CN107418052B - Graphene microchip/polymer composite material and preparation method thereof - Google Patents
Graphene microchip/polymer composite material and preparation method thereof Download PDFInfo
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- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
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- C08L27/02—Compositions 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; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions 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; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
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Abstract
本发明提供了一种石墨烯微片/聚合物复合材料，由包括以下组分的原料制备而成：聚合物85重量份～99重量份；复配石墨烯片层1重量份～15重量份；润滑剂0.1重量份～5重量份；偶联剂0.01重量份～0.5重量份；所述复配石墨烯片层由片径不同的石墨烯微片组成。与现有技术相比，本发明从影响材料性能的理论出发，充分利用材料自身属性的优劣，通过改进材料固有属性，以复配石墨烯片层为复合材料的增强体，从而有效改善石墨烯片层的剥离和分散效果，得到的产品在力学性能稳定的基础上，具有更为优异的导电、导热性能。实验结果表明，本发明提供的石墨烯微片/聚合物复合材料的电导率能够达到7.5×10‑1S/m，热导率能够达到0.981W/mk，抗拉强度能够达到34.8MPa。
The invention provides a graphene micro-sheet/polymer composite material, which is prepared from raw materials including the following components: 85 to 99 parts by weight of a polymer; 1 to 15 parts by weight of a composite graphene sheet layer 0.1 to 5 parts by weight of lubricant; 0.01 to 0.5 part by weight of coupling agent; the composite graphene sheet is composed of graphene micro-sheets with different sheet diameters. Compared with the prior art, the present invention starts from the theory of affecting material properties, makes full use of the advantages and disadvantages of the properties of the material itself, and uses the composite graphene sheet as the reinforcement of the composite material by improving the inherent properties of the material, thereby effectively improving the graphite. The peeling and dispersing effect of the olefin layer, the obtained product has more excellent electrical and thermal conductivity on the basis of stable mechanical properties. The experimental results show that the electrical conductivity of the graphene microsheet/polymer composite material provided by the present invention can reach 7.5×10 -1 S/m, the thermal conductivity can reach 0.981W/mk, and the tensile strength can reach 34.8MPa.
Description
Technical Field
The invention relates to the technical field of composite materials, in particular to a graphene microchip/polymer composite material and a preparation method thereof.
Background
The graphene nanoplatelets are used as members of newly discovered carbon-based materials, integrates the advantages of other carbon-based fillers, has low conductive percolation threshold, excellent electrical conductivity, thermal conductivity and mechanical properties and lower cost than single-layer graphene, and provides a new development direction for modification of polymers. The graphene nanoplatelets are added into the polymer as a reinforcing material, so that the electrical conductivity and the thermal conductivity of the polymer-based composite material can be greatly improved, and the graphene nanoplatelets have wide application prospects in the fields of conductive materials, heat conduction materials, shielding materials, electronic packaging and the like.
In order to realize the low-cost and large-scale preparation of the graphene microchip/polymer composite material, researchers have conducted extensive research. At present, the melt blending method is widely accepted as the most promising preparation method due to the universality, environmental protection and economy, and is suitable for industrial production. However, since the graphene nanoplatelets have large specific surface area and surface free energy and strong electrostatic force and van der waals force between the graphene nanoplatelets, they are usually present in the form of aggregates in the polymer, which is not good for improving the performance of the polymer-based composite material, especially for peeling and dispersing the graphene nanoplatelets when they are prepared by a melt-kneading method. Reports show that the stripping and dispersing effects of the graphene nanoplatelets have great influence on the polymer crystallinity and the establishment of a conductive network, so that the performances of the graphene nanoplatelets/polymer composite materials prepared by the graphene nanoplatelets are greatly different.
At present, the prior art generally adopts the improvement of the shearing force in the processing force field to achieve the peeling of the graphene micro-sheets and the uniform low dispersion of the graphene micro-sheets in the polymer, thereby changing the comprehensive performance of the graphene micro-sheets. However, the above technical solutions have poor improvement effects, and are difficult to implement and popularize due to the improvement of mechanical equipment.
Disclosure of Invention
In view of the above, the present invention provides a graphene nanoplatelet/polymer composite material and a preparation method thereof, and the preparation method can effectively improve the peeling and dispersing effects of graphene sheets by improving the inherent properties of the material, and the prepared product has good comprehensive properties.
The invention provides a graphene microchip/polymer composite material which is prepared from the following raw materials:
85 to 99 parts by weight of a polymer;
1-15 parts by weight of compound graphene sheet layer;
0.1 to 5 parts by weight of a lubricant;
0.01 to 0.5 weight portion of coupling agent;
the compound graphene lamellar layer is composed of graphene micro-sheets with different sheet diameters.
Preferably, the graphene nanoplatelets have a sheet diameter of 5 to 100 μm and a sheet thickness of 5 to 100 nm.
Preferably, the graphene nanoplatelets having different sheet diameters are selected from two of graphene nanoplatelets having sheet diameters of 5 to 20 μm, graphene nanoplatelets having sheet diameters of 30 to 50 μm, and graphene nanoplatelets having sheet diameters of 60 to 100 μm.
Preferably, the polymer is selected from one or more of polyethylene, polypropylene, polystyrene, polyvinyl chloride, polycarbonate, polyamide, polyoxymethylene, styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene copolymer, polysulfone, polyethylene terephthalate, polybutylene terephthalate, polyphenylene sulfide and polyether ketone.
Preferably, the coupling agent is selected from one or more of silane coupling agent, titanate coupling agent, aluminate coupling agent and phosphate coupling agent.
The invention also provides a preparation method of the graphene nanoplatelets/polymer composite material, which comprises the following steps:
a) mixing a polymer, a compound graphene sheet layer, a lubricant and a coupling agent to obtain a reaction mixture; the compound graphene lamellar layer consists of graphene micro-sheets with different sheet diameters;
b) melting and blending the reaction mixture obtained in the step a), and then extruding and granulating to obtain granules;
c) carrying out hot-press molding on the granules obtained in the step b), and cooling to obtain the graphene microchip/polymer composite material.
Preferably, the step a) is specifically as follows:
and mixing the compounded graphene sheet layer and an ethanol solution of a coupling agent for the first time, drying, and mixing with a polymer and a lubricant for the second time to obtain a reaction mixture.
Preferably, the first mixing mode is ultrasonic stirring for 10-30 min;
the drying temperature is 80-100 ℃, and the drying time is 10-18 h;
the temperature of the second mixing is 70-105 ℃, and the time is 5-15 min.
Preferably, the melt blending in the step b) is performed by using a twin-screw extruder, and the length-diameter ratio of the twin-screw extruder is (25-60): 1; the rotating speed of the screw is 100 rpm-400 rpm, and the temperature is 150-250 ℃.
Preferably, the hot-press molding in the step c) is carried out at the temperature of 180-250 ℃ and under the pressure of 10-20 MPa for 5-10 min.
The invention provides a graphene microchip/polymer composite material which is prepared from the following raw materials: 85 to 99 parts by weight of a polymer; 1-15 parts by weight of compound graphene sheet layer; 0.1 to 5 parts by weight of a lubricant; 0.01 to 0.5 weight portion of coupling agent; the compound graphene lamellar layer is composed of graphene micro-sheets with different sheet diameters. Compared with the prior art, the invention starts from the theory of influencing the material performance, fully utilizes the advantages and disadvantages of the material properties, improves the inherent properties of the material, and takes the compound graphene lamellar layer as the reinforcement of the composite material, thereby effectively improving the stripping and dispersing effects of the graphene lamellar layer, and the obtained product has more excellent electric conduction and heat conduction performance on the basis of stable mechanical properties. Experimental results show that the conductivity of the graphene nanoplatelet/polymer composite material provided by the invention can reach 7.5 multiplied by 10-1S/m, the thermal conductivity can reach 0.981W/mk, and the tensile strength can reach 34.8 MPa.
Drawings
Fig. 1 is a scanning electron microscope image of the graphene nanoplatelets/polymer composite provided in example 1;
fig. 2 is a comparison diagram of the conductive network structure of the graphene nanoplatelets/polymer composite material provided in examples 1 to 3 after compounding graphene nanoplatelets with different sheet diameters.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a graphene microchip/polymer composite material which is prepared from the following raw materials:
85 to 99 parts by weight of a polymer;
1-15 parts by weight of compound graphene sheet layer;
0.1 to 5 parts by weight of a lubricant;
0.01 to 0.5 weight portion of coupling agent;
the compound graphene lamellar layer is composed of graphene micro-sheets with different sheet diameters.
According to the graphene microchip/polymer composite material, the polymer is used as a matrix, the graphene microchip is used as a reinforcing material, the inherent properties of the material are improved, and the compounded graphene lamellar layer is used as a reinforcing body of the composite material, so that the stripping and dispersing effects of the graphene lamellar layer are effectively improved, and the obtained product has good comprehensive performance.
In the present invention, the polymer is preferably selected from one or more of polyethylene, polypropylene, polystyrene, polyvinyl chloride, polycarbonate, polyamide, polyoxymethylene, styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene copolymer, polysulfone, polyethylene terephthalate, polybutylene terephthalate, polyphenylene sulfide, and polyether ketone, and more preferably polyethylene, polypropylene, polystyrene, polyvinyl chloride, polycarbonate, or acrylonitrile-butadiene-styrene copolymer. In the present invention, the polyethylene includes high density polyethylene, low density polyethylene and chlorinated polyethylene well known to those skilled in the art. The source of the polymer is not particularly limited in the present invention, and commercially available products known to those skilled in the art may be used. In the present invention, the graphene nanoplatelets/polymer composite comprises 85 to 99 parts by weight of a polymer, preferably 90 to 95 parts by weight.
In the invention, the compound graphene sheet layer is composed of graphene micro sheets with different sheet diameters. In the invention, the sheet diameter of the graphene nanoplatelets is preferably 5-100 μm; the complex that graphene nanoplatelets with different sheet diameters are compounded can change a melting and mixing force field to strip and uniformly disperse the graphene nanoplatelets in the polymer, so that the composite material with a better conductive network structure is obtained. In the invention, the graphene nanoplatelets with different sheet diameters are selected from two of graphene nanoplatelets with sheet diameters of 5-20 μm, graphene nanoplatelets with sheet diameters of 30-50 μm and graphene nanoplatelets with sheet diameters of 60-100 μm. According to the invention, two graphene nanoplatelets with different sheet diameters are preferably compounded to obtain a compounded graphene sheet layer, and the mass ratio of the graphene nanoplatelets with large sheet diameters to the graphene nanoplatelets with small sheet diameters is preferably 9: 1-1: 9, more preferably 8: 2-5: 5.
in the present invention, the thickness of the graphene nanoplatelets is preferably 5nm to 100 nm.
The source of the graphene nanoplatelets is not particularly limited in the present invention, and commercially available products known to those skilled in the art may be used, and preferably, graphene nanoplatelets KNG180, graphene nanoplatelets CZ030, graphene nanoplatelets G5, graphene nanoplatelets KNG182, and graphene nanoplatelets KNG150 are used. In a preferred embodiment of the invention, the compound graphene lamellar layer is prepared by mixing 100nm thick graphene micro-platelets KNG180 with a platelet diameter of 100 μm and 30nm thick graphene micro-platelets CZ030 with a platelet diameter of 40 μm according to a mass ratio of 8: 2, preparing a composition; in another preferred embodiment of the invention, the compound graphene lamellar layer is prepared by mixing 100nm thick graphene micro-sheets KNG180 with a sheet diameter of 100 μm and 5nm thick graphene micro-sheets G5 with a sheet diameter of 8 μm in a mass ratio of 5: 5, preparing a composition; in another preferred embodiment of the invention, the compound graphene sheet layer is prepared by mixing 30 nm-thick graphene micro-sheets CZ030 with a sheet diameter of 40 μm and 5 nm-thick graphene micro-sheets G5 with a sheet diameter of 8 μm in a mass ratio of 8: 2, preparing a composition; in another preferred embodiment of the invention, the compounded graphene lamellar layer is prepared by mixing 100nm thick graphene micro-platelets KNG182 with a platelet diameter of 40 μm and 100nm thick graphene micro-platelets KNG180 with a platelet diameter of 100 μm according to a mass ratio of 9: 1, preparing a composition; in another preferred embodiment of the invention, the compounded graphene lamellar layer is prepared by mixing graphene micro-sheets G5 with the thickness of 5nm and the sheet diameter of 8 μm and graphene micro-sheets KNG182 with the thickness of 100nm and the sheet diameter of 40 μm according to the mass ratio of 7: 3, preparing a composition; in another preferred embodiment of the invention, the compound graphene lamellar layer is prepared by mixing 100nm thick graphene micro-sheets KNG180 with a sheet diameter of 100 μm and 5nm thick graphene micro-sheets G5 with a sheet diameter of 8 μm in a mass ratio of 6: 4, preparing a composition; in another preferred embodiment of the invention, the compound graphene lamellar layer is prepared by mixing 100nm thick graphene micro-sheets KNG180 with a sheet diameter of 100 μm and 5nm thick graphene micro-sheets G5 with a sheet diameter of 8 μm in a mass ratio of 3: 7.
In the invention, the graphene nanoplatelets/polymer composite material comprises 1 to 15 parts by weight of compound graphene sheet layer, preferably 6 to 12 parts by weight.
In the present invention, the lubricant is preferably selected from one or more of polypropylene wax, polyethylene wax, magnesium stearate, methyl silicone oil and zinc stearate, and more preferably polypropylene wax or polyethylene wax. The source of the lubricant is not particularly limited in the present invention, and commercially available products of the above-mentioned polypropylene wax, polyethylene wax, magnesium stearate, methyl silicone oil and zinc stearate, which are well known to those skilled in the art, may be used. In the present invention, the graphene nanoplatelets/polymer composite includes 0.1 to 5 parts by weight of a lubricant, preferably 0.5 to 3 parts by weight.
In the present invention, the coupling agent is preferably selected from one or more of a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, and a phosphate coupling agent, and more preferably a silane coupling agent or a titanate coupling agent. The source of the coupling agent is not particularly limited in the present invention, and commercially available products of the above-mentioned silane coupling agent, titanate coupling agent and phosphate coupling agent, which are well known to those skilled in the art, may be used. In the present invention, the graphene nanoplatelets/polymer composite comprises 0.01 to 0.5 parts by weight of a coupling agent, preferably 0.05 to 0.45 parts by weight.
The invention also provides a preparation method of the graphene nanoplatelets/polymer composite material, which comprises the following steps:
a) mixing a polymer, a compound graphene sheet layer, a lubricant and a coupling agent to obtain a reaction mixture; the compound graphene lamellar layer consists of graphene micro-sheets with different sheet diameters;
b) melting and blending the reaction mixture obtained in the step a), and then extruding and granulating to obtain granules;
c) carrying out hot-press molding on the granules obtained in the step b), and cooling to obtain the graphene microchip/polymer composite material.
According to the invention, a polymer, a compound graphene sheet layer, a lubricant and a coupling agent are mixed to obtain a reaction mixture. In the present invention, the polymer, the compound graphene sheet layer, the lubricant, and the coupling agent are the same as those described in the above technical solution, and are not described herein again. In the invention, the process of mixing the polymer, the compound graphene sheet layer, the lubricant and the coupling agent is preferably as follows:
and mixing the compounded graphene sheet layer and an ethanol solution of a coupling agent for the first time, drying, and mixing with a polymer and a lubricant for the second time to obtain a reaction mixture. According to the invention, the compound graphene sheet layer and the ethanol solution of the coupling agent are mixed for the first time, so that the compound graphene sheet layer and the coupling agent can be uniformly mixed. In the present invention, the first mixing is preferably performed by ultrasonic stirring; the ultrasonic stirring device is not particularly limited in the present invention, and an ultrasonic tank well known to those skilled in the art may be used. In the present invention, the time for the first mixing is preferably 10 to 30min, and more preferably 20 min.
In the present invention, the purpose of the drying is to completely remove the ethanol; the drying equipment is not particularly limited in the present invention, and an oven known to those skilled in the art may be used. In the present invention, the drying temperature is preferably 80 to 100 ℃, and more preferably 90 ℃; the drying time is preferably 10 to 18 hours, and more preferably 12 to 15 hours.
In the present invention, the second mixing is preferably carried out in a high-speed mixer; the temperature of the second mixing is preferably 70-105 ℃, and more preferably 70-80 ℃; the time for the second mixing is preferably 5 to 15min, more preferably 5 to 10 min.
After the reaction mixture is obtained, the obtained reaction mixture is subjected to melt blending, and then is extruded and granulated to obtain granules. In the present invention, the melt blending is preferably carried out using a twin-screw extruder; the length-diameter ratio of the double-screw extruder is preferably (25-60): 1, more preferably 40: 1. in the present invention, the rotation speed of the melt-blending screw is preferably 100rpm to 400rpm, more preferably 200rpm to 300 rpm; the melt blending temperature is preferably 150 ℃ to 250 ℃, more preferably 160 ℃ to 210 ℃.
The extrusion process is not particularly limited, and the product obtained by melt blending is extruded by a die head. The equipment for said granulation is not particularly restricted by the present invention, and a granulator well known to those skilled in the art may be used. The present invention preferably further includes cooling the extruded product before the granulation, and the present invention is not particularly limited thereto.
After the granules are obtained, the obtained granules are subjected to hot press molding and cooled to obtain the graphene microchip/polymer composite material. In the invention, the hot-press forming process is preferably carried out in a hot-press die by adopting a flat plate molding press; the flat plate molding press is preferably subjected to a preheating treatment before hot press molding, and the temperature of the preheating treatment is preferably 10 to 20min, and more preferably 15 min.
In the invention, the temperature of the hot-press molding is preferably 180-250 ℃, and more preferably 205-210 ℃; the pressure of the hot-press molding is preferably 10MPa to 20MPa, and more preferably 12MPa to 15 MPa; the time for hot press molding is preferably 5min to 10 min.
In the present invention, the cooling is preferably performed with circulating cooling water; the cooling time is preferably 5min to 10 min.
Hair brushThe invention provides a graphene microchip/polymer composite material, which is prepared from the following raw materials: 85 to 99 parts by weight of a polymer; 1-15 parts by weight of compound graphene sheet layer; 0.1 to 5 parts by weight of a lubricant; 0.01 to 0.5 weight portion of coupling agent; the compound graphene lamellar layer is composed of graphene micro-sheets with different sheet diameters. Compared with the prior art, the invention starts from the theory of influencing the material performance, fully utilizes the advantages and disadvantages of the material properties, improves the inherent properties of the material, and takes the compound graphene lamellar layer as the reinforcement of the composite material, thereby effectively improving the stripping and dispersing effects of the graphene lamellar layer, and the obtained product has more excellent electric conduction and heat conduction performance on the basis of stable mechanical properties. Experimental results show that the conductivity of the graphene nanoplatelet/polymer composite material provided by the invention can reach 7.5 multiplied by 10-1S/m, the thermal conductivity can reach 0.981W/mk, and the tensile strength can reach 34.8 MPa.
In addition, the invention does not need the improvement of mechanical equipment, has simple operation and low cost; the graphene microchip/polymer composite material is prepared by adopting a melt mixing method, the possibility of realizing large-scale and continuous production by the method is fully considered, and the graphene microchip/polymer composite material has the advantages of easiness in processing and forming; meanwhile, the preparation method has the advantages of simple steps, no environmental pollution and high production efficiency, and is suitable for industrial production.
To further illustrate the present invention, the following examples are provided for illustration. The raw materials used in the following examples are all commercially available products; wherein the polypropylene (PP) is tiadiningnibo, 3204; the graphene nanoplatelets are provided by Xiamen Kanna graphene technology Co.Ltd; the Polystyrene (PS) brand is Zhenjianqimei, PG-33; acrylonitrile-butadiene-styrene copolymer (ABS) is available under the trade designation british, 720; the trade mark of polyvinyl chloride (PVC) is Shanghai Feng, S-02; high Density Polyethylene (HDPE) is available under the trade designation Nexus Resin, 1062; polycarbonate (PC) is available under the trademark jiaxingdi, 3810.
Example 1
(1) Mixing 100 nm-thick graphene micro-slabs KNG180 with the sheet diameter of 100 mu m and 30 nm-thick graphene micro-slabs CZ030 with the sheet diameter of 40 mu m according to the mass ratio of 8: 2, compounding to obtain a compounded graphene sheet layer;
(2) taking 6g of the compound graphene sheet obtained in the step (1), adding the compound graphene sheet into an ethanol solution (formed by mixing 0.18g of silane coupling agent A151 and 100mL of ethanol) of silane coupling agent A151, placing the mixture into an ultrasonic pool, stirring at a high speed for 20min, placing the mixture into a 90 ℃ oven, drying for 15h, completely removing the ethanol, and then mixing the mixture with 94g of PP and 1g of polypropylene wax micropowder in a high-speed mixer at 70 ℃ for 5min to obtain a reaction mixture;
(3) and (3) accurately feeding the reaction mixture obtained in the step (2) into a feeding device with the length-diameter ratio of 40: 1, extruding by a double-screw extruder at the screw rotating speed of 200rpm and the temperature of each zone between 160 ℃ and 210 ℃, cooling by a cooling water channel and granulating by a granulator in sequence to obtain granules; and finally, putting the granules into a hot-pressing die, carrying out hot-pressing molding for 5min (12 times of exhaust) at 205 ℃ and 12MPa by using a flat-plate molding press (the preheating time is 15min), and cooling by circulating cooling water for 5min to obtain the graphene microchip/polymer composite material.
The scanning electron micrograph of the graphene nanoplatelet/polymer composite provided in example 1 is shown in fig. 1. As can be seen from fig. 1, the preparation method provided in embodiment 1 of the present invention can effectively improve the peeling and dispersing effects of the graphene sheet layer by improving the intrinsic properties of the material.
Comparative example 1
The preparation process provided in example 1 was used with the difference that: the compound graphene lamellar layer is replaced by graphene micro-sheet CZ030(6g) with the thickness of 30nm and the sheet diameter of 40 mu m.
Comparative example 2
The preparation process provided in example 1 was used with the difference that: the graphene nanoplatelets KNG180(6g) with the thickness of 100nm and the sheet diameter of 100 mu m are used for replacing the compound graphene sheet layer.
The electric conductivity, the heat conductivity and the mechanical properties of the graphene nanoplatelets/polymer composite materials provided in the example 1 and the comparative examples 1-2 are tested by taking the Chinese national standard GB/T15662-1995 for electric conduction, the American standard ASTM-E1461 for heat conduction and the national standard GB/T1040.2-2006 for mechanical properties as test standards, and the results are shown in Table 1.
Table 1 each performance data of graphene nanoplatelets/polymer composites provided in example 1 and comparative examples 1-2
| Conductivity (S/m) | Thermal conductivity (W/mk) | Tensile strength (MPa) | |
| Example 1 | 3.3×10-6 | 0.524 | 32.8 |
| Comparative example 1 | 5.0×10-7 | 0.463 | 32.1 |
| Comparative example 2 | 7.0×10-10 | 0.423 | 30.1 |
As can be seen from table 1, on the basis of stable mechanical properties, the graphene nanoplatelets/polymer composite material provided in embodiment 1 of the present invention has greatly improved electrical conductivity and thermal conductivity, and has good comprehensive properties.
Therefore, the invention provides a method for improving the material performance by compounding the material by fully utilizing the advantages and disadvantages of the material property from the theory of influencing the material performance. The graphene microchip/polymer composite material prepared by the preparation method provided by the invention has the characteristics of excellent electric conductivity and heat conductivity, good product size stability and the like. In addition, the invention does not need the improvement of mechanical equipment, has simple operation and low cost; the graphene microchip/polymer composite material is prepared by adopting a melt mixing method, the possibility of realizing large-scale and continuous production by the method is fully considered, and the graphene microchip/polymer composite material has the advantages of easiness in processing and forming; meanwhile, the preparation method has the advantages of simple steps, no environmental pollution and high production efficiency, and is suitable for industrial production.
Example 2
(1) Mixing 100 nm-thick graphene micro-slabs KNG180 with the sheet diameter of 100 mu m and 5 nm-thick graphene micro-slabs G5 with the sheet diameter of 8 mu m according to the mass ratio of 5: 5, compounding to obtain a compounded graphene sheet layer;
(2) adding 9g of the compound graphene sheet obtained in the step (1) into an ethanol solution of a silane coupling agent (formed by mixing 0.27g of the silane coupling agent and 100mL of ethanol), placing the mixture in an ultrasonic pool, stirring at a high speed for 30min, placing the mixture in a 100 ℃ oven, drying for 12h, completely removing ethanol, and then mixing the mixture with 91g of PP and 1g of polypropylene wax in a high-speed mixer at 80 ℃ for 10min to obtain a reaction mixture;
(3) and (3) accurately feeding the reaction mixture obtained in the step (2) into a feeding device with the length-diameter ratio of 25: 1, the rotating speed of a screw is 100rpm, the temperature of each zone is 170-220 ℃, and then the mixture is extruded by a die head, cooled by a cooling water channel and granulated by a granulator in sequence to obtain granules; and finally, putting the granules into a hot-pressing die, carrying out hot-pressing molding for 5min (exhausting for 10 times) at 205 ℃ and 10MPa by using a flat-plate molding press (preheating time is 10min), and cooling by circulating cooling water for 8min to obtain the graphene microchip/polymer composite material.
The graphene nanoplatelets/polymer composite material provided in example 2 is tested by the testing method provided in example 1, and the result shows that the conductivity of the graphene nanoplatelets/polymer composite material provided in example 2 is 9.0 × 10-7S/m, thermal conductivity of 0.486W/mk, and tensile strength of 31.8 MPa.
Example 3
(1) Mixing 30 nm-thick graphene nanoplatelets CZ030 with the sheet diameter of 40 μm and 5 nm-thick graphene nanoplatelets G5 with the sheet diameter of 8 μm according to a mass ratio of 8: 2, compounding to obtain a compounded graphene sheet layer;
(2) taking 12g of the compound graphene sheet obtained in the step (1), adding the compound graphene sheet into an ethanol solution of a titanate coupling agent (formed by mixing 0.3g of the titanate coupling agent and 100mL of ethanol), placing the mixture into an ultrasonic pool, stirring at a high speed for 30min, placing the mixture into a 90 ℃ oven, drying for 18h, completely removing ethanol, and then mixing the mixture with 88g of ABS and 0.5g of polyethylene wax in a high-speed mixer at 80 ℃ for 15min to obtain a reaction mixture;
(3) accurately feeding the reaction mixture obtained in the step (2) into a feeding device with the length-diameter ratio of 60: 1, extruding by a double-screw extruder at the screw rotating speed of 300rpm and the temperature of each zone between 160 ℃ and 210 ℃, cooling by a cooling water channel and granulating by a granulator in sequence to obtain granules; and finally, putting the granules into a hot-pressing die, carrying out hot-pressing molding for 10min (exhausting 15 times) at 210 ℃ and 15MPa by adopting a flat-plate molding press (preheating time is 20min), and cooling by circulating cooling water for 10min to obtain the graphene microchip/polymer composite material.
The graphene nanoplatelets/polymer composite material provided in example 3 is tested by the testing method provided in example 1, and the result shows that the conductivity of the graphene nanoplatelets/polymer composite material provided in example 3 is 1.0 × 10-1S/m, thermal conductivity of 0.723W/mk, and tensile strength of 34.8 MPa.
A comparison graph of the conductive network structure of the graphene nanoplatelets compounded with different sheet diameters in the graphene nanoplatelets/polymer composite material provided in embodiments 1-3 is shown in fig. 2.
Example 4
(1) Mixing 100 nm-thick graphene micro-slabs KNG182 with the sheet diameter of 40 μm and 100 nm-thick graphene micro-slabs KNG180 with the sheet diameter of 100 μm according to a mass ratio of 9: 1, compounding to obtain a compounded graphene sheet layer;
(2) taking 2g of the compound graphene sheet layer obtained in the step (1), adding the compound graphene sheet layer into an ethanol solution of an aluminate coupling agent (formed by mixing 0.05g of a zinc stearate coupling agent and 100mL of ethanol), placing the mixture into an ultrasonic pool, stirring at a high speed for 10min, placing the mixture into an oven at 85 ℃, drying for 15h, completely removing ethanol, and then mixing the mixture with 98g of PVC and 1g of methyl silicone oil in a high-speed mixer at 70 ℃ for 10min to obtain a reaction mixture;
(3) and (3) accurately feeding the reaction mixture obtained in the step (2) into a feeding device with the length-diameter ratio of 40: 1, extruding by a double-screw extruder at a screw rotating speed of 250rpm and at the temperature of 150-200 ℃ in each zone, and then sequentially extruding by a die head, cooling by a cooling water channel and granulating by a granulator to obtain granules; and finally, putting the granules into a hot-pressing die, carrying out hot-pressing molding for 5min (exhausting 8 times) at 180 ℃ and 20MPa by adopting a flat-plate molding press (preheating time is 20min), and cooling by circulating cooling water for 5min to obtain the graphene microchip/polymer composite material.
The graphene nanoplatelets/polymer composite material provided in example 4 is tested by the testing method provided in example 1, and the result shows that the conductivity of the graphene nanoplatelets/polymer composite material provided in example 4 is 2.0 × 10-6S/m, thermal conductivity of 0.512W/mk, tensile strength of 32.8 MPa.
Example 5
(1) Mixing graphene nanoplatelets G5 with the thickness of 5nm and the sheet diameter of 8 μm and graphene nanoplatelets KNG182 with the thickness of 100nm and the sheet diameter of 40 μm according to a mass ratio of 7: 3, compounding to obtain a compounded graphene sheet layer;
(2) taking 10g of the compound graphene sheet obtained in the step (1), adding the compound graphene sheet into an ethanol solution of a titanate coupling agent (formed by mixing 0.32g of the titanate coupling agent and 100mL of ethanol), placing the mixture into an ultrasonic pool, stirring at a high speed for 20min, placing the mixture into a 95 ℃ oven, drying for 12h, completely removing ethanol, and then mixing the mixture with 90g of HDPE and 3g of polyethylene wax in a high-speed mixer at 85 ℃ for 10min to obtain a reaction mixture;
(3) and (3) accurately feeding the reaction mixture obtained in the step (2) into a feeding device with the length-diameter ratio of 25: 1, the rotating speed of a screw is 150rpm, the temperature of each zone is 180-230 ℃, and then the mixture is extruded by a die head, cooled by a cooling water channel and granulated by a granulator in sequence to obtain granules; and finally, putting the granules into a hot-pressing die, carrying out hot-pressing molding for 6min (12 times of exhaust) at 215 ℃ and 18MPa by adopting a flat-plate molding press (the preheating time is 15min), and cooling by circulating cooling water for 6min to obtain the graphene microchip/polymer composite material.
The graphene nanoplatelets/polymer composite material provided in example 5 is tested by the testing method provided in example 1, and the result shows that the conductivity of the graphene nanoplatelets/polymer composite material provided in example 5 is 2.5 × 10-3S/m, thermal conductivity of 0.734W/mk, tensile strength of 33.2 MPa.
Example 6
(1) Mixing 100 nm-thick graphene micro-slabs KNG180 with the sheet diameter of 100 mu m and 5 nm-thick graphene micro-slabs G5 with the sheet diameter of 8 mu m according to the mass ratio of 6: 4, compounding to obtain a compounded graphene sheet layer;
(2) adding 9g of the compound graphene sheet obtained in the step (1) into an ethanol solution of a silane coupling agent (formed by mixing 0.27g of the silane coupling agent and 100mL of ethanol), placing the mixture in an ultrasonic pool, stirring at a high speed for 12min, placing the mixture in a 90 ℃ oven, drying for 10h, completely removing ethanol, and then mixing the mixture with 91g of PP and 1g of polypropylene wax in a high-speed mixer at 80 ℃ for 8min to obtain a reaction mixture;
(3) and (3) accurately feeding the reaction mixture obtained in the step (2) into a feeding device with the length-diameter ratio of 40: 1, extruding by a double-screw extruder at the screw rotating speed of 200rpm and the temperature of each zone between 160 ℃ and 210 ℃, cooling by a cooling water channel and granulating by a granulator in sequence to obtain granules; and finally, putting the granules into a hot-pressing die, carrying out hot-pressing molding for 8min (exhausting 20 times) at 205 ℃ and 15MPa by using a flat-plate molding press (preheating time is 12min), and cooling with circulating cooling water for 10min to obtain the graphene microchip/polymer composite material.
The graphene nanoplatelets/polymer composite material provided in example 6 is tested by the testing method provided in example 1, and the result shows that the conductivity of the graphene nanoplatelets/polymer composite material provided in example 6 is 4.5 × 10-5S/m, thermal conductivity of 0.541W/mk, and tensile strength of 33.9 MPa.
Example 7
(1) Mixing 100 nm-thick graphene nanoplatelets KNG180 with the sheet diameter of 100 mu m and 5 nm-thick graphene nanoplatelets G5 with the sheet diameter of 8 mu m according to the mass ratio of 3: 7, compounding to obtain a compounded graphene sheet layer;
(2) taking 15g of the compound graphene sheet obtained in the step (1), adding the compound graphene sheet into an ethanol solution (formed by mixing 0.45g of stearic acid coupling agent and 100mL of ethanol) of a titanate coupling agent, placing the mixture in an ultrasonic pool, stirring at a high speed for 20min, placing the mixture in an oven at 85 ℃, drying for 18h, completely removing ethanol, and then mixing the mixture with 85g of PBT and 3g of polyethylene wax in a high-speed mixer at 105 ℃ for 15min to obtain a reaction mixture;
(3) and (3) accurately feeding the reaction mixture obtained in the step (2) into a feeding device with the length-diameter ratio of 25: 1, extruding by a double-screw extruder at the screw rotating speed of 400rpm and the temperature of each zone between 180 and 250 ℃, cooling by a cooling water channel and granulating by a granulator in sequence to obtain granules; and finally, putting the granules into a hot-pressing die, carrying out hot-pressing molding for 5min (exhausting 20 times) at 250 ℃ and 20MPa by using a flat-plate molding press (preheating time is 20min), and cooling by circulating cooling water for 8min to obtain the graphene microchip/polymer composite material.
The graphene nanoplatelets/polymer composite material provided in example 7 is tested by the testing method provided in example 1, and the result shows that the conductivity of the graphene nanoplatelets/polymer composite material provided in example 7 is 7.5 × 10-1S/m, thermal conductivity of 0.981W/mk, and tensile strength of 34.3 MPa.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
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| CN104552947A (en) * | 2014-12-30 | 2015-04-29 | 张辉开 | Graphene fused deposition 3D printing method and application thereof |
| CN104592950A (en) * | 2014-12-26 | 2015-05-06 | 苏州格瑞丰纳米科技有限公司 | High-thermal conductivity graphite alkenyl polymer heat conducting film and preparation method thereof |
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