CN113150487B - Preparation method of thermoplastic shielding material - Google Patents
Preparation method of thermoplastic shielding material Download PDFInfo
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- CN113150487B CN113150487B CN202110168458.8A CN202110168458A CN113150487B CN 113150487 B CN113150487 B CN 113150487B CN 202110168458 A CN202110168458 A CN 202110168458A CN 113150487 B CN113150487 B CN 113150487B
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
- C08J3/21—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase
- C08J3/215—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase at least one additive being also premixed with a liquid phase
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- C—CHEMISTRY; METALLURGY
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- C08J2353/00—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
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
Abstract
The invention discloses a preparation method of a thermoplastic shielding material, and belongs to the technical field of power cables. The method comprises the following steps: adding ethylene-propylene block copolymer polypropylene into an organic solvent, heating, adding an antioxidant, and stirring until the ethylene-propylene block copolymer polypropylene is completely dissolved; adding carbon black and graphene into the same organic solvent, adding a coupling agent, and performing ultrasonic treatment to obtain a carbon black-graphene dispersion liquid; then adding the carbon black-graphene dispersion liquid into a polypropylene solution, stirring, adding an extracting agent, carrying out suction filtration, and carrying out vacuum drying on the obtained solid; and finally, extruding and granulating to obtain the thermoplastic shielding material. The invention adopts the ultrasonic dispersion filler, effectively establishes the conductive network, reduces the seepage threshold value of the thermoplastic shielding material and enhances the conductivity.
Description
Technical Field
The invention relates to a preparation method of a thermoplastic shielding material, and belongs to the technical field of power cables.
Background
The power cable is an important component of a power transmission and distribution system as an important power device. Crosslinked polyethylene (XLPE) insulated cables are generally adopted at the present stage, materials cannot be recycled after the service life is exhausted, and the materials can only be incinerated and buried, so that the environment is greatly damaged. In order to improve the compatibility of the material and the environment, polypropylene (PP) is used as a green environment-friendly recyclable non-crosslinked thermoplastic cable insulating material for replacing XLPE insulation at present, and the development trend is met, and the low-carbon environment-friendly guide of the current society is met. The research on the matched thermoplastic shielding material also has very important significance.
The semi-conductive shielding layer plays an important role in the cable, can homogenize an electric field, bear the stress of a strong electric field, reduce air gaps between a conductor and an insulating layer and protect main insulation, and the performance of the semi-conductive shielding layer influences the service life of the cable. The semiconductive shielding material is mainly made of a polymer composite material, and a matrix resin PP of the polypropylene-based thermoplastic shielding material has the advantages of excellent insulating property, high temperature resistance level, plasticizing recycling and the like. However, polypropylene also has poor low-temperature toughness and insufficient mechanical strength, so that the application range of the polypropylene is limited.
It has been found that when conductive carbon black is added to polypropylene as a barrier filler, the performance of polypropylene is greatly enhanced. However, carbon black has a small particle diameter, easily aggregates, and is poor in dispersibility. At present, graphene is also used as a conductive filler, has higher surface energy, is very easy to stack, and further increases the conductive difficulty. Therefore, how to uniformly disperse carbon black and graphene is a key technology and difficulty of a preparation method of the polypropylene-based thermoplastic shielding material.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a preparation method of a thermoplastic shielding material.
In order to achieve the purpose, the invention adopts the technical scheme that: a method of making a thermoplastic shielding material, comprising the steps of:
(1) Adding ethylene-propylene block copolymer polypropylene into an organic solvent, heating in an oil bath, adding an antioxidant, and stirring until the ethylene-propylene block copolymer polypropylene is completely dissolved to obtain a polypropylene solution;
(2) Adding carbon black and graphene into the same organic solvent as the organic solvent in the step (1), adding a coupling agent, and performing ultrasonic treatment to obtain a carbon black-graphene dispersion liquid;
(3) Adding the carbon black-graphene dispersion liquid obtained in the step (2) into the polypropylene solution obtained in the step (1), stirring, adding an extracting agent, performing suction filtration, and performing vacuum drying on the solid obtained by suction filtration to obtain a mixed material;
(4) And (4) extruding and granulating the mixed material obtained in the step (3) to obtain the thermoplastic shielding material.
The filling type shielding material consists of synthetic resin with better electrical insulating property, conductive filler with excellent electrical conductivity and other additives, and has the advantages of small specific gravity, integration of molding and shielding, convenient processing, convenient mass production, low cost and the like. The polypropylene resin has the advantages of excellent insulating property, high temperature resistance level, plasticizing recycling and the like. The ethylene-propylene block copolymerization polypropylene has high crystallinity, higher rigidity and better low-temperature toughness, thereby being used as a base material of the thermoplastic shielding material.
The carbon black has good conductivity, a conductive chain or a local conductive network is formed in the material, under the action of electromagnetic waves, polarization is generated in the medium, and the intensity vector of the polarization lags behind the electric field by an angle, so that current in the same phase with the electric field is generated, and eddy current is established, so that electric energy is converted into heat energy to be consumed. Meanwhile, the carbon black particles have small particle size, high structure and multiple gaps, which is beneficial to the uniform dispersion of the carbon black in the matrix, and the electromagnetic waves form multiple scattering points, so that the electromagnetic waves are scattered for multiple times to consume energy, thereby achieving the purpose of absorbing the electromagnetic waves. The carbon black has the advantages of low price, low density, difficult sedimentation, strong corrosion resistance and the like. Graphene is a known conductor with the fastest electron transfer speed at room temperature, is the optical speed, and has the electron movement speed far higher than that of a common conductor; secondly, the carbon atoms in the graphene are connected with each other very flexibly, and when the carbon atoms are subjected to external force, the carbon atom surfaces can absorb energy through bending deformation without rearrangement, so that the stability of the graphene structure and the stability of electron transmission are ensured.
As a preferred embodiment of the method for preparing the thermoplastic shielding material of the present invention, in the step (1), the mass ratio of the ethylene-propylene block copolymer polypropylene to the organic solvent is 1:10 to 20.
As a preferred embodiment of the method for preparing the thermoplastic shielding material of the present invention, the organic solvent is toluene, xylene or decalin.
As a preferred embodiment of the method for producing a thermoplastic shielding material of the present invention, in the step (1), the temperature of oil bath heating is 120 to 135 ℃.
Polypropylene is a high molecular compound, the molecular weight is between 10 and 30 ten thousand, the molecular weight is large, a molecular main chain and a molecular branch chain are not easy to move at normal temperature, and the polypropylene can resist corrosion of acid, alkali, salt solution and various organic solvents at the temperature of below 80 ℃, so the polypropylene needs to be heated and dissolved.
As a preferred embodiment of the method for preparing the thermoplastic shielding material of the present invention, in the step (1), the antioxidant is at least one of antioxidant 1010, antioxidant 300, and antioxidant 1076.
The antioxidant can affect the service life of the shielding material, and the addition of the antioxidant can stabilize the volume resistivity of the shielding material and prolong the service life of the shielding material to a certain extent. Meanwhile, the antioxidant can effectively prevent thermal oxidation degradation of the thermoplastic shielding material in a long-term aging process, and can improve the color change resistance of the thermoplastic shielding material under a high-temperature processing condition.
As a preferred embodiment of the method for preparing the thermoplastic shielding material of the present invention, in the step (2), the mass ratio of the total mass of the carbon black and the graphene to the organic solvent is 1:50 to 200.
The mass ratio of carbon black to graphene to organic solvent affects the shielding performance and the elongation at break of the shielding material. The volume resistivity of the shielding material can be improved by adding the carbon black and the graphene, a system is converted from an insulating material into a semiconductor material or even a conductive material, and the performance of the shielding material cannot be improved by adding too little amount of the carbon black and the graphene; when the addition amount is too large, carbon black and graphene cannot be dispersed in a polymer system, and the carbon black and the graphene are agglomerated with each other to form defects, so that the mechanical property of the shielding material is reduced.
As a preferable embodiment of the method for preparing the thermoplastic shielding material of the present invention, in the step (2), the time of the ultrasonic treatment is 15 to 50min.
The dispersion degree of the carbon black and the graphene is one of the main factors influencing the performance of the thermoplastic shielding material. Researches show that the dispersion of graphene mainly has the following difficulties: the density phase difference of graphene and polypropylene is large, the viscosity of polypropylene after being dissolved is also large, and graphene has large surface energy and is extremely easy to stack, so that graphene and carbon black are not easy to be uniformly dispersed in a polypropylene solution, and the overall performance of the thermoplastic shielding material is influenced. The cavitation of the ultrasonic wave in the medium transmission process can cause the violent impact action among liquid particles, and the particles can be uniformly dispersed in the liquid.
As a preferred embodiment of the method for preparing the thermoplastic shielding material of the present invention, in the step (3), the stirring time is 4 to 6 hours.
As a preferred embodiment of the method for preparing the thermoplastic shielding material of the present invention, in the step (3), the extracting agent is acetone, ethanol or deionized water.
As a preferred embodiment of the method for preparing the thermoplastic shielding material of the present invention, in the step (3), the vacuum drying conditions are as follows: the drying temperature is 70-90 ℃, and the drying time is 4-8 h.
Compared with the prior art, the invention has the beneficial effects that: according to the invention, the filler is dispersed by ultrasonic, so that the dispersion of carbon black is promoted, a conductive network is effectively established, the layering of graphene is promoted, the synergistic effect of carbon black and graphene is enhanced, the percolation threshold of the thermoplastic shielding material is reduced, and the conductivity is enhanced.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples.
Example 1
The preparation method of the thermoplastic shielding material in the embodiment comprises the following steps:
(1) Adding 20 parts by weight of ethylene-propylene block copolymer polypropylene into 200 parts by weight of dimethylbenzene, heating in an oil bath, heating to 120 ℃, adding 0.1 part by weight of antioxidant 1010, and mechanically stirring for 1h until the ethylene-propylene block copolymer polypropylene is completely dissolved to obtain a polypropylene solution;
(2) Adding 0.2 part by weight of graphene into 150 parts by weight of dimethylbenzene, and adding 0.1 part by weight of coupling agent a172 for ultrasonic oscillation dispersion for 30min; adding 1.3 parts by weight of carbon black, and continuing ultrasonic oscillation for 15min to obtain a carbon black-graphene dispersion liquid;
(3) Adding the carbon black-graphene dispersion liquid obtained in the step (2) into the polypropylene solution obtained in the step (1), mechanically stirring for 4 hours, adding acetone, placing in a suction filtration device, carrying out suction filtration, placing in a vacuum oven, drying for 4 hours at 90 ℃, removing redundant organic solvent and extractant, and obtaining a mixed material;
(4) And (4) placing the mixed material obtained in the step (3) into a double-screw extruder for extrusion granulation to obtain the thermoplastic shielding material.
Example 2
The preparation method of the thermoplastic shielding material in the embodiment comprises the following steps:
(1) Adding 20 parts by weight of ethylene-propylene block copolymer polypropylene into 250 parts by weight of decalin, heating in an oil bath, heating to 125 ℃, adding 0.1 part by weight of antioxidant 1010, and mechanically stirring for 2 hours until the ethylene-propylene block copolymer polypropylene is completely dissolved to obtain a polypropylene solution;
(2) Adding 0.2 part by weight of graphene into 150 parts by weight of decalin, and adding 0.1 part by weight of coupling agent a172 for ultrasonic oscillation and dispersion for 30min; adding 1.3 parts by weight of carbon black, and continuing ultrasonic oscillation for 15min to obtain a carbon black-graphene dispersion liquid;
(3) Adding the carbon black-graphene dispersion liquid obtained in the step (2) into the polypropylene solution obtained in the step (1), mechanically stirring for 5 hours, adding acetone, placing in a suction filtration device, carrying out suction filtration, placing in a vacuum oven, drying for 6 hours at 90 ℃, removing redundant organic solvent and extractant, and obtaining a mixed material;
(4) And (4) placing the mixed material obtained in the step (3) into a double-screw extruder for extrusion granulation to obtain the thermoplastic shielding material.
Example 3
The preparation method of the thermoplastic shielding material in the embodiment comprises the following steps:
(1) Adding 20 parts by weight of ethylene-propylene block copolymer polypropylene into 300 parts by weight of dimethylbenzene, heating in an oil bath, heating to 135 ℃, adding 0.1 part by weight of antioxidant 1010, and mechanically stirring for 2 hours until the ethylene-propylene block copolymer polypropylene is completely dissolved to obtain a polypropylene solution;
(2) Adding 0.2 part by weight of graphene into 150 parts by weight of decalin, and adding 0.1 part by weight of coupling agent a172 for ultrasonic oscillation and dispersion for 30min; adding 1.3 parts by weight of carbon black, and continuing ultrasonic oscillation for 15min to obtain a carbon black-graphene dispersion liquid;
(3) Adding the carbon black-graphene dispersion liquid obtained in the step (2) into the polypropylene solution obtained in the step (1), mechanically stirring for 6 hours, adding ethanol, placing in a suction filtration device, carrying out suction filtration, placing in a vacuum oven, drying for 8 hours at 90 ℃, removing redundant organic solvent and extractant, and obtaining a mixed material;
(4) And (4) placing the mixed material obtained in the step (3) into a double-screw extruder for extrusion granulation to obtain the thermoplastic shielding material.
Example 4
The preparation method of the thermoplastic shielding material in the embodiment comprises the following steps:
(1) Adding 20 parts by weight of ethylene-propylene block copolymer polypropylene into 250 parts by weight of toluene, heating in an oil bath, heating to 135 ℃, adding 0.1 part by weight of antioxidant, and mechanically stirring for 2 hours until the ethylene-propylene block copolymer polypropylene is completely dissolved to obtain a polypropylene solution;
(2) Adding 0.2 part by weight of graphene into 200 parts by weight of dimethylbenzene, and adding 0.1 part by weight of coupling agent a172 for ultrasonic oscillation dispersion for 30min; adding 1.3 parts by weight of carbon black, and continuing ultrasonic oscillation for 20min to obtain a carbon black-graphene dispersion liquid;
(3) Adding the carbon black-graphene dispersion liquid obtained in the step (2) into the polypropylene solution obtained in the step (1), mechanically stirring for 6 hours, adding acetone, placing in a suction filtration device, carrying out suction filtration, placing in a vacuum oven, drying for 8 hours at 80 ℃, removing redundant organic solvent and extractant, and obtaining a mixed material;
(4) And (4) placing the mixed material obtained in the step (3) into a double-screw extruder for extrusion granulation to obtain the thermoplastic shielding material.
Example 5
The preparation method of the thermoplastic shielding material in the embodiment comprises the following steps:
(1) Adding 20 parts by weight of ethylene-propylene block copolymer polypropylene into 300 parts by weight of dimethylbenzene, heating in an oil bath, heating to 135 ℃, adding 0.1 part by weight of antioxidant 1076, and mechanically stirring for 0.5h until the ethylene-propylene block copolymer polypropylene is completely dissolved to obtain a polypropylene solution;
(2) Adding 0.2 part by weight of graphene into 100 parts by weight of dimethylbenzene, and adding 0.1 part by weight of coupling agent a172 for ultrasonic oscillation dispersion for 30min; adding 1.3 parts by weight of carbon black, and continuing ultrasonic oscillation for 15min to obtain a carbon black-graphene dispersion liquid;
(3) Adding the carbon black-graphene dispersion liquid obtained in the step (2) into the polypropylene solution obtained in the step (1), mechanically stirring for 4 hours, adding acetone, placing in a suction filtration device, carrying out suction filtration, removing redundant organic solvent and extractant, and placing in a vacuum oven for drying for 8 hours at 70 ℃ to obtain a mixed material;
(4) And (4) placing the mixed material obtained in the step (3) into a double-screw extruder for extrusion granulation to obtain the thermoplastic shielding material.
Example 6
The preparation method of the thermoplastic shielding material in the embodiment comprises the following steps:
(1) Adding 20 parts by weight of ethylene-propylene block copolymer polypropylene into 200 parts by weight of dimethylbenzene, heating in an oil bath, heating to 120 ℃, adding 0.1 part by weight of antioxidant 1010, and mechanically stirring for 2 hours until the ethylene-propylene block copolymer polypropylene is completely dissolved to obtain a polypropylene solution;
(2) Adding 0.2 part by weight of graphene into 150 parts by weight of dimethylbenzene, and adding 0.1 part by weight of coupling agent a172 for ultrasonic oscillation dispersion for 10min; adding 1.3 parts by weight of carbon black, and continuing ultrasonic oscillation for 5min to obtain a carbon black-graphene dispersion liquid;
(3) Adding the carbon black-graphene dispersion liquid obtained in the step (2) into the polypropylene solution obtained in the step (1), mechanically stirring for 4 hours, adding deionized water, placing in a suction filtration device, carrying out suction filtration, placing in a vacuum oven, drying for 6 hours at 90 ℃, removing redundant organic solvent and extractant, and obtaining a mixed material;
(4) And (4) placing the mixed material obtained in the step (3) into a double-screw extruder for extrusion granulation to obtain the thermoplastic shielding material.
Example 7
The preparation method of the thermoplastic shielding material in the embodiment comprises the following steps:
(1) Adding 20 parts by weight of ethylene-propylene block copolymer polypropylene into 400 parts by weight of dimethylbenzene, heating in an oil bath, raising the temperature to 120 ℃, adding 0.1 part by weight of antioxidant 1010, and mechanically stirring for 1 hour until the ethylene-propylene block copolymer polypropylene is completely dissolved to obtain a polypropylene solution;
(2) Adding 0.2 part by weight of graphene into 75 parts by weight of dimethylbenzene, and adding 0.1 part by weight of coupling agent a172 for ultrasonic oscillation dispersion for 30min; adding 1.3 parts by weight of carbon black, and continuing ultrasonic oscillation for 15min to obtain a carbon black-graphene dispersion liquid;
(3) Adding the carbon black-graphene dispersion liquid obtained in the step (2) into the polypropylene solution obtained in the step (1), mechanically stirring for 4 hours, adding acetone, placing in a suction filtration device, carrying out suction filtration, placing in a vacuum oven, drying for 4 hours at 90 ℃, removing redundant organic solvent and extractant, and obtaining a mixed material;
(4) And (4) placing the mixed material obtained in the step (3) into a double-screw extruder for extrusion granulation to obtain the thermoplastic shielding material.
Example 8
The preparation method of the thermoplastic shielding material in the embodiment comprises the following steps:
(1) Adding 20 parts by weight of ethylene-propylene block copolymer polypropylene into 200 parts by weight of dimethylbenzene, heating in an oil bath, heating to 120 ℃, adding 0.1 part by weight of antioxidant 1010, and mechanically stirring for 1h until the ethylene-propylene block copolymer polypropylene is completely dissolved to obtain a polypropylene solution;
(2) Adding 0.2 part by weight of graphene into 300 parts by weight of dimethylbenzene, and adding 0.1 part by weight of coupling agent a172 for ultrasonic oscillation dispersion for 30min; adding 1.3 parts by weight of carbon black, and continuing ultrasonic oscillation for 15min to obtain a carbon black-graphene dispersion liquid;
(3) Adding the carbon black-graphene dispersion liquid obtained in the step (2) into the polypropylene solution obtained in the step (1), mechanically stirring for 4 hours, adding acetone, placing in a suction filtration device, carrying out suction filtration, placing in a vacuum oven, drying for 4 hours at 90 ℃, removing redundant organic solvent and extractant, and obtaining a mixed material;
(4) And (4) placing the mixed material obtained in the step (3) into a double-screw extruder for extrusion granulation to obtain the thermoplastic shielding material.
The electrical and mechanical properties of the thermoplastic shielding materials obtained in the examples were measured, and the results are shown in table 1.
TABLE 1 Properties of thermoplastic Shielding materials
The results in Table 1 show that the semiconductive shielding material has excellent mechanical properties and lower volume resistivity, and the properties of the material meet the performance requirements of JB/T10738-2007 on thermoplastic semiconductive shielding materials.
Comparative example 1
The preparation method of the thermoplastic shielding material of the present comparative example includes the steps of:
(1) Adding 0.2 part by weight of graphene into 150 parts by weight of dimethylbenzene, and adding 0.1 part by weight of coupling agent a172 for ultrasonic oscillation dispersion for 30min; adding 1.3 parts of carbon black, and continuing ultrasonic oscillation for 15min to obtain a carbon black-graphene dispersion liquid;
(2) Adding acetone into the carbon black-graphene dispersion liquid obtained in the step (1), placing the mixture into a suction filtration device, carrying out suction filtration, placing the suction filtration device in a vacuum oven, drying the mixture for 4 hours at 90 ℃, and removing redundant organic solvent and extractant to obtain a mixture;
(3) Placing the mixture obtained in the step (2) and 20 parts by weight of polypropylene in a torque rheometer, mixing for 20min under the condition of a rotating speed of 40r/min, and uniformly mixing to obtain a mixed material;
(4) And (4) placing the mixed material obtained in the step (3) into a double-screw extruder for extrusion granulation to obtain the thermoplastic shielding material.
Comparative example 2
The preparation method of the thermoplastic shielding material of the present comparative example includes the steps of:
(1) Adding 20 parts by weight of ethylene-propylene block copolymer polypropylene into 250 parts by weight of decalin, heating in an oil bath, heating to 125 ℃, adding 0.1 part by weight of antioxidant 1010, and mechanically stirring for 2 hours until the ethylene-propylene block copolymer polypropylene is completely dissolved to obtain a polypropylene solution;
(2) Adding 0.2 part by weight of graphene into 150 parts by weight of decalin, adding 0.1 part by weight of coupling agent a172, and mechanically stirring for 30min; adding 1.3 parts by weight of carbon black, and mechanically stirring for 15min to obtain a carbon black-graphene dispersion liquid;
(3) Adding the carbon black-graphene dispersion liquid obtained in the step (2) into the polypropylene solution obtained in the step (1), mechanically stirring for 5 hours, adding acetone, placing in a suction filtration device, carrying out suction filtration, placing in a vacuum oven, drying for 6 hours at 90 ℃, removing redundant organic solvent and extractant, and obtaining a mixed material;
(4) And (4) placing the mixed material obtained in the step (3) into a double-screw extruder for extrusion granulation to obtain the thermoplastic shielding material.
Comparative example 3
The preparation method of the thermoplastic shielding material of the present comparative example includes the steps of:
mixing 0.2 part by weight of graphene, 1.3 parts by weight of carbon black and 20 parts by weight of polypropylene, adding the mixture into a torque rheometer, mixing for 20min under the condition of a rotating speed of 40r/min, uniformly mixing, and placing the mixture into a double-screw extruder for extrusion granulation to obtain the thermoplastic shielding material.
Comparative example 4
The preparation method of the thermoplastic shielding material of the present comparative example includes the steps of:
(1) Adding 20 parts by weight of ethylene-propylene block copolymer polypropylene into 160 parts by weight of dimethylbenzene, heating in an oil bath, heating to 120 ℃, adding 0.1 part by weight of antioxidant 1010, and mechanically stirring for 1h until the ethylene-propylene block copolymer polypropylene is completely dissolved to obtain a polypropylene solution;
(2) Adding 0.2 part by weight of graphene into 150 parts by weight of dimethylbenzene, and adding 0.1 part by weight of coupling agent a172 for ultrasonic oscillation dispersion for 30min; adding 1.3 parts by weight of carbon black, and continuing ultrasonic oscillation for 15min to obtain a carbon black-graphene dispersion liquid;
(3) Adding the carbon black-graphene dispersion liquid obtained in the step (2) into the polypropylene solution obtained in the step (1), mechanically stirring for 4 hours, adding acetone, placing in a suction filtration device, carrying out suction filtration, placing in a vacuum oven, drying for 4 hours at 90 ℃, removing redundant organic solvent and extractant, and obtaining a mixed material;
(4) And (4) placing the mixed material obtained in the step (3) into a double-screw extruder for extrusion granulation to obtain the thermoplastic shielding material.
Comparative example 5
The preparation method of the thermoplastic shielding material of the present comparative example includes the steps of:
(1) Adding 20 parts by weight of ethylene-propylene block copolymer polypropylene into 440 parts by weight of xylene, heating in an oil bath, heating to 120 ℃, adding 0.1 part by weight of antioxidant 1010, and mechanically stirring for 1 hour until the ethylene-propylene block copolymer polypropylene is completely dissolved to obtain a polypropylene solution;
(2) Adding 0.2 part by weight of graphene into 150 parts by weight of dimethylbenzene, and adding 0.1 part by weight of coupling agent a172 for ultrasonic oscillation dispersion for 30min; adding 1.3 parts by weight of carbon black, and continuing ultrasonic oscillation for 15min to obtain a carbon black-graphene dispersion liquid;
(3) Adding the carbon black-graphene dispersion liquid obtained in the step (2) into the polypropylene solution obtained in the step (1), mechanically stirring for 4 hours, adding acetone, placing in a suction filtration device, carrying out suction filtration, placing in a vacuum oven, drying for 4 hours at 90 ℃, removing redundant organic solvent and extractant, and obtaining a mixed material;
(4) And (4) placing the mixed material obtained in the step (3) into a double-screw extruder for extrusion granulation to obtain the thermoplastic shielding material.
Comparative example 6
The preparation method of the thermoplastic shielding material of the present comparative example includes the steps of:
(1) Adding 20 parts by weight of ethylene-propylene block copolymer polypropylene into 200 parts by weight of dimethylbenzene, heating in an oil bath, heating to 120 ℃, adding 0.1 part by weight of antioxidant 1010, and mechanically stirring for 1h until the ethylene-propylene block copolymer polypropylene is completely dissolved to obtain a polypropylene solution;
(2) Adding 0.2 part by weight of graphene into 60 parts by weight of dimethylbenzene, and adding 0.1 part by weight of coupling agent a172 for ultrasonic oscillation dispersion for 30min; adding 1.3 parts by weight of carbon black, and continuing ultrasonic oscillation for 15min to obtain a carbon black-graphene dispersion liquid;
(3) Adding the carbon black-graphene dispersion liquid obtained in the step (2) into the polypropylene solution obtained in the step (1), mechanically stirring for 4 hours, adding acetone, placing in a suction filtration device, carrying out suction filtration, placing in a vacuum oven, drying for 4 hours at 90 ℃, removing redundant organic solvent and extractant, and obtaining a mixed material;
(4) And (4) placing the mixed material obtained in the step (3) into a double-screw extruder for extrusion granulation to obtain the thermoplastic shielding material.
Comparative example 7
The preparation method of the thermoplastic shielding material of the present comparative example includes the steps of:
(1) Adding 20 parts by weight of ethylene-propylene block copolymer polypropylene into 200 parts by weight of dimethylbenzene, heating in an oil bath, heating to 120 ℃, adding 0.1 part by weight of antioxidant 1010, and mechanically stirring for 1h until the ethylene-propylene block copolymer polypropylene is completely dissolved to obtain a polypropylene solution;
(2) Adding 0.2 part by weight of graphene into 330 parts by weight of dimethylbenzene, and adding 0.1 part by weight of coupling agent a172 for ultrasonic oscillation dispersion for 30min; adding 1.3 parts by weight of carbon black, and continuing ultrasonic oscillation for 15min to obtain a carbon black-graphene dispersion liquid;
(3) Adding the carbon black-graphene dispersion liquid obtained in the step (2) into the polypropylene solution obtained in the step (1), mechanically stirring for 4 hours, adding acetone, placing in a suction filtration device, carrying out suction filtration, placing in a vacuum oven, drying for 4 hours at 90 ℃, removing redundant organic solvent and extractant, and obtaining a mixed material;
(4) And (4) placing the mixed material obtained in the step (3) into a double-screw extruder for extrusion granulation to obtain the thermoplastic shielding material.
Comparative example 8
The preparation method of the thermoplastic shielding material of the present comparative example includes the steps of:
(1) Adding 20 parts by weight of ethylene-propylene block copolymer polypropylene into 200 parts by weight of dimethylbenzene, heating in an oil bath, raising the temperature to 120 ℃, adding 0.1 part by weight of antioxidant 1010, and mechanically stirring for 1 hour until the ethylene-propylene block copolymer polypropylene is completely dissolved to obtain a polypropylene solution;
(2) Adding 0.2 part by weight of graphene into 150 parts by weight of dimethylbenzene, and adding 0.1 part by weight of coupling agent a172 for ultrasonic oscillation dispersion for 5min; adding 1.3 parts by weight of carbon black, and continuing ultrasonic oscillation for 5min to obtain a carbon black-graphene dispersion liquid;
(3) Adding the carbon black-graphene dispersion liquid obtained in the step (2) into the polypropylene solution obtained in the step (1), mechanically stirring for 4 hours, adding acetone, placing in a suction filtration device, carrying out suction filtration, placing in a vacuum oven, drying for 4 hours at 90 ℃, removing redundant organic solvent and extractant, and obtaining a mixed material;
(4) And (4) placing the mixed material obtained in the step (3) into a double-screw extruder for extrusion granulation to obtain the thermoplastic shielding material.
The thermoplastic shielding material obtained in the comparative example was tested for electrical and mechanical properties, and the results are shown in table 2.
TABLE 2 Properties of thermoplastic Shielding materials
As can be seen from the comparison between Table 2 and Table 1, the thermoplastic shielding material prepared by the present invention has higher elongation at break and smaller resistivity, and can meet the standard requirements.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (5)
1. A method for preparing a thermoplastic shielding material is characterized by comprising the following steps:
(1) Adding ethylene-propylene block copolymer polypropylene into an organic solvent, heating in an oil bath, adding an antioxidant, and stirring until the ethylene-propylene block copolymer polypropylene is completely dissolved to obtain a polypropylene solution;
(2) Adding carbon black and graphene into the same organic solvent as the organic solvent in the step (1), adding a coupling agent, and performing ultrasonic treatment to obtain a carbon black-graphene dispersion liquid;
(3) Adding the carbon black-graphene dispersion liquid obtained in the step (2) into the polypropylene solution obtained in the step (1), stirring, adding an extracting agent, performing suction filtration, and performing vacuum drying on the solid obtained by suction filtration to obtain a mixed material;
(4) Extruding and granulating the mixed material obtained in the step (3) to obtain a thermoplastic shielding material;
wherein in the step (1), the mass ratio of the ethylene-propylene block copolymer polypropylene to the organic solvent is 1:10 to 20 ℃, and the oil bath heating temperature is 120 to 135 ℃; in the step (2), the mass ratio of the total mass of the carbon black and the graphene to the organic solvent is 1: 50-200, and the ultrasonic time is 15-50min; the organic solvent is xylene.
2. The method of claim 1, wherein in step (1), the antioxidant is at least one of antioxidant 1010, antioxidant 300, and antioxidant 1076.
3. The method for producing a thermoplastic shielding material according to claim 1, wherein in the step (3), the stirring time is 4 to 6 hours.
4. The method of claim 1, wherein in step (3), the extractant is acetone, ethanol or deionized water.
5. The method for preparing a thermoplastic shielding material according to claim 1, wherein in the step (3), the vacuum drying conditions are as follows: the drying temperature is 70 to 90 ℃, and the drying time is 4 to 8 hours.
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