/7476—Systems, i.e. flow charts or diagrams; Plants
- B29B7/7495—Systems, i.e. flow charts or diagrams; Plants for mixing rubber
-
- 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
- C08K7/00—Use of ingredients characterised by shape
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
- B29B7/34—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
- B29B7/52—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices with rollers or the like, e.g. calenders
- B29B7/56—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices with rollers or the like, e.g. calenders with co-operating rollers, e.g. with repeated action, i.e. the material leaving a set of rollers being reconducted to the same set or being conducted to a next set
-
- 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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
-
- 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
- C08K3/02—Elements
- C08K3/04—Carbon
-
- 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
- C08K3/02—Elements
- C08K3/06—Sulfur
-
- 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
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
-
- 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
- C08K3/38—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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The invention discloses a kind of heat-conductivity polymer composite and its preparation method using mill, make to have using the shearing force between double roller and be orientated along sheet material direction compared with the sheet or bar-shaped heat filling of big L/D ratio, then sheet material can be added to arbitrary thickness, the orientation of filler is maintained in product using hot-forming under less than flow temperature.Product heat conductivility has anisotropy, has preferable heat conductivility in the differently- oriented directivity of filler, and thermal conductivity factor can reach 10W/mK, and 3W/mK is then less than in the thermal conductivity factor in differently- oriented directivity.
Description
Technical field
The invention belongs to technical field of polymer materials, specifically refer to a kind of heat-conductivity polymer composite and its utilize open
The method for preparing heat-conductivity polymer composite of mill.
Background technology
In recent years, developing rapidly with intensive electronic device industry, the amount of heat pole that equipment is produced in operation
The service life and stability of big reduction equipment.Heat-conductivity polymer composite is widely applied to electronic device field,
But macromolecular material has poor heat conductivility, its thermal conductivity factor typically only has 0.2-0.4W/mK.Its traditional preparation method
Mainly there are fusion method, solvent method and in-situ synthesized.But these preparation methods are difficult to prepare thermal conductivity factor answering more than 3W/mK
Condensation material, and the preparation cost that the filler of high-volume fractional increased composite is added, reduce the mechanical performance of material.
Some heat fillings such as BN, Graphene, graphene microchip, crystalline flake graphite, CNT and carbon fiber etc. have non-
Spherical structure, and with anisotropic heat conductivility.Its hot crystalline flake graphite can reach along (002) crystal plane direction thermal conductivity factor
To 2000W/mK, and there was only 40W/mK perpendicular to web direction thermal conductivity factor.BN with hexagonal crystallographic texture is along lamella side
To thermal conductivity factor (600W/mK) be vertically oriented 20 times of (30W/mK).Therefore, it is system that control filler is orientated in the polymer
One Critical policies of standby high thermal conductivity coefficient polymer composite.Many scholars realize filler and exist using electric field or magnetic field
It is orientated in liquid polymer, then the filler of orientation is fixed up by crosslinking or solidification.Some researchers utilize and are cast into
The method of type or drippage film prepares heat-conducting polymer film, but this heat-conducting polymer film has only on the direction along film
There is thermal conductivity factor higher, and most electronic equipment requirement Heat Conduction Material has preferable thermal conductivity in vertical direction
Energy.And the electric field method and magnetic field method for using are mainly used in epoxy resin and complex process, it is difficult to be applied to actual industrial life
In product.
Based on this, method and heat conduction high score that a kind of utilization mill of design prepares macromolecule heat conduction material are studied and developed
Sub- composite.
The content of the invention
It is an object of the invention to：A kind of preparation method of macromolecule heat conduction material is provided, using between mill double roller
Shearing force by macromolecular material compression be squeezed into sheet material, under less than flow temperature using hot press forming technology taking filler
To being maintained in finished product, finished product has preferable heat conductivility perpendicular to differently- oriented directivity, solves existing application and preparation in electricity
The method of the heat-conductivity polymer composite of sub- equipment is complicated, and macromolecular material heat conductivility difference etc. is asked in vertical direction
Topic.
Another object of the present invention is to：Heat-conductivity polymer composite prepared by a kind of utilization mill is provided, this is led
Hot polymer composite possesses thermal conductivity factor higher along certain orientation.
The present invention is achieved through the following technical solutions：
A kind of heat-conductivity polymer composite, the material by following weight portion material composition, 100 parts of polymer, gather
Compound is selected from styrenic elastomer, polyurethane elastomer, polyester elastomer, ethylene octane copolymer, natural rubber, butylbenzene
The thing of one or more blendings in rubber, EP rubbers, butyl rubber, butadiene rubber, neoprene, silicon rubber
Matter；
5-300 parts of heat filling, heat filling is selected from boron nitride, boron nitride nanosheet, Graphene, graphene microchip, squama
The material of one or more blendings in piece graphite, CNT, carbon fiber；
0-5 parts of vulcanizing agent, 0-5 parts of accelerator, 0-5 parts of activator.
It is preferred that, the vulcanizing agent is any one in sulphur, peroxide, phenolic resin.
It is preferred that, the accelerator is selected from Vulcanization accelerator TMTD, rubber accelerator TMTM, accelerator ZDC, accelerant NOBS, rush
The material of one or more blendings entered in agent NA-22, Urotropinum, accelerator ZIX.
It is preferred that, the activator is selected from the material of one or two blendings in zinc oxide, stearic acid.
The present invention also provides a kind of method that utilization mill prepares macromolecule heat conduction material, including following operating procedure：
Step 1)：Polymer, heat filling are respectively dried first；
Step 2)：By step 1) obtain drying and processing after polymer be placed in mill, at 25-200 DEG C plastify
2-10min, bag roller；
Step 3)：Heat filling after drying, vulcanizing agent, accelerator, activator are added sequentially to through step 2) plasticizing
In polymer after treatment；
Step 4)：The double roller gap of mill is adjusted to 0.05-0.5mm, then polymer is squeezed with the shape of sheet material
Go out；
Step 5)：By step 4) extrusion sheet material cut, and by multiple cut after sheet material stacked compression shaping, system
Obtain final finished.
The traditional preparation method of macromolecular material described in the technical program is fusion method, solvent method, in-situ synthesized, is used
The macromolecular material that above-mentioned preparation method is obtained, its thermal conductivity factor is respectively less than 3W/mk, and heat conductivility is poor.Found through numerous studies,
The Key Strategy for preparing the macromolecular material of high thermal conductivity coefficient is the orientation for controlling filler in material, such as passes through electric field or magnetic field
Control filler orientation in the polymer, and fix the filler of orientation by way of being crosslinked or solidifying, or using drippage
The method of film or flow casting molding prepares heat-conducting polymer film, but finished product only the leading along film direction that the method is prepared
Hot coefficient is higher, be unsatisfactory for the Heat Conduction Material that electronic equipment applied have in vertical direction high thermal conductivity can requirement.
Inventor is directed to the defect of prior art, and the larger shearing force pair produced between the double roller structure using mill adds
Enter to have heat filling, vulcanizing agent, accelerator, the polymer of activator to be plasticated or kneaded.Adjust the double roller gap of mill
It is 0.05-0.5mm, rotating ratio is adjusted to 1.1-1.5, then the shearing force between double roller can make the sheet for having compared with big L/D ratio
Or bar-shaped filler is orientated along extrusion sheet direction, through hot-forming, filler orientation can be maintained in finished product.Be tod with existing
Heat filling prepares ratio with resin simple blend, and the technical program prepares a special construction, heat filling is entered
Row is orderly aligned and forms passage of heat.It is logical that this orientation texture makes Heat Conduction Material form more preferably heat conduction in differently- oriented directivity
Road, produces less thermal contact resistance, and this macromolecular material with sandwich construction has heat conduction higher along a direction
Coefficient, the control that realization is orientated in the polymer to heat filling.
The sheet material extruded is overlapped in the technical program, then compressed forming operation, wherein, compressing and forming process
Orientation texture in heat filling can be fixed, then there is taking for heat filling in the product that final compression forming is obtained
To, it is ensured that prepare thermal conductivity factor of the gained heat-conductivity polymer composite in certain orientation.
Gap between the technical program preferred pair mill double roller is adjusted, and is set to 0.05-0.5mm, mill
Double roller gap directly determines filler shearing force size suffered in the polymer, excessive when double roller gap is less than 0.05mm
Shearing force can heavy damage laminal filter size, filler size reduces and is then unfavorable for the raising of heat conductivility；When double roller
When gap is more than 0.5mm, filler size retains more complete, but double roller gap, when being more than 0.5mm, shearing force is smaller can not to be made
Filler is orientated in the polymer, is also unfavorable for the raising of heat conductivility.
Fusion time in the technical program to polymer in mill is improved, preferably 2-10min, works as plasticizing
When time is less than 2min, polymer mixes uneven in mill, influence subsequent packet roller operation treatment effect；If during plasticizing
Between more than 10min when, polymer can reach in mill and be sufficiently mixed uniform, reach best mixed effect, if
Continue to increase fusion time, the effect that is uniformly dispersed is not up to further effect of optimization, can conversely increase the whole operation time, increase
Weight production cost.
It is preferred that, the step 3) in heat filling using being dividedly in some parts treatment, and make a call to 3-5 triangle bags.Set heat conduction
Filler, vulcanizing agent, accelerator, activator are sequentially added in polymer, i.e., by the way of first filler after cure system, can be maximum
Degree ground reduces the possibility of the cross-linking reaction of polymer generation in process, because the flowing of cross-linking reaction reduction polymer
Property is unfavorable for the orientation of filler.
It is preferred that, the step 1) in be by the specific processing method that polymer, heat filling are respectively dried, at 35-65 DEG C
Under the conditions of, 18-24h of drying time in vacuum drying oven.Drying temperature to polymer, heat filling is carried out preferably, wherein to drying
The improvement of dry temperature is changed according to the species of polymer, heat filling, and the drying temperature for setting is less than polymer, leads
Hot filler starts the initial temperature for softening；And the setting of drying time, according to polymer, the species of heat filling, and its storage
The factors such as situation carry out accommodation.
It is preferred that, the step 5) concrete operation method is：The step 5) concrete operation method is：By step 4) from mill
The sheet material extruded between the double roller of machine is cut into consistent with die size, is placed in mould after then sheet material is superimposed together, piece
The superposition thickness of material be 1-100cm, compression forming at the temperature, 3-15MPa pressure at 70-210 DEG C, obtained finished product with
Mold cavity size is identical.Processing temperature to compression forming is carried out preferably, the flowing of the processing temperature less than polymer of setting
Temperature, realizes the orientation texture in fixed heat filling.
It is preferred that, the step 4) in mill double roller rotating ratio be 1.1-1.5.
It is preferred that, the step 4) in extrusion sheet thickness be 0.1-0.5mm.
The present invention compared with prior art, has the following advantages and advantages：
(1) preparation method for preparing macromolecular material of the present invention is made with larger using the shearing force between double roller
The sheet of draw ratio or bar-shaped heat filling are orientated along sheet material direction, and then sheet material can be added to arbitrary thickness,
The orientation of filler is maintained in product using hot-forming less than under flow temperature.Product heat conductivility has anisotropy,
There is preferable heat conductivility in the differently- oriented directivity of filler, thermal conductivity factor can reach 10W/mK, in differently- oriented directivity
Thermal conductivity factor is then less than 3W/mK.
(2) utilization mill of the present invention prepares orientation sheet material and then in hot-forming preparation method, with work
Skill is simple, low cost, the advantages of product heat conductivility and excellent mechanical performance.
(3) macromolecular material prepared using scheme of the present invention, is had preferable in the differently- oriented directivity of filler
Heat conductivility, thermal conductivity factor can reach 10W/mK, and 3W/mK is then less than in the thermal conductivity factor in differently- oriented directivity.
Specific embodiment
To make the object, technical solutions and advantages of the present invention become more apparent, with reference to embodiment, the present invention is made
Further to describe in detail, exemplary embodiment of the invention and its explanation are only used for explaining the present invention, are not intended as to this
The restriction of invention.
Embodiment 1：
One kind prepares heat-conductivity polymer composite using mill, and its preparation is carried out in accordance with the following steps：In 40 DEG C of bars
Under part, POE elastomers (also known as ethylene octane copolymer) and natural scale graphite heat filling are placed into vacuum drying oven
Row drying 18h.Under the conditions of 95 DEG C, the POE elastomers of 100g are added in the gap of mill double roller and plastify 5min.Then
The natural scale graphite of 80g point is added to for 5 times in the POE elastomers for having plastified and kneads triangle bag that is uniform and making a call to 3 times.Will be mixed
It is the sheet material of 0.2mm that the POE elastomers for having refined extrude thickness in double roller gap is for the mill of 0.05mm.
The sheet material that will be extruded cuts the size as die size, and the thickness of the 10mm that is then added to is put into mould,
The hot pressing 10min at a temperature of 85 DEG C.Finally, it is 0.9W/mK along the thermal conductivity factor of thickness direction, perpendicular to thickness direction
Thermal conductivity factor is 3.1W/mK, is 3.4 times of thickness direction perpendicular to the thermal conductivity factor of thickness direction.
Embodiment 2：
A kind of method that utilization mill prepares heat-conductivity polymer composite, its preparation is carried out in accordance with the following steps：
Under the conditions of 40 DEG C, POE elastomers and hexagonal boron nitride heat filling are placed into vacuum drying oven carries out drying 18h.At 95 DEG C
Under the conditions of, the POE elastomers of 100g are added in the gap of mill double roller and plastify 5min.Then six sides of 80g are nitrogenized
Boron point kneads triangle bag that is uniform and making a call to 3 times in being added to the POE elastomers for having plastified for 5 times.The POE elastomers that will be kneaded exist
Double roller gap is the sheet material of 0.1mm to extrude thickness in the mill of 0.2mm.
The sheet material that will be extruded cuts the size as die size, and the thickness of the 10mm that is then added to is put into mould,
The hot pressing 10min at a temperature of 85 DEG C.Finally, it is 0.8W/mK along the thermal conductivity factor of thickness direction, perpendicular to thickness direction
Thermal conductivity factor is 2.2W/mK, is 2.8 times of thickness direction perpendicular to the thermal conductivity factor of thickness direction.
Embodiment 3：
A kind of method that utilization mill prepares heat-conductivity polymer composite, its preparation is carried out in accordance with the following steps：
Under the conditions of 60 DEG C, natural rubber and hexagonal boron nitride heat filling are placed into vacuum drying oven carries out drying 20h.In 45 DEG C of bars
Under part, the natural rubber of 100g is added in the gap of mill double roller and plastifies 2min.Then by 5g zinc oxide, 2g is stearic
Acid, 2.5g sulphur, 0.6NOBS, 100g hexagonal boron nitride kneads uniform and making a call to 3 times three in being added to the natural rubber for having plastified
Wrap at angle.It is the sheet material of 0.3mm that the natural rubber that will be kneaded extrudes thickness in double roller gap is for the mill of 0.2mm.
The sheet material that will be extruded cuts the size as die size, and the thickness of the 50cm that is then added to is put into mould,
The hot pressing 10min at a temperature of 145 DEG C.Finally, it is 0.4W/mK along the thermal conductivity factor of thickness direction, perpendicular to thickness direction
The thermal conductivity factor for being is 1.9W/mK, is 4.8 times of thickness direction perpendicular to the thermal conductivity factor of thickness direction.
Embodiment 4：
A kind of method that utilization mill prepares heat-conductivity polymer composite, its preparation is carried out in accordance with the following steps：
Under the conditions of 65 DEG C, methyl vinyl silicone rubber and hexagonal boron nitride nanosheet heat filling are placed into vacuum drying oven and are dried
Dry 24h.Under the conditions of 25 DEG C, the methyl vinyl silicone rubber of 100g is added in the gap of mill double roller and plastifies 5min.
Then mixing is uniform simultaneously in 1g DCP and 100g hexagonal boron nitride nanosheets being added into the methyl vinyl silicone rubber for having plastified
Make a call to the triangle bag of 3 times.It is 0.3mm's that the natural rubber that will be kneaded extrudes thickness in double roller gap is for the mill of 0.5mm
Sheet material.
The sheet material that will be extruded cuts the size as die size, and the thickness of the 100cm that is then added to is put into mould,
The hot pressing 10min at a temperature of 210 DEG C.Finally, it is 0.6W/mK along the thermal conductivity factor of thickness direction, perpendicular to thickness direction
It is that thermal conductivity factor is 3.0W/mK, is 5 times of thickness direction perpendicular to the thermal conductivity factor of thickness direction.
Embodiment 5：
A kind of method that utilization mill prepares heat-conductivity polymer composite, its preparation is carried out in accordance with the following steps：
Under the conditions of 40 DEG C, EP rubbers and CNT heat filling are placed into vacuum drying oven carries out drying 18h.In 110 DEG C of bars
Under part, the EP rubbers of 100g is added in the gap of mill double roller and plastifies 5min.Then 10g CNTs are added to
Triangle bag that is uniform and making a call to 3 times is kneaded in the EP rubbers for having plastified.The EP rubbers that will be kneaded is 0.5mm in double roller gap
Mill extrusion thickness for 0.2mm sheet material
The sheet material that will be extruded cuts the size as die size, and the thickness of the 10mm that is then added to is put into mould,
The hot pressing 10min at a temperature of 150 DEG C.Finally, it is 0.5W/mK along the thermal conductivity factor of thickness direction, perpendicular to thickness direction
It is that thermal conductivity factor is 1.8W/mK, is 3.6 times of thickness direction perpendicular to the thermal conductivity factor of thickness direction.
Comparative example：
Heat-conductivity polymer composite：It is composed of the following components, basic material：10-100 parts, basic material be selected from 10-
800000 molecular weight ethenyl blocking silicon polymers, 10-100 ten thousand hydroxy-end capped silicon polymers of molecular weight, 10-100 ten thousand molecular weight
One or more in methyl blocking silicon polymer；
Heat filling：100-1000 parts, vulcanizing agent：0.5-10 parts, processing aid：1-20 parts；
In the case of identical heat filling number, the polymer composite prepared using the inventive method is being orientated
The thermal conductivity factor in direction is 3-10 times of comparative example, and the thermal conductivity factor in differently- oriented directivity is comparative example
0.5-1 times.Therefore the heat conductivility of macromolecule heat conduction material for preparing of the present embodiment 1-5 methods describeds to be substantially better than contrast real
The heat-conductivity polymer composite described in example is applied, and the orientation of filler can be maintained in finished product, described in embodiment 1-5
Heat-conductivity polymer composite heat conductivility is greatly improved in vertical direction, relative to thickness direction, perpendicular to
The thermal conductivity factor of thickness direction is 3-6 times of thickness direction.
Above-described specific embodiment, has been carried out further to the purpose of the present invention, technical scheme and beneficial effect
Describe in detail, should be understood that and the foregoing is only specific embodiment of the invention, be not intended to limit the present invention
Protection domain, all any modification, equivalent substitution and improvements within the spirit and principles in the present invention, done etc. all should include
Within protection scope of the present invention.
Claims (10)
1. a kind of heat-conductivity polymer composite, it is characterised in that：The material by following weight portion material composition, polymer
100 parts, polymer is selected from styrenic elastomer, polyurethane elastomer, polyester elastomer, ethylene octane copolymer, natural
One or more blendings in rubber, butadiene-styrene rubber, EP rubbers, butyl rubber, butadiene rubber, neoprene, silicon rubber
Material；
5-300 parts of heat filling, heat filling is selected from boron nitride, boron nitride nanosheet, Graphene, graphene microchip, scale stone
The material of one or more blendings in ink, CNT, carbon fiber；
0-5 parts of vulcanizing agent, 0-5 parts of accelerator, 0-5 parts of activator.
2. a kind of heat-conductivity polymer composite according to claim 1, it is characterised in that：The vulcanizing agent be sulphur,
Any one in peroxide, phenolic resin.
3. a kind of heat-conductivity polymer composite according to claim 1, it is characterised in that：The accelerator is selected from and promotes
In agent TMTD, rubber accelerator TMTM, accelerator ZDC, accelerant NOBS, accelerant N A-22, Urotropinum, accelerator ZIX
The material of one or more blendings.
4. a kind of heat-conductivity polymer composite according to claim 1, it is characterised in that：The activator is selected from oxidation
The material of one or two blendings in zinc, stearic acid.
5. a kind of method that utilization mill prepares the heat-conductivity polymer composite as described in claim 1-4 any one, its
It is characterised by：Including following operating procedure,
Step 1)：Polymer, heat filling are respectively dried first；
Step 2)：By step 1) obtain drying and processing after polymer be placed in mill, at 25-200 DEG C plastify 2-
10min, bag roller；
Step 3)：Heat filling after drying, vulcanizing agent, accelerator, activator are added sequentially to through step 2) plastics processing
In polymer afterwards；
Step 4)：The double roller gap of mill is adjusted to 0.05-0.5mm, then polymer is extruded with the shape of sheet material；
Step 5)：By step 4) extrusion sheet material cut, and by multiple cut after sheet material stacked compression shaping, be obtained most
Finally finished.
6. the method that a kind of utilization mill according to claim 5 prepares heat-conductivity polymer composite, its feature exists
In：The step 3) in heat filling using being dividedly in some parts in the polymer of plasticizing, and make a call to 3-5 triangle bags.
7. the method that a kind of utilization mill according to claim 5 prepares heat-conductivity polymer composite, its feature exists
In：The step 1) in be by the specific processing method that polymer, heat filling are respectively dried, under the conditions of 35-65 DEG C, very
18-24h of drying time in empty baking oven.
8. the method that a kind of utilization mill according to claim 5 prepares heat-conductivity polymer composite, its feature exists
In：The step 5) concrete operation method is：By step 4) it is cut into and mould chi from the sheet material extruded between the double roller of mill
It is very little consistent, it is placed in mould after then sheet material is superimposed together, the superposition thickness of sheet material is 1-100cm, at 70-210 DEG C
Temperature, 3-15MPa pressure under compression forming, obtained finished product is identical with mold cavity size.
9. a kind of utilization mill according to claim 5 prepares method of the heat-conducting polymer in composite, its feature
It is：The step 4) in mill double roller rotating ratio be 1.1-1.5.
10. the method that a kind of utilization mill according to claim 5 prepares heat-conductivity polymer composite, its feature exists
In：The step 4) in extrusion sheet thickness be 0.1-0.5mm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710177143.3A CN106867094A (en) | 2017-03-23 | 2017-03-23 | A kind of heat-conductivity polymer composite and its preparation method using mill |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710177143.3A CN106867094A (en) | 2017-03-23 | 2017-03-23 | A kind of heat-conductivity polymer composite and its preparation method using mill |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106867094A true CN106867094A (en) | 2017-06-20 |
Family
ID=59173039
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710177143.3A Pending CN106867094A (en) | 2017-03-23 | 2017-03-23 | A kind of heat-conductivity polymer composite and its preparation method using mill |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106867094A (en) |
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107501644A (en) * | 2017-09-29 | 2017-12-22 | 广东石油化工学院 | A kind of preparation method of heat-conducting type abrasion-resistant rubber |
| CN108976618A (en) * | 2018-08-08 | 2018-12-11 | 南通迅达橡塑制造有限公司 | A kind of graphene modified EPT rubber composite material and preparation method thereof |
| CN109082014A (en) * | 2018-08-03 | 2018-12-25 | 浙江久运汽车零部件有限公司 | A kind of thermally conductive EPDM sebific duct and preparation method thereof |
| CN110105638A (en) * | 2019-05-05 | 2019-08-09 | 华南协同创新研究院 | A kind of low-density high thermal conductivity non-silicon material and its preparation method and application |
| CN110157048A (en) * | 2018-02-07 | 2019-08-23 | 陕西永安减震科技有限公司 | A kind of high thermal conductivity engineering rubber material and preparation method thereof |
| CN110157153A (en) * | 2018-02-11 | 2019-08-23 | 中国科学院深圳先进技术研究院 | A kind of boron nitride composite and preparation method thereof of epoxy resin/orderly |
| CN110437807A (en) * | 2019-08-15 | 2019-11-12 | 常州富烯科技股份有限公司 | Interface Heat Conduction Material and preparation method thereof |
| CN110524922A (en) * | 2019-07-26 | 2019-12-03 | 华南理工大学 | A kind of preparation method of thermally conductive silicone rubber composite material |
| CN110684285A (en) * | 2019-09-05 | 2020-01-14 | 上海阿莱德实业股份有限公司 | Rubber-based graphene heat conduction material |
| CN110746622A (en) * | 2019-09-23 | 2020-02-04 | 深圳大学 | Method for improving conductivity of high polymer material and high polymer material with high conductivity |
| CN111267434A (en) * | 2020-03-06 | 2020-06-12 | 深圳先进技术研究院 | Heat-conducting electromagnetic shielding material with oriented structure and preparation method thereof |
| CN111825894A (en) * | 2020-06-17 | 2020-10-27 | 吉祥三宝高科纺织有限公司 | Anti-slip material and preparation method thereof |
| CN113150408A (en) * | 2021-05-13 | 2021-07-23 | 慕思健康睡眠股份有限公司 | Temperature-reducing and heat-insulating graphene latex as well as preparation method and application thereof |
| CN113150557A (en) * | 2021-04-08 | 2021-07-23 | 华南理工大学 | Silicon rubber composite material with directional arrangement and three-dimensional structure construction for improving heat conductivity, and preparation method and application thereof |
| CN113278163A (en) * | 2020-11-18 | 2021-08-20 | 百色学院 | Method for improving heat conductivity coefficient of flaky alumina/polymer composite sheet material through electric field induction |
| CN113278370A (en) * | 2021-05-19 | 2021-08-20 | 常州安迪新材料有限公司 | HBN-containing heat-conducting POE packaging adhesive film |
| CN113337103A (en) * | 2021-06-03 | 2021-09-03 | 上海交通大学 | Low-dielectric and high-thermal-conductivity polymer-based composite material and preparation method thereof |
| CN114133761A (en) * | 2021-12-01 | 2022-03-04 | 中国科学院工程热物理研究所 | Vertically-arranged hexagonal boron nitride filled resin-based silicon-free heat conduction gasket and preparation method thereof |
| CN115490889A (en) * | 2022-08-26 | 2022-12-20 | 四川大学 | Method for realizing in-situ stripping of two-dimensional filler by using high-elasticity polymer |
| CN115505265A (en) * | 2021-06-23 | 2022-12-23 | 嘉兴超维新材料科技有限公司 | High-thermal-conductivity silicone rubber gasket and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104327515A (en) * | 2014-10-20 | 2015-02-04 | 中国科学院金属研究所 | Graphene-containing silicon rubber heat-conducting composite material and preparation method thereof |
-
2017
- 2017-03-23 CN CN201710177143.3A patent/CN106867094A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104327515A (en) * | 2014-10-20 | 2015-02-04 | 中国科学院金属研究所 | Graphene-containing silicon rubber heat-conducting composite material and preparation method thereof |
Cited By (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107501644A (en) * | 2017-09-29 | 2017-12-22 | 广东石油化工学院 | A kind of preparation method of heat-conducting type abrasion-resistant rubber |
| CN110157048A (en) * | 2018-02-07 | 2019-08-23 | 陕西永安减震科技有限公司 | A kind of high thermal conductivity engineering rubber material and preparation method thereof |
| CN110157153A (en) * | 2018-02-11 | 2019-08-23 | 中国科学院深圳先进技术研究院 | A kind of boron nitride composite and preparation method thereof of epoxy resin/orderly |
| CN109082014A (en) * | 2018-08-03 | 2018-12-25 | 浙江久运汽车零部件有限公司 | A kind of thermally conductive EPDM sebific duct and preparation method thereof |
| CN108976618A (en) * | 2018-08-08 | 2018-12-11 | 南通迅达橡塑制造有限公司 | A kind of graphene modified EPT rubber composite material and preparation method thereof |
| CN110105638A (en) * | 2019-05-05 | 2019-08-09 | 华南协同创新研究院 | A kind of low-density high thermal conductivity non-silicon material and its preparation method and application |
| CN110524922A (en) * | 2019-07-26 | 2019-12-03 | 华南理工大学 | A kind of preparation method of thermally conductive silicone rubber composite material |
| CN110437807A (en) * | 2019-08-15 | 2019-11-12 | 常州富烯科技股份有限公司 | Interface Heat Conduction Material and preparation method thereof |
| CN110684285A (en) * | 2019-09-05 | 2020-01-14 | 上海阿莱德实业股份有限公司 | Rubber-based graphene heat conduction material |
| CN110684285B (en) * | 2019-09-05 | 2021-11-30 | 上海阿莱德实业股份有限公司 | Rubber-based graphene heat conduction material |
| CN110746622A (en) * | 2019-09-23 | 2020-02-04 | 深圳大学 | Method for improving conductivity of high polymer material and high polymer material with high conductivity |
| CN110746622B (en) * | 2019-09-23 | 2022-09-20 | 深圳大学 | Method for improving conductivity of high polymer material and high polymer material with high conductivity |
| CN111267434A (en) * | 2020-03-06 | 2020-06-12 | 深圳先进技术研究院 | Heat-conducting electromagnetic shielding material with oriented structure and preparation method thereof |
| CN111267434B (en) * | 2020-03-06 | 2022-03-22 | 深圳先进技术研究院 | Heat-conducting electromagnetic shielding material with oriented structure and preparation method thereof |
| CN111825894A (en) * | 2020-06-17 | 2020-10-27 | 吉祥三宝高科纺织有限公司 | Anti-slip material and preparation method thereof |
| CN111825894B (en) * | 2020-06-17 | 2022-05-27 | 吉祥三宝高科纺织有限公司 | Anti-slip material and preparation method thereof |
| CN113278163A (en) * | 2020-11-18 | 2021-08-20 | 百色学院 | Method for improving heat conductivity coefficient of flaky alumina/polymer composite sheet material through electric field induction |
| CN113150557A (en) * | 2021-04-08 | 2021-07-23 | 华南理工大学 | Silicon rubber composite material with directional arrangement and three-dimensional structure construction for improving heat conductivity, and preparation method and application thereof |
| CN113150408A (en) * | 2021-05-13 | 2021-07-23 | 慕思健康睡眠股份有限公司 | Temperature-reducing and heat-insulating graphene latex as well as preparation method and application thereof |
| CN113278370A (en) * | 2021-05-19 | 2021-08-20 | 常州安迪新材料有限公司 | HBN-containing heat-conducting POE packaging adhesive film |
| CN113337103A (en) * | 2021-06-03 | 2021-09-03 | 上海交通大学 | Low-dielectric and high-thermal-conductivity polymer-based composite material and preparation method thereof |
| CN115505265A (en) * | 2021-06-23 | 2022-12-23 | 嘉兴超维新材料科技有限公司 | High-thermal-conductivity silicone rubber gasket and preparation method and application thereof |
| CN114133761A (en) * | 2021-12-01 | 2022-03-04 | 中国科学院工程热物理研究所 | Vertically-arranged hexagonal boron nitride filled resin-based silicon-free heat conduction gasket and preparation method thereof |
| CN115490889A (en) * | 2022-08-26 | 2022-12-20 | 四川大学 | Method for realizing in-situ stripping of two-dimensional filler by using high-elasticity polymer |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106867094A (en) | A kind of heat-conductivity polymer composite and its preparation method using mill | |
| Wu et al. | Structure of carboxylated acrylonitrile‐butadiene rubber (CNBR)–clay nanocomposites by co‐coagulating rubber latex and clay aqueous suspension | |
| CN105175842B (en) | It is a kind of to have efficient heat-conductive characteristic and the polymer-based insulating heat-conductive composite of excellent mechanical performance concurrently | |
| CN102786815B (en) | Method for modifying surface of BN (boron nitride) powder, modified BN and polymer composite material | |
| CN112341662B (en) | Gray antistatic polypropylene composite foaming bead with skin-core structure and molded product thereof | |
| CN103588983B (en) | Preparation method for flexible high-molecular PTC material | |
| CN104262971B (en) | A kind of high heat conduction heat vulcanized silicone rubber composite and preparation method thereof | |
| CN101979444B (en) | Methods for preparing quaternary phosphonium salt ionic liquid pillaring-modified montmorillonite and polymer/montmorillonite nanocomposite | |
| CN110524922B (en) | Preparation method of heat-conducting silicone rubber composite material | |
| CN108440824B (en) | A kind of High-heat-conductiviinsulation insulation material and its method prepared by waste aluminium plastic packaging material | |
| CN108943921A (en) | A kind of multilayer insulation thermal interfacial material and preparation method thereof | |
| CN102220007A (en) | Insulation material for silicone rubber composite cable used in nuclear power station | |
| CN113799286A (en) | Preparation method of polymer blend with controllable dispersed phase size and dimension | |
| CN104629251A (en) | Flame retardant composition and application thereof | |
| CN108017820A (en) | A kind of fiber reinforcement high density polyethylene (HDPE)/graphene composite material and preparation method thereof | |
| CN102146175B (en) | Microwave continuous foaming plate made from tire reclaimed rubber and preparation method of microwave continuous foaming plate | |
| CN110483904B (en) | Sizing material for sealing gasket, preparation method of sealing gasket and plate heat exchanger comprising sealing gasket | |
| CN102604313B (en) | SBS (Styrene-Butadiene-Styrene) crosslinking elastomer composite material and preparation method thereof | |
| CN112080081B (en) | Low-cost high-gas-barrier thermoplastic vulcanized rubber for bicycle tire and preparation method thereof | |
| CN111303500B (en) | Preparation method of graphene oxide/butyronitrile latex nanocomposite | |
| CN108017804A (en) | A kind of fiber reinforcement high density polyethylene (HDPE)/graphite composite material and preparation method thereof | |
| EP3719098B1 (en) | Process for manufacturing super thermal-conductive graphene curing bladder | |
| CN108048062A (en) | A kind of water plugging profile control agent and preparation method thereof | |
| CN112029172A (en) | Polymer-based heat-conducting composite material and preparation method thereof | |
| CN113527869B (en) | Carbon nanotube modified polyurethane thermoplastic vulcanized rubber 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 | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170620 |