CN110343315A - Containing Monodispersed, polymer bond's film of highly oriented graphene and preparation method thereof - Google Patents

Containing Monodispersed, polymer bond's film of highly oriented graphene and preparation method thereof Download PDF

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Publication number
CN110343315A
CN110343315A CN201910599210.XA CN201910599210A CN110343315A CN 110343315 A CN110343315 A CN 110343315A CN 201910599210 A CN201910599210 A CN 201910599210A CN 110343315 A CN110343315 A CN 110343315A
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graphene
film
highly oriented
parts
polymer
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Inventor
徐欢
徐玮彤
朱亚坤
翟乐
刘芳芳
刘婷婷
刘耕成
曲波
马青喜
李金来
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Jiangsu Jiangnan Elenyl Graphene Technology Co Ltd
Jiangsu Xinao Carbon Nano Materials Application Technology Research Institute Co Ltd
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Jiangsu Jiangnan Elenyl Graphene Technology Co Ltd
Jiangsu Xinao Carbon Nano Materials Application Technology Research Institute Co Ltd
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Priority to CN201910599210.XA priority Critical patent/CN110343315A/en
Publication of CN110343315A publication Critical patent/CN110343315A/en
Priority to CN201911058061.2A priority patent/CN110591209A/en
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
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    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
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    • C08J2453/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2453/02—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers of vinyl aromatic monomers and conjugated dienes
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Abstract

The present invention relates to carbon nano-composite material high performance and Functionalization fields more particularly to a kind of containing Monodispersed, polymer bond's film of highly oriented graphene and preparation method thereof.Thermally conductive film material is made of following components: polymeric matrix, graphene, the second heat filling, surface treating agent, filler covering, processing aid.The technology path combined using " high shear melting dispersion " and " super drawing ", promote graphene nanometer sheet and other heat fillings are evenly dispersed in a polymer matrix and acquisition is height-oriented, utilize continuous, the three-dimensional hydridization heat conduction network structure of graphene itself building long-range, overcome graphene anisotropy, constructs and stablize effective heat conduction network.

Description

Containing Monodispersed, polymer bond's film of highly oriented graphene and preparation method thereof
Technical field
The present invention relates to a kind of polymer bond's film more particularly to a kind of polymerizations containing Monodispersed, highly oriented graphene Object thermally conductive film and preparation method thereof.
Background technique
Due to its multi-functional and workability, heat of the heat-conducting type polymer material in modern electrical system and electronic equipment The fields such as management application play the effect to become more and more important.Polymer material has excellent electrical insulation capability, flexibility and design Freedom degree, in fields such as Electronic Packagings using more and more extensive, but its poor intrinsic thermal conductivity ability limit they One of applicability in heat management, be a problem to be solved.With the quick evolution of electrical system and electronic equipment performance, pass The polymer composites of system have been unable to meet many high requirements of heat management, for example, molding thickness<100 μm, thermal conductivity> 5 W/m∙K。
The composite material of the above-mentioned advantage of conjugated polymer and filler high-termal conductivity is considered as ideal solution, and mesh The exploitation of preceding heat-conductive composite material is also mostly based on the filling-modified polymer of conductive particle.With high heat conductance and mechanical property it is good Good polymer material is widely used to light emitting diode (LED), integrated-optic device, energy stores and converting system, with And in military weapon and aerospace industry, to realize heat management appropriate.However, filler enhancing polymer composites are led Hot raising is usually using the deterioration of lightweight loss, flexibility and processability as cost.
Conductive particle forms good thermal conducting path and particle physics size and surface chemistries inside polymeric matrix Matter and processing and forming technology are inseparable.It is many kinds of due to polymeric matrix and conductive particle, polymeric matrix it is molten Melt-viscosity, glass transition temperature, solubility, polarity etc. and the configuration of surface of particle, surface nature, particle size and its with The differences such as matrix compatibility, so corresponding different resins-filler systems need different processing according to different performance requirements Method.
For the requirements at the higher level that current thermal control field proposes material, it is badly in need of opening up processing, the power of regulation thin polymer film The new method with heating conduction is learned, to expand it in the application prospect of higher-end businesses.
The shortcomings that prior art:
(1) filler-matrix compatibility is poor: the poor compatibility of heat filling and polymeric matrix, interface cohesion are weaker, in matrix Difficulties in dispersion becomes the major obstacle of heating conduction promotion, and especially building improves thermal conducting path and needs a large amount of heat fillings In the case of.
(2) be difficult to meet multi-functional demand: high-end applications propose the urgent need of multi-functional, example to thermally conductive film Such as, existing electronic chip packaging material only has certain capacity of heat transmission, and simultaneously by external high frequency circuit when chip operation The electromagnetic interference of generation, it is the important directions studied now that exploitation, which has both the encapsulating material of effectiveness,.
(3) poor heat resistance: can generate larger heat under many application scenarios such as power-type LED and flexible heater device, Heat is easy to accumulate and cause overheat.However, low, poor heat resistance is limited by polymeric matrix heat-sinking capability, composite material is thin Film is easily ruined being partially formed the concurrent raw burn of higher temperature.
(4) fatigue durability is poor: flexible electronic device, that is, device all can be functioned normally in bending and after bending, be answered Electrode material for flexible electronic device is also easy to produce fatigue of materials, causes mechanics and electric conductivity to be decayed, resulting devices Performance can not be played normally and reduce service life.
(5) poor in processability: when using traditional heat filling (such as aluminium oxide and boron nitride), required additive amount often compared with High (generally higher than 30 vol %), are easy to cause the serious deterioration of composite materials property and processing performance.
Summary of the invention
Present invention seek to address that drawbacks described above, provides a kind of polymer bond's film containing Monodispersed, highly oriented graphene And preparation method thereof.For solving above-mentioned deficiency present in existing Heat Conduction Material technology, provide can be widely applied to it is thermally conductive, change Hot, heat dissipation and field of heat management high thermal conductivity composite film material.The present invention is using " high shear melting dispersion " and " high power is drawn Stretch " technology path that combines, promote graphene nanometer sheet and other heat fillings evenly dispersed in a polymer matrix and obtain It is height-oriented, using continuous, the three-dimensional hydridization heat conduction network structure of graphene itself building long-range, overcome graphene respectively to The opposite sex constructs and stablizes effective heat conduction network.Meanwhile super drawing off field, polymer matrix body portion is mainly by crystalline state The nanofiber of highly oriented platelet and amorphous state composition greatly reduces phonon caused by crystal defect and grain boundary and dissipates It penetrates, can get the thin polymer film with high thermal conductivity.It is equally important that height-oriented platelet, strand, graphene and its His heat filling also has significant mechanics enhancement effect, and barrier properties for gases, toughness and the ductility of laminated film is greatly improved. The production technology simplicity that this method is taken is easy to large-scale production, and production cost is low, has broad prospect of application.
In order to overcome defect present in background technique, the technical solution adopted by the present invention to solve the technical problems is: The thermally conductive film material is made of following components:
30 80 parts of polymeric matrix；
5 40 parts of graphene；
Second 10 30 parts of heat filling；
0.015 4 parts of surface treating agent；
1 40 parts of filler covering；
0.5 20 parts of processing aid.
According to another embodiment of the invention, further comprise the polymeric matrix be polyethylene, polypropylene, polychlorostyrene Ethylene, Kynoar, polystyrene, polyamide, polycarbonate, polybutylene terephthalate (PBT) or poly terephthalic acid At least one of glycol ester.
According to another embodiment of the invention, the maximum radial dimension for further comprising the graphene is 0.5 40 μ M, with a thickness of 1 20 nm.
According to another embodiment of the invention, further comprise second heat filling be boron nitride, silicon carbide, boron Sour magnesium, aluminium borate, magnesium carbonate, aluminium oxide, zinc oxide, magnesia, magnesium hydroxide, calcium carbonate, calcium sulfate, graphite, can swollen graphite, At least one of expanded graphite, carbon fiber or carbon nanotube.
According to another embodiment of the invention, further comprise the surface treating agent be silane coupling agent when, surface Inorganic agent and the graphene and the ratio of heat filling gross mass are 2 10:100；
Or the surface treating agent is octadecylamine, isocyanates, Aluminate or when titanate coupling agent, surface treating agent with The graphene and the ratio of heat filling gross mass are 0.3 1.5:100.
According to another embodiment of the invention, further comprise the filler covering be paraffin, thermoplastic elastomer (TPE) (TPE), polyolefin elastomer (POE), polyethylene wax, ethylene propylene diene rubber (EPDM), styrene analog thermoplastic elastomer (SBS), ethylene-vinyl acetate copolymer (EVA), butadiene-styrene rubber (SBR), ethylene-methyl acrylate copolymer (EMA), second In alkene-ethyl acrylate copolymer (EEA), ethylene-butyl acrylate copolymer (EBA) and polyester elastomer (TPEE) at least It is a kind of.
According to another embodiment of the invention, further comprise the processing aid be epoxidized soybean oil, ACR, CPE, MBS, SMA, white oil, stearic acid, stearate, irgasfos 168, antioxidant 300, antioxidant 1010 and thiodipropionic acid dilauryl osmanthus At least one of ester (DLTDP).
Preparation method containing Monodispersed, polymer bond's film of highly oriented graphene, the preparation method include following step It is rapid:
The first step, high shear melt blending: temperature be 120 300 DEG C at, by polymer, graphene, the second heat filling, Surface treating agent, covering and processing aid carry out melt blended, the output energy of Blending Processes under high shear strength in proportion The ratio between amount and all mixture quality are 0.1 5 kWh/kg, then through cooling and dicing or are directly granulated, acquisition Monodispersed graphite Alkene is filled polymer-modified；
Second step, high power mechanically thermal stretching: in the case where temperature is 160 300 DEG C, Monodispersed graphene described in the first step is filled Polymer-modified carry out high power mechanical stretching, stretching ratio be 2 200, obtain the polymerization containing Monodispersed, highly oriented graphene Object thermally conductive film, the molding thickness of thermally conductive film are 10 800 μm.
It according to another embodiment of the invention, further comprise melt blending equipment in the first step is reciprocating Screw extruder, double screw extruder, high-speed mixer, open mill, convertible mixer, continuous internal mixer, Z-type are mediated At least one of machine, screw mixer, vacuum kneader and Horizontal double-spiral mixing machine.
It according to another embodiment of the invention, further comprise that mechanically thermal stretching equipment is squeezed in the second step for sheet material At least one of machine, film blow molding machine and cast film machine out.
The beneficial effects of the present invention are:
1, the technology path combined using " high shear blending " and " super drawing ", ensure that the cleaning of nanocomposite Change, serialization, large-scale production can fast implement industrialization, low cost production on existing conventional processing equipment；
2, the technology path combined using " high shear blending " and " super drawing ", realizes graphene and other heat fillings It is abundant removing, evenly dispersed, height-oriented and network struction, to the mechanical property of composite material, heating conduction and gas hinder Separating performance, which has, to be obviously improved, and application range is greatly enlarged；
3, by obtaining Oriented thin film to the polymer-modified progress super drawing of graphene, promote thermally conductive fill out off field strongly tensile Material and strand align, and improve filler orientation degree and polymer ordered property and crystallinity, greatly reduce crystal defect With phon scattering caused by grain boundary, the thin polymer film with high thermal conductivity can get；
4, it is improved using the graphene coated agent of high tenacity, while nanometer sheet being bonded very well to reduce difficulty of processing multiple The toughness and ductility of condensation material, ensure that composite material performance balance and low temperature under anti-impact toughness, be guarantee composite wood Expect the premise of large-scale application；
5, the technical method has very strong adaptability, can be widely applied to the nanocomposite processing of other systems, right The large-scale production and application for pushing nanocomposite will generate positive effect.
Detailed description of the invention
Present invention will be further explained below with reference to the attached drawings and examples.
Fig. 1 is the dispersing morphology that graphene and carbon nanotube in embodiment 2 are observed by transmission electron microscope (TEM) Structural schematic diagram, wherein it is high power transmission electron microscope observing that label a, which is low power, b and c,；
Fig. 2 is the structural schematic diagram of the dispersing morphology by 3 graphene of tem observation embodiment and magnesia；
Fig. 3 illustrates the forming process schematic diagram of Monodispersed, highly oriented graphene and the second heat filling in laminated film.
Specific embodiment
Embodiment 1
A kind of preparation method containing Monodispersed, polymer bond's film of highly oriented graphene, comprising the following steps:
The first step, graphene modified composite material: at 160 DEG C, by 30 parts of PE, 40 parts of graphenes (trade mark ENN-HTC-5L, Xin Ao graphene Technology Co., Ltd.), 30 parts of boron nitride, 20 parts of EVA, 20 parts of paraffin, 4 parts of silane coupling agent KH560,13 parts it is white Tipping bucket type mixer is added in oil, 2 parts of ACR, 2 parts of MBS, 1.5 parts of zinc stearates, 0.5 part of irgasfos 168 and 1 part of antioxidant 1010 Middle progress " high shear melt blending ", after being kneaded output the ratio between energy and all mixture qualities and reaching 1 kWh/kg, through cold But granulation obtains graphene modified composite material；
The modified thermally conductive film of second step, graphene: graphene modified composite material obtained by S11 is squeezed at 180 DEG C by sheet material Machine carries out " high power hot-stretch " process out, and draw ratio (drawing ratio, DR) is set as 5, reaches in film forming thickness It forms and winds after 100 μm, obtain the modified thermally conductive film of graphene.
Embodiment 2
A kind of preparation method containing Monodispersed, polymer bond's film of highly oriented graphene, comprising the following steps:
The first step, graphene modified composite material: at 120 DEG C, by 80 parts of PVC, 5 parts of graphenes (trade mark ENN-HTC-5L, Xin Ao graphene Technology Co., Ltd.), 15 parts of carbon nanotubes (trade mark ENN-CMw11, Xin Ao graphene Technology Co., Ltd.), 10 Part paraffin, 0.015 part of titanate esters and 5 parts of epoxidized soybean oils are added in high-speed mixers and carry out " high shear melt blending ", mixed After refining output the ratio between energy and all mixture qualities reach 0.1 kWh/kg, graphene modified composite material is obtained；
The modified thermally conductive film of second step, graphene: by graphene modified composite material obtained by S21 by equipped with cone at 160 DEG C The sheet extruder of shape double screw extruder carries out " high power hot-stretch " process, and DR is set as 2, reaches in film forming thickness It forms and winds after 100 μm, obtain the modified thermally conductive film of graphene.
Embodiment 3
A kind of preparation method containing Monodispersed, polymer bond's film of highly oriented graphene, comprising the following steps:
The first step, graphene modified composite material: at 250 DEG C, by 60 parts of PC, 20 parts of graphenes (trade mark ENN-HTC-5L, Xin Ao graphene Technology Co., Ltd.), 20 parts of magnesia, 10 parts of SBS, 2 parts of Aluminates, 0.4 part of irgasfos 168 and 0.8 part it is anti- Oxygen agent 1010 adds twin-screw extrude progress " high shear melt blending ", is being kneaded output energy and all mixture qualities The ratio between reach 2 kWh/kg after, obtain graphene modified composite material；
The modified thermally conductive film of second step, graphene: graphene modified composite material obtained by S31 is passed through into casting films at 250 DEG C Machine carries out " high power hot-stretch " process, and DR is set as 20, forms and wind after film forming thickness reaches 100 μm, obtains stone The modified thermally conductive film of black alkene.
Embodiment 4
A kind of preparation method containing Monodispersed, polymer bond's film of highly oriented graphene, comprising the following steps:
The first step, graphene modified composite material: at 270 DEG C, by 70 parts of PET, 30 parts of graphenes (trade mark ENN-HTC-5L, Xin Ao graphene Technology Co., Ltd.), 10 parts of aluminium oxide, 5 parts of EVA, 5 parts of EMA, 5 parts of polyethylene waxes, 1.5 parts of silane coupling agents KH550,0.5 part of irgasfos 168 and 1 part of antioxidant 1010 are added in continuous internal mixer and carry out " high shear melt blending ", After mixing output the ratio between energy and all mixture qualities reach 2.5 kWh/kg, graphene modified composite material is obtained；
The modified thermally conductive film of second step, graphene: graphene modified composite material obtained by S41 is squeezed at 290 DEG C by sheet material Machine carries out " high power hot-stretch " process out, and DR is set as 200, forms and wind after film forming thickness reaches 100 μm, obtain Obtain the modified thermally conductive film of graphene.
Embodiment 5
A kind of preparation method containing Monodispersed, polymer bond's film of highly oriented graphene, comprising the following steps:
The first step, graphene modified composite material: at 230 DEG C, by 60 parts of PS, 10 parts of graphenes (trade mark ENN-HTC-5L, Xin Ao graphene Technology Co., Ltd.), 30 parts of micro powder graphites, 10 parts of SBS, 5 parts of polyethylene waxes, 4 parts of octadecylamines, 2 parts it is white Progress in convertible mixer is added in oil, 1.5 parts of zinc stearates, 0.5 part of DLTDP and 1 part of antioxidant 1010, and " high shear melting is altogether It is mixed ", after being kneaded output the ratio between energy and all mixture qualities and reaching 5 kWh/kg, obtain graphene modified composite material；
The modified thermally conductive film of second step, graphene: graphene modified composite material obtained by S51 is squeezed at 240 DEG C by sheet material Machine carries out " high power hot-stretch " process out, and DR is set as 10, forms and wind after film forming thickness reaches 100 μm, obtains Graphene is modified thermally conductive film.
Embodiment 6
A kind of preparation method containing Monodispersed, polymer bond's film of highly oriented graphene, comprising the following steps:
The first step, graphene modified composite material: at 210 DEG C, by 50 parts of PP, 5 parts of graphenes (trade mark ENN-HTC-5L, newly Graphene Technology Co., Ltd. difficult to understand), 45 parts of aluminium nitride, 1 part of EPDM, 0.1 part of isocyanates, 2 parts of white oils, 2 parts of zinc stearates, 15 ACR and 1 part of antioxidant 300 of part adds twin-screw extrude progress " high shear melt blending ", is being kneaded output energy and institute After thering is the ratio between mixture quality to reach 3 kWh/kg, graphene modified composite material is obtained；
The modified thermally conductive film of second step, graphene: graphene modified composite material obtained by S61 is passed through into casting films at 230 DEG C Machine carries out " high power hot-stretch " process, and DR is set as 50, forms and wind after film forming thickness reaches 100 μm, obtains stone The modified thermally conductive film of black alkene.
Comparative example 1
The first step, graphene modified composite material: at 160 DEG C, by 30 parts of PE, 40 parts of graphenes (trade mark ENN-HTC-5L, Xin Ao graphene Technology Co., Ltd.), 30 parts of boron nitride, 20 parts of EVA, 20 parts of paraffin, 4 parts of silane coupling agent KH560,13 parts it is white Tipping bucket type mixer is added in oil, 2 parts of ACR, 2 parts of MBS, 1.5 parts of zinc stearates, 0.5 part of irgasfos 168 and 1 part of antioxidant 1010 Middle progress " high shear melt blending ", after being kneaded output the ratio between energy and all mixture qualities and reaching 1 kWh/kg, through cold But granulation obtains graphene modified composite material；
The modified thermally conductive film of second step, graphene: by graphene modified composite material obtained by D11 180 DEG C, etc. lead under static pressure It crosses compression molding forming machine to be formed, obtains the modified thermally conductive film of graphene that thickness reaches 100 μm.
Comparative example 2
The first step, graphene modified composite material: at 160 DEG C, by 30 parts of PE, 40 parts of graphenes (trade mark ENN-HTC-5L, Xin Ao graphene Technology Co., Ltd.), 20 parts of EVA, 20 parts of paraffin, 4 parts of silane coupling agent KH560,13 parts of white oils, 2 parts of ACR, 2 Progress in tipping bucket type mixer is added in part MBS, 1.5 parts of zinc stearates, 0.5 part of irgasfos 168 and 1 part of antioxidant 1010, and " height is cut Cut melt blending ", after being kneaded output the ratio between energy and all mixture qualities and reaching 1 kWh/kg, stone is obtained through cooling pelletization Black alkene modified composite material；
The modified thermally conductive film of second step, graphene: graphene modified composite material obtained by D21 is squeezed at 180 DEG C by sheet material Machine carries out " high power hot-stretch " process out, and draw ratio (drawing ratio, DR) is set as 5, reaches in film forming thickness It forms and winds after 100 μm, obtain the modified thermally conductive film of graphene.
Heating conduction, mechanics to thin-film material in each embodiment and comparative example of the present invention (thickness is 100 μm) Performance and gas barrier property are tested, and specifically include table 1, table 2, shown in table 3, method of evaluating performance and testing standard Are as follows:
Determination of conductive coefficients: according to Determination of conductive coefficients standard in the ASTM E1461 of American Society for Testing Materials, Germany is used The resistance to 447 model conductometer of LFA speeded carries out performance evaluation to composite material.Every group is at least tested 3 parallel samples, is as a result taken Its average value.
Mechanics Performance Testing: according to plastic tensile performance test mark in the ASTM D638-2003 of American Society for Testing Materials Standard tests the tensile property of composite material using the universal tensile machine (model 5900) of Instron company, the U.S..Every group At least guarantee 3 parallel test samples, as a result takes its average value.
Oxygen permeability coefficient test: according to the Ministry of Aero-Space Industry, People's Republic of China (PRC) aerospace industry standard " organic material Expect gas permeability coefficient test method (QJ 2194-91) ", oxygen permeability coefficient of the thermally conductive film at 25 DEG C is tested, often Group at least tests 3 parallel samples, as a result takes its average value.
The proportion by weight of each component in the polymer-modified thermally conductive film of 1. graphene of table
The moulding process and parameter of the polymer-modified thermally conductive film of 2. graphene of table
The performance test results of the polymer-modified thermally conductive film of 3. graphene of table
Experimental result:
As shown in Figure 1 and Figure 2, using the dispersing morphology of graphene and the second heat filling in transmission electron microscope observing thermally conductive film, Confirmation takes technology path of the invention that can obtain sufficiently removing, evenly dispersed, high-orientation graphene nanometer sheet, nanometer It is mutually overlapped between piece and nanometer sheet or between nanometer sheet and the second heat filling, as shown in figure 3, constructing the network knot of connection Structure, this unique network structure greatly improve the heating conduction and mechanical property of graphene modified film.
As shown in table 3, the test result of thermal coefficient shows be successfully introduced into highly oriented, Monodispersed graphene nano After the network of the-the second heat filling of piece, being obviously improved occurs in the thermal coefficient of laminated film, by taking preferably embodiment 1 as an example, When graphene content is 24.4 wt%, boron nitride content is 18.3 wt%, thermal coefficient has reached 205.8 W/m K, compared with without The comparative example 1(7.9 W/m K of super drawing) and comparative example 2(12.5 W/m K without boron nitride hydridization) be respectively increased it is super 25 times and 15 times are crossed, for highest in existing open report.
More importantly: the network structure of highly oriented, Monodispersed graphene and the building of the second heat filling, to composite wood The mechanical property and oxygen resistance of material improve significantly, have both improved the tensile strength of film, and have also reduced oxygen permeability coefficient, such as Shown in table 2.By taking embodiment 4 as an example, when adding 25.4 wt% graphenes and 8.7 wt% aluminium oxide, the stretching of thermally conductive film is strong Degree and oxygen permeability coefficient are 2784 MPa and 0.1 cm3∙μm/m2Day kPa presents excellent mechanics-barrier balance.
As it can be seen that graphene nanometer sheet can be promoted using the technology path that " high shear blending " and " super drawing " combine With other heat fillings are evenly dispersed in a polymer matrix, height-oriented and network structure building, solve conventional films It is high in material processing method to fill multiple material difficulty processing, difficult dispersion, challenge easy to reunite, while obtaining the highly oriented platelet of crystalline state Have with the nanofiber of amorphous state to greatly improve the heating conduction of laminated film, mechanical property and gas barrier property It hopes and greatly expands polymer material in the application range in thermal control field.

Claims (10)

1. a kind of polymer bond's film containing Monodispersed, highly oriented graphene, it is characterised in that: the thermally conductive film material by Following components is constituted:
30 80 parts of polymeric matrix；
5 40 parts of graphene；
Second 10 30 parts of heat filling；
0.015 4 parts of surface treating agent；
1 40 parts of filler covering；
0.5 20 parts of processing aid.
2. polymer bond's film containing Monodispersed, highly oriented graphene as described in claim 1, it is characterised in that: described Polymeric matrix is polyethylene, polypropylene, polyvinyl chloride, Kynoar, polystyrene, polyamide, polycarbonate, gathers to benzene At least one of dioctyl phthalate butanediol ester or polyethylene terephthalate.
3. polymer bond's film containing Monodispersed, highly oriented graphene as described in claim 1, it is characterised in that: described The maximum radial dimension of graphene is 0.5 40 μm, with a thickness of 1 20 nm.
4. polymer bond's film containing Monodispersed, highly oriented graphene as described in claim 1, it is characterised in that: described Second heat filling is boron nitride, silicon carbide, antifungin, aluminium borate, magnesium carbonate, aluminium oxide, zinc oxide, magnesia, hydroxide Magnesium, calcium carbonate, calcium sulfate, graphite, can at least one of swollen graphite, expanded graphite, carbon fiber or carbon nanotube.
5. polymer bond's film containing Monodispersed, highly oriented graphene as described in claim 1, it is characterised in that: described When surface treating agent is silane coupling agent, surface treating agent and the graphene and the ratio of heat filling gross mass are 2 10: 100；
Or the surface treating agent is octadecylamine, isocyanates, Aluminate or when titanate coupling agent, surface treating agent with The graphene and the ratio of heat filling gross mass are 0.3 1.5:100.
6. polymer bond's film containing Monodispersed, highly oriented graphene as described in claim 1, it is characterised in that: described Filler covering is paraffin, thermoplastic elastomer (TPE) (TPE), polyolefin elastomer (POE), polyethylene wax, ethylene propylene diene rubber (EPDM), styrene analog thermoplastic elastomer (SBS), ethylene-vinyl acetate copolymer (EVA), butadiene-styrene rubber (SBR), second Alkene-methyl acrylate copolymer (EMA), ethylene-ethyl acrylate copolymer (EEA), ethylene-butyl acrylate copolymer (EBA) and at least one of polyester elastomer (TPEE).
7. polymer bond's film containing Monodispersed, highly oriented graphene as described in claim 1, it is characterised in that: described Processing aid is epoxidized soybean oil, ACR, CPE, MBS, SMA, white oil, stearic acid, stearate, irgasfos 168, antioxidant 300, at least one of antioxidant 1010 and dilauryl thiodipropionate (DLTDP).
8. the preparation method containing Monodispersed, polymer bond's film of highly oriented graphene as described in claim 1, feature It is:
The preparation method the following steps are included:
The first step, high shear melt blending: temperature be 120 300 DEG C at, by polymer, graphene, the second heat filling, Surface treating agent, covering and processing aid carry out melt blended, the output energy of Blending Processes under high shear strength in proportion The ratio between amount and all mixture quality are 0.1 5 kWh/kg, then through cooling and dicing or are directly granulated, acquisition Monodispersed graphite Alkene is filled polymer-modified；
Second step, high power mechanically thermal stretching: in the case where temperature is 160 300 DEG C, Monodispersed graphene described in the first step is filled Polymer-modified carry out high power mechanical stretching, stretching ratio be 2 200, obtain the polymerization containing Monodispersed, highly oriented graphene Object thermally conductive film, the molding thickness of thermally conductive film are 10 800 μm.
9. the preparation method containing Monodispersed, polymer bond's film of highly oriented graphene as claimed in claim 8, feature Be: the melt blending equipment in the first step is reciprocating screw extruding machine, double screw extruder, high-speed mixer, opens Mill, convertible mixer, continuous internal mixer, Z-type kneader, screw mixer, vacuum kneader and Horizontal double-spiral are mixed At least one of conjunction machine.
10. the preparation method containing Monodispersed, polymer bond's film of highly oriented graphene as claimed in claim 8, special Sign is: mechanically thermal stretching equipment is at least one in sheet extruder, film blow molding machine and cast film machine in the second step Kind.
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