CN104072868A - Graphene-like modified thermal conductive plastic and preparation method thereof - Google Patents

Graphene-like modified thermal conductive plastic and preparation method thereof Download PDF

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Publication number
CN104072868A
CN104072868A CN201410258384.7A CN201410258384A CN104072868A CN 104072868 A CN104072868 A CN 104072868A CN 201410258384 A CN201410258384 A CN 201410258384A CN 104072868 A CN104072868 A CN 104072868A
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class graphene
plastic
powder
graphene
density
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CN104072868B (en
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袁奕琳
陆卓君
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NINGBO SINYUAN CARBON MATERIAL INCORPORATED Co.
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NINGBO SINYUAN GRAPHITE Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00Use of pretreated ingredients
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/02Elements
    • C08K3/04Carbon
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/002Physical properties
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/002Physical properties
    • C08K2201/003Additives being defined by their diameter

Abstract

The invention belongs to the technical field of modified thermal conductive plastics and in particular relates to a graphene-like modified thermal conductive plastic and a preparation method thereof. The graphene-like modified thermal conductive plastic comprises the components of a plastic base material and graphene-like, wherein the plastic base material accounts for 80-90 weight percentage of total mass; the graphene-like accounts for 10-20 weight percentage of total mass; and the carbon content of the graphene-like is more than or equal to 97 percent; the bulk density of the graphene-like is 0.15-0.3g/ml. Because the graphene-like modified thermal conductive plastic is prepared by mixing high-density graphene-like powder and the plastic base material, and the bulk density of the graphene-like powder reaches 0.15-0.3g/ml, so that the graphene-like powder can be fully mixed with the plastic base material, and the graphene-like powder in a layered structure can be uniformly distributed in the plastic base material and forms a meshed structure with a plastic high polymer. Therefore, various mechanical properties of the plastics are remained to the greatest degree, and the plastic has excellent thermal conductive performance.

Description

One kind Graphene modification heat-conducting plastic and preparation method thereof
Technical field
The invention belongs to modification heat-conducting plastic technical field, relate in particular to kind Graphene modification heat-conducting plastic and preparation method thereof.
Background technology
Along with industrial production and scientific and technical development, people are more and more higher to the requirement of thermally conductive material over-all properties, and traditional metallic substance cannot meet the service requirements of some special occasions.Heat run-up and increase as electronics produces, can cause device cisco unity malfunction, therefore heat radiation has in time become the important factor that affects its life-span.So be badly in need of the heat-conducting insulation material of the excellent combination property of development high reliability, high-cooling property, replace traditional material.Heat-conducting polymer material especially heat-conducting plastic owing to having, lightweight, resistance to chemical attack, easily machine-shaping, electrical insulation capability are excellent, mechanics and the feature such as anti-fatigue performance is good, more and more be subject to people's attention, become gradually the new role in heat conduction field, the focus of international and domestic research and development in recent years.
Macromolecular material insulate, but as thermally conductive material, pure macromolecular material is generally inefficient, because macromolecular material is hot poor conductor mostly, macromolecular material thermal conductivity is about 1/500 ~ 1/600 of metal.The thermal conductivity of porous plastics only has 0.02 ~ 0.046 w/m.K, is about 1/1500 of metal, 1/40 of cement concrete, and the l/20 of common brick, is desirable thermal insulation material, expand it in the application in heat conduction field, must carry out modification to macromolecular material.
At present, be mainly to add graphene powder at macromolecular material, because added graphene powder in macromolecular material, because carbon has good heat-conductive characteristic, make also there is good heat conductivility through the macromolecular material of Graphene modification.The heat conductivility of the macromolecular material of process Graphene modification depends on the content of carbon and the degree of uniformity of carbon and macromolecular material fusion.The tap density of the graphene powder that existing technique makes is below 0.15g/ml, because the tap density of graphene powder is too small, make graphene powder be difficult to fully merge with polymer particles, carbon is skewness in macromolecular material, makes the heat conductivility of the macromolecular material after modification not ideal enough.
Summary of the invention
The object of the invention is to provides a kind Graphene modification heat-conducting plastic for the deficiencies in the prior art, and it adopts highly close class graphene powder, and class graphene powder and plastic base instinct are fully merged, and overcomes the deficiencies in the prior art.
For achieving the above object, class Graphene modification heat-conducting plastic of the present invention adopts following technical scheme: a kind Graphene modification heat-conducting plastic, its component comprises plastic basis material and class Graphene, the weight percent that described plastic basis material accounts for total mass is 80%~90%, the weight percent that described class Graphene accounts for total mass is 10%~20%, and the tap density of described class Graphene is 0.15~0.3g/ml.
The granularity of described class Graphene is 25~300 um.
The thickness of described class Graphene is 3~60nm.
The carbon content of described class Graphene is more than or equal to 97%.
Described component also comprises coupling agent, and the weight percent that described coupling agent accounts for total mass is 0.1%~1%.
Described plastic basis material is PP plastics, PVA plastics, PVE plastics, HDPE plastics or PE-RT plastics.
The beneficial effect of class Graphene modification heat-conducting plastic of the present invention: because the present invention adopts highly close class graphene powder to mix with plastic basis material, wherein, the tap density of class graphene powder reaches 0.15~0.3g/ml, class graphene powder can fully be mixed with plastic basis material, the class Graphene powder of laminate structure can be uniformly distributed in plastic basis material, and form reticulated structure with plastics polymer, make the present invention farthest retain every mechanical property of plastics, and there is good heat conductivility, thermal conductivity can reach 1~5W/M.K, the oxygen transmission rate of the tubing that use the present invention makes is lower than 50mg/L.D.
The present invention also provides a kind of method of preparing class Graphene modification heat-conducting plastic, and its step comprises:
The first step, first carries out chemical acidification processing by natural graphite scale, with strong oxidation intercalator, inserts natural graphite interlayer, forms hydrate, ready for opening the interlayer structure of natural graphite; Then under the hot environment of 800~1200 ℃, heat-treat, moment high temperature make hydrate moment gasification of interlayer intercalation, the caused volume change that gasifies is opened natural graphite layer moment, forms vermiform graphite;
Second step, roll processing, the vermiform graphite that the first step is made is after cylinder roll compacting, make thickness and be and be less than or equal to 1.0mm, density to be more than or equal to the natural graphite of 1.0g/ml rectangular, then carrying out fine powder for the first time processes, low-density class graphene powder in making, in the density of low-density class graphene powder for being less than or equal to 0.15 g/ml;
The 3rd step, during second step is made, low-density class graphene powder is molded into piece processing, make graphite block, graphite block density is more than or equal to 1.5g/ml, and then enter pulverizer and carry out separating twice, make highdensity class graphene powder, the tap density of highdensity class graphene powder is 0.15~0.3g/ml;
The 4th step, the highdensity class graphene powder that the 3rd step is made and plastic basis material add twin screw continuous granulation machine to carry out combination treatment, and class graphene powder and plastic basis material make class Graphene modification heat-conducting plastic after fully merging.
In the 3rd step, the highdensity class graphene powder making is carried out to interlayer slip processing.
In the 4th step, while adopting twin screw continuous granulation machine to mix class graphene powder and plastic basis material, make class graphene powder in plastic basis material, form many Graphene chains.
In the 3rd step, in the highdensity class graphene powder making, add coupling agent, activation treatment is carried out in class graphene powder surface.
The beneficial effect of preparing the method for class Graphene modification heat-conducting plastic of the present invention: the present invention is when preparation class graphene powder, the class graphene powder of centering density is molded into piece and processes, make the graphite block that density is 1.5g/ml, carry out again the processing of secondary fine powder, make highdensity class graphene powder, the tap density of highdensity class graphene powder is 0.15~0.3g/ml, highdensity class graphene powder is fully mixed with plastic basis material, the class Graphene powder of laminate structure can be uniformly distributed in plastic basis material, and form reticulated structure with plastics polymer, make the present invention farthest retain every mechanical property of plastics, and there is good heat conductivility, thermal conductivity can reach 1~5W/M.K, the oxygen transmission rate of the tubing that use the present invention makes is lower than 50mg/L.D.
Specific embodiment
Embodiment 1
One kind Graphene modification heat-conducting plastic, its component comprises plastic basis material and class Graphene, and plastic basis material is PP plastics, and the weight percent that plastic basis material accounts for total mass is 80%, the weight percent that class Graphene accounts for total mass is 20%, and the tap density of class Graphene is 0.15g/ml.
The granularity of class Graphene is 25um.
The thickness of class Graphene is 3nm.
The carbon content of class Graphene is 97%.
Embodiment 2
One kind Graphene modification heat-conducting plastic, its component comprises plastic basis material and class Graphene, and plastic basis material is PP plastics, and the weight percent that plastic basis material accounts for total mass is 90%, the weight percent that class Graphene accounts for total mass is 10%, and the tap density of class Graphene is 0.20g/ml.
The granularity of class Graphene is 100um.
The thickness of class Graphene is 20nm.
The carbon content of class Graphene is 99%.
Embodiment 3
One kind Graphene modification heat-conducting plastic, its component comprises plastic basis material and class Graphene, and plastic basis material is PP plastics, and the weight percent that plastic basis material accounts for total mass is 84%, the weight percent that class Graphene accounts for total mass is 16%, and the tap density of class Graphene is 0.25g/ml.
The granularity of class Graphene is 200um.
The thickness of class Graphene is 45nm.
The carbon content of class Graphene is 99%.
Embodiment 4
One kind Graphene modification heat-conducting plastic, its component comprises plastic basis material and class Graphene, and plastic basis material is PP plastics, and the weight percent that plastic basis material accounts for total mass is 88%, the weight percent that class Graphene accounts for total mass is 12%, and the tap density of class Graphene is 0.30g/ml.
The granularity of class Graphene is 300um.
The thickness of class Graphene is 60nm.
The carbon content of class Graphene is 99%.
Embodiment 5
One kind Graphene modification heat-conducting plastic, its component comprises plastic basis material and class Graphene, plastic basis material is PP plastics, the weight percent that plastic basis material accounts for total mass is 89.9%, the weight percent that class Graphene accounts for total mass is 10%, component also comprises coupling agent, and the weight percent that coupling agent accounts for total mass is 0.1%, and the tap density of class Graphene is 0.23g/ml.
The granularity of class Graphene is 250um.
The thickness of class Graphene is 50nm.
The carbon content of class Graphene is 99%.
Embodiment 6
A method of preparing class Graphene modification heat-conducting plastic, its step comprises:
The first step, first carries out chemical acidification processing by natural graphite scale, with strong oxidation intercalator, inserts natural graphite interlayer, forms hydrate, ready for opening the interlayer structure of natural graphite; Then under the hot environment of 800 ℃, heat-treat, moment high temperature make hydrate moment gasification of interlayer intercalation, the caused volume change that gasifies is opened natural graphite layer moment, forms vermiform graphite;
Second step, roll processing, the vermiform graphite that the first step is made is after cylinder roll compacting, the natural graphite that to make thickness and be 1.0mm, density be 1.0g/ml is rectangular, then carrying out fine powder for the first time processes, low-density class graphene powder in making, in the density of low-density class graphene powder be 0.12 g/ml;
The 3rd step, during second step is made, low-density class graphene powder is molded into piece processing, make graphite block, graphite block density is 1.5g/ml, and then enter pulverizer and carry out separating twice, make highdensity class graphene powder, the tap density of highdensity class graphene powder is 0.15g/ml;
The 4th step, the highdensity class graphene powder that the 3rd step is made and plastic basis material add twin screw continuous granulation machine to carry out combination treatment, and class graphene powder and plastic basis material make class Graphene modification heat-conducting plastic after fully merging.
In the 3rd step, the highdensity class graphene powder making is carried out to interlayer slip processing.
In the 4th step, while adopting twin screw continuous granulation machine to mix class graphene powder and plastic basis material, make class graphene powder in plastic basis material, form many Graphene chains.
In the 3rd step, in the highdensity class graphene powder making, add coupling agent, activation treatment is carried out in class graphene powder surface.
Embodiment 7
A method of preparing class Graphene modification heat-conducting plastic, its step comprises:
The first step, first carries out chemical acidification processing by natural graphite scale, with strong oxidation intercalator, inserts natural graphite interlayer, forms hydrate, ready for opening the interlayer structure of natural graphite; Then under the hot environment of 1000 ℃, heat-treat, moment high temperature make hydrate moment gasification of interlayer intercalation, the caused volume change that gasifies is opened natural graphite layer moment, forms vermiform graphite;
Second step, roll processing, the vermiform graphite that the first step is made is after cylinder roll compacting, the natural graphite that to make thickness and be 0.3mm, density be 1.2g/ml is rectangular, then carrying out fine powder for the first time processes, low-density class graphene powder in making, in the density of low-density class graphene powder be 0.14 g/ml;
The 3rd step, during second step is made, low-density class graphene powder is molded into piece processing, make graphite block, graphite block density is 1.9g/ml, and then enter pulverizer and carry out separating twice, make highdensity class graphene powder, the tap density of highdensity class graphene powder is 0.25g/ml;
The 4th step, the highdensity class graphene powder that the 3rd step is made and plastic basis material add twin screw continuous granulation machine to carry out combination treatment, and class graphene powder and plastic basis material make class Graphene modification heat-conducting plastic after fully merging.
In the 3rd step, the highdensity class graphene powder making is carried out to interlayer slip processing.
In the 4th step, while adopting twin screw continuous granulation machine to mix class graphene powder and plastic basis material, make class graphene powder in plastic basis material, form many Graphene chains.
In the 3rd step, in the highdensity class graphene powder making, add coupling agent, activation treatment is carried out in class graphene powder surface.
Embodiment 8
A method of preparing class Graphene modification heat-conducting plastic, its step comprises:
The first step, first carries out chemical acidification processing by natural graphite scale, with strong oxidation intercalator, inserts natural graphite interlayer, forms hydrate, ready for opening the interlayer structure of natural graphite; Then under the hot environment of 1000 ℃, heat-treat, moment high temperature make hydrate moment gasification of interlayer intercalation, the caused volume change that gasifies is opened natural graphite layer moment, forms vermiform graphite;
Second step, roll processing, the vermiform graphite that the first step is made is after cylinder roll compacting, the natural graphite that to make thickness and be 0.9mm, density be 1.3g/ml is rectangular, then carrying out fine powder for the first time processes, low-density class graphene powder in making, in the density of low-density class graphene powder be 0.145g/ml;
The 3rd step, during second step is made, low-density class graphene powder is molded into piece processing, make graphite block, graphite block density is 2.0g/ml, and then enter pulverizer and carry out separating twice, make highdensity class graphene powder, the tap density of highdensity class graphene powder is 0.3g/ml;
The 4th step, the highdensity class graphene powder that the 3rd step is made and plastic basis material add twin screw continuous granulation machine to carry out combination treatment, and class graphene powder and plastic basis material make class Graphene modification heat-conducting plastic after fully merging.
In the 3rd step, the highdensity class graphene powder making is carried out to interlayer slip processing.
In the 4th step, while adopting twin screw continuous granulation machine to mix class graphene powder and plastic basis material, make class graphene powder in plastic basis material, form many Graphene chains.
In the 3rd step, in the highdensity class graphene powder making, add coupling agent, activation treatment is carried out in class graphene powder surface.
The announcement of book and instruction according to the above description, those skilled in the art in the invention can also change and revise above-mentioned embodiment.Therefore, the present invention is not limited to above-mentioned embodiment, and any apparent improvement, replacement or modification that every those skilled in the art have done on basis of the present invention all belong to protection scope of the present invention.In addition,, although used some specific terms in this specification sheets, these terms just for convenience of description, do not form any restriction to the present invention.

Claims (10)

1. a kind Graphene modification heat-conducting plastic, its component comprises plastic basis material and class Graphene, it is characterized in that: the weight percent that described plastic basis material accounts for total mass is 80%~90%, the weight percent that described class Graphene accounts for total mass is 10%~20%, and the tap density of described class Graphene is 0.15~0.3g/ml.
2. class Graphene modification heat-conducting plastic according to claim 1, is characterized in that: the granularity of described class Graphene is 25~300um.
3. class Graphene modification heat-conducting plastic according to claim 1, is characterized in that: the thickness of described class Graphene is 3~60nm.
4. class Graphene modification heat-conducting plastic according to claim 1, is characterized in that: the carbon content of described class Graphene is more than or equal to 97%.
5. class Graphene modification heat-conducting plastic according to claim 1, is characterized in that: described component also comprises coupling agent, and the weight percent that described coupling agent accounts for total mass is 0.1%~1%.
6. class Graphene modification heat-conducting plastic according to claim 1, is characterized in that: described plastic basis material is PP plastics, PVA plastics, PVE plastics, HDPE plastics or PE-RT plastics.
7. the method for the class Graphene modification heat-conducting plastic described in preparation claim 1 to 6 any one, its step comprises:
The first step, first carries out chemical acidification processing by natural graphite scale, with strong oxidation intercalator, inserts natural graphite interlayer, forms hydrate, ready for opening the interlayer structure of natural graphite; Then under the hot environment of 800~1200 ℃, heat-treat, moment high temperature make hydrate moment gasification of interlayer intercalation, the caused volume change that gasifies is opened natural graphite layer moment, forms vermiform graphite;
Second step, roll processing, the vermiform graphite that the first step is made is after cylinder roll compacting, make thickness and be and be less than or equal to 1.0mm, density to be more than or equal to the natural graphite of 1.0g/ml rectangular, then carrying out fine powder for the first time processes, low-density class graphene powder in making, in the density of low-density class graphene powder for being less than or equal to 0.15 g/ml;
The 3rd step, during second step is made, low-density class graphene powder is molded into piece processing, make graphite block, graphite block density is more than or equal to 1.5g/ml, and then enter pulverizer and carry out separating twice, make highdensity class graphene powder, the tap density of highdensity class graphene powder is 0.15~0.3g/ml;
The 4th step, the highdensity class graphene powder that the 3rd step is made and plastic basis material add twin screw continuous granulation machine to carry out combination treatment, and class graphene powder and plastic basis material make class Graphene modification heat-conducting plastic after fully merging.
8. the method for preparing class Graphene modification heat-conducting plastic according to claim 7, is characterized in that: in the 3rd step, the highdensity class graphene powder making is carried out to interlayer slip processing.
9. the method for preparing class Graphene modification heat-conducting plastic according to claim 7; it is characterized in that: in the 4th step; while adopting twin screw continuous granulation machine to mix class graphene powder and plastic basis material, make class graphene powder in plastic basis material, form many Graphene chains.
10. the method for preparing class Graphene modification heat-conducting plastic according to claim 7, is characterized in that: in the 3rd step, in the highdensity class graphene powder making, add coupling agent, activation treatment is carried out in class graphene powder surface.
CN201410258384.7A 2014-06-12 2014-06-12 Graphene-like modified thermal conductive plastic and preparation method thereof Active CN104072868B (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN202279696U (en) * 2011-10-27 2012-06-20 中科恒达石墨股份有限公司 Continuous expansible graphite production device
CN103087404A (en) * 2011-10-31 2013-05-08 上海杰事杰新材料(集团)股份有限公司 Graphene filled polymer matrix composite material and its preparation method

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2835262A1 (en) * 2011-05-06 2012-11-15 The Research Foundation For The State University Of New York Magnetic graphene-like nanoparticles or graphitic nano-or microparticles and method of production and uses thereof
CN103641119B (en) * 2013-12-03 2015-10-28 江苏大学 The preparation method of one kind grapheme material

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN202279696U (en) * 2011-10-27 2012-06-20 中科恒达石墨股份有限公司 Continuous expansible graphite production device
CN103087404A (en) * 2011-10-31 2013-05-08 上海杰事杰新材料(集团)股份有限公司 Graphene filled polymer matrix composite material and its preparation method

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Effective date of registration: 20201023

Address after: 315311 Chao Sheng Road, Cixi Binhai Economic Development Zone, Ningbo, Zhejiang Province, No. 1515

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Patentee before: NINGBO SINYUAN GRAPHITE Co.,Ltd.