CN114437451A - Semiconductive EVA master batch for shielding and production method thereof - Google Patents
Semiconductive EVA master batch for shielding and production method thereof Download PDFInfo
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Abstract
The invention discloses a semiconductive EVA master batch for shielding and a production method thereof; relates to the technical field of new material production, and is prepared from the following components: ethylene-vinyl acetate copolymer, conductive carbon black, modified ethylene propylene diene monomer, zinc oxide, a coupling agent, hydroxyapatite, dicumyl peroxide, chlorinated paraffin, an antioxidant and a dispersing agent; the semiconductive EVA master batch for shielding prepared by the invention can be used for homogenizing the electric field distribution in the cable insulating layer, preventing partial discharge, improving the electric strength of the cable and finally prolonging the service life of the cable.
Description
Technical Field
The invention belongs to the technical field of new material production, and particularly relates to a semiconductive EVA master batch for shielding and a production method thereof.
Background
With the development of information transmission integration, broadband, intellectualization and digitization, various lines in the comprehensive wiring system engineering of buildings and building groups are more and more intensively arranged together, high-speed data streams are subjected to mutual interference of common-frequency electromagnetism, and the problems of electromagnetic interference (EMI) and electromagnetic compatibility (EMC) are increasingly obvious.
The semi-conductive shielding material prevents partial discharge by electric field distribution in a uniform insulating layer, thereby improving the electric strength of the cable and prolonging the service life of the cable.
Therefore, further improvements to the prior art are needed to improve the performance of semiconductive shield materials.
Disclosure of Invention
The invention aims to provide a semiconductive EVA master batch for shielding and a production method thereof, which aim to solve the defects in the prior art.
The technical scheme adopted by the invention is as follows:
the semiconductive EVA master batch for shielding is prepared from the following components in parts by weight: 70-80 parts of ethylene-vinyl acetate copolymer, 23-26 parts of conductive carbon black, 20-25 parts of modified ethylene propylene diene monomer, 2-5 parts of zinc oxide, 1-3 parts of coupling agent, 8-15 parts of hydroxyapatite, 1-2 parts of dicumyl peroxide, 2-4 parts of chlorinated paraffin, 1.5-2.5 parts of antioxidant and 3-5 parts of dispersant.
As a further technical scheme: the content of vinyl acetate in the ethylene-vinyl acetate copolymer is 12 percent.
As a further technical scheme: the preparation method of the modified ethylene propylene diene monomer rubber comprises the following steps:
(1) adding tetramethyl orthosilicate into an ethanol solution, and uniformly stirring to obtain a premixed solution;
(2) sequentially adding graphene and kaolin into a stirrer to be stirred and mixed at a high speed to obtain a solid mixture;
(3) adding the obtained fixed mixture into a premixed solution, stirring at the rotating speed of 500r/min for 2 hours, and then performing ultrasonic dispersion treatment for 10 minutes to obtain a dispersion solution;
(4) heating and drying the dispersion liquid, and then crushing to obtain an intercalation material;
(5) and sequentially adding the intercalation material and the ethylene propylene diene monomer rubber into a mixing roll to be mixed for 30min, then discharging and cooling to obtain the ethylene propylene diene monomer.
As a further technical scheme: the mixing mass ratio of the tetramethyl orthosilicate to the ethanol solution is 1: 3;
the mass fraction of the ethanol solution is 60%.
As a further technical scheme: the mixing mass ratio of the graphene to the kaolin is 1: 5;
the kaolin is obtained by treating with an acidic solution:
adding kaolin into a nitric acid solution according to the mass ratio of 1:6, adjusting the temperature to 80 ℃, preserving heat, stirring for 40min, then filtering, washing with water to be neutral, and drying to constant weight;
the mass fraction of the nitric acid solution is 3.5%.
As a further technical scheme: the mixing mass ratio of the fixed mixture to the premixed liquid is 1: 6;
the ultrasonic frequency is 40 kHz.
As a further technical scheme: the mixing mass ratio of the interlayer material to the ethylene propylene diene monomer is 1: 10;
the mixing temperature was 138 ℃.
As a further technical scheme: the coupling agent is an organosilane coupling agent;
as a further technical scheme: the antioxidant is zinc dialkyl dithiophosphate;
the dispersing agent is zinc stearate.
A preparation method of a semiconductive EVA master batch for shielding comprises the following steps:
(1) weighing ethylene-vinyl acetate copolymer, conductive carbon black, modified ternary rubber, zinc oxide, coupling agent, hydroxyapatite, chlorinated paraffin, antioxidant and dispersing agent according to the weight parts, and placing the ethylene-vinyl acetate copolymer, the conductive carbon black, the modified ternary rubber, the zinc oxide, the coupling agent, the chlorinated paraffin, the antioxidant and the dispersing agent into dry ethylene propylene rubber, the zinc oxide, the coupling agent, the hydroxyapatite, dicumyl peroxide, the chlorinated paraffin, the antioxidant and the dispersing agent;
(2) drying ethylene-vinyl acetate copolymer, conductive carbon black and modified ethylene propylene diene monomer in a dryer at the drying temperature of 60 ℃ for 1 hour to obtain a dried material;
(3) adding the obtained dry materials into a mixer for uniform mixing, and then adding into a mixing roll for mixing treatment to obtain mixed materials, wherein the mixing temperature is 138 ℃, and the mixing time is 30 min;
(4) and (3) adding the mixing materials and dicumyl peroxide into an internal mixer in sequence for internal mixing treatment, and then discharging, wherein the internal mixing temperature is 125 ℃, and the internal mixing time is 35 min.
Chlorinated paraffin is an organic substance, namely a chlorinated derivative of paraffin, has the advantages of low volatility, flame retardance, good electrical insulation, low price and the like, and can be used as a flame retardant and an auxiliary plasticizer. It can be widely used for producing cable material, floor material, hose, artificial leather, rubber and other products. The invention introduces chlorinated paraffin to improve the flame retardant property of the material.
Zinc oxide is an inorganic substance, has a chemical formula of ZnO, and is an oxide of zinc. Is insoluble in water and soluble in acid and strong base. Zinc oxide is a commonly used chemical additive, and is widely applied to the manufacture of products such as plastics, silicate products, synthetic rubber, lubricating oil, paint, coating, ointment, adhesive, food, batteries, flame retardant and the like. The zinc oxide has large energy band gap and exciton constraint energy, high transparency and excellent normal temperature luminous performance, and is applied to products such as liquid crystal displays, thin film transistors, light emitting diodes and the like in the semiconductor field. In addition, the zinc oxide of fine particles also starts to function in the related art as a nano material. The zinc oxide is introduced into the invention and mainly used as a reinforcing filler.
Ethylene-vinyl acetate copolymer (EVA) is usually obtained by high pressure polymerization of ethylene monomer and vinyl acetate monomer, Ca in hydroxyapatite molecule2+Can generate complex reaction with carboxyl and amino, the surface of the hydroxyapatite is rough, is rich in polar groups, has stronger chemical activity, can be combined with other components in the material, and enhances the comprehensive performance of the EVA material.
By introducing the modified ethylene propylene diene monomer, the modified ethylene propylene diene monomer is fully diffused and contacted in the EVA matrix, and the adhesive force between the modified ethylene propylene diene monomer and the EVA matrix is obviously enhanced, so that the mechanical property of the EVA material is greatly improved, particularly the tensile strength property is obviously improved, meanwhile, the modified ethylene propylene diene monomer can be tightly combined with the polymer molecules of the matrix, the combination property is improved, and the aging resistance of the prepared semiconductive EVA master batch for shielding is improved.
Advantageous effects
The semiconductive EVA master batch for shielding, prepared by the invention, can be used for uniformly distributing an electric field in an insulating layer of a cable, preventing partial discharge, improving the electrical strength of the cable and finally prolonging the service life of the cable.
Drawings
FIG. 1 is a graph comparing the effect of different amounts of modified EPDM on the tensile strength of a material.
Detailed Description
The semiconductive EVA master batch for shielding is prepared from the following components in parts by weight: 70-80 parts of ethylene-vinyl acetate copolymer, 23-26 parts of conductive carbon black, 20-25 parts of modified ethylene propylene diene monomer, 2-5 parts of zinc oxide, 1-3 parts of coupling agent, 8-15 parts of hydroxyapatite, 1-2 parts of dicumyl peroxide, 2-4 parts of chlorinated paraffin, 1.5-2.5 parts of antioxidant and 3-5 parts of dispersant.
The vinyl acetate content of the ethylene-vinyl acetate copolymer is 12 percent.
The preparation method of the modified ethylene propylene diene monomer rubber comprises the following steps:
(1) adding tetramethyl orthosilicate into an ethanol solution, and uniformly stirring to obtain a premixed solution;
(2) sequentially adding graphene and kaolin into a stirrer, and stirring and mixing at a high speed to obtain a solid mixture;
(3) adding the obtained fixed mixture into the premixed solution, stirring for 2 hours at the rotating speed of 500r/min, and then carrying out ultrasonic dispersion treatment for 10 minutes to obtain a dispersion solution;
(4) heating and drying the dispersion liquid, and then crushing to obtain an intercalation material;
(5) and sequentially adding the intercalation material and the ethylene propylene diene monomer rubber into a mixing roll to be mixed for 30min, then discharging and cooling to obtain the ethylene propylene diene monomer.
The mixing mass ratio of the tetramethyl orthosilicate to the ethanol solution is 1: 3;
the mass fraction of the ethanol solution is 60%.
The mixing mass ratio of the graphene to the kaolin is 1: 5;
the kaolin is obtained by treating with an acidic solution:
adding kaolin into a nitric acid solution according to the mass ratio of 1:6, adjusting the temperature to 80 ℃, preserving heat, stirring for 40min, then filtering, washing with water to be neutral, and drying to constant weight;
the mass fraction of the nitric acid solution is 3.5%.
The mixing mass ratio of the fixed mixture to the premixed liquid is 1: 6;
the ultrasonic frequency is 40 kHz.
The mixing mass ratio of the interlayer material to the ethylene propylene diene monomer is 1: 10;
the mixing temperature was 138 ℃.
The coupling agent is an organic silane coupling agent;
the antioxidant is zinc dialkyl dithiophosphate;
the dispersing agent is zinc stearate.
A preparation method of a semiconductive EVA master batch for shielding comprises the following steps:
(1) weighing ethylene-vinyl acetate copolymer, conductive carbon black, modified ethylene propylene diene monomer, zinc oxide, coupling agent, hydroxyapatite, dicumyl peroxide, chlorinated paraffin, antioxidant and dispersant according to the weight parts;
(2) putting ethylene-vinyl acetate copolymer, conductive carbon black, modified ethylene propylene diene monomer, zinc oxide, a coupling agent, hydroxyapatite, chlorinated paraffin, an antioxidant and a dispersing agent into a dryer for drying treatment, wherein the drying temperature is 60 ℃, and the drying time is 1 hour, so as to obtain a dried material;
(3) adding the obtained dry materials into a mixer for uniform mixing, and then adding into a mixing roll for mixing treatment to obtain mixed materials, wherein the mixing temperature is 138 ℃, and the mixing time is 30 min;
(4) and (3) adding the mixing materials and dicumyl peroxide into an internal mixer in sequence for internal mixing treatment, and then discharging, wherein the internal mixing temperature is 125 ℃, and the internal mixing time is 35 min.
The following will clearly and completely describe the technical solutions of the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all 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.
Example 1
The semiconductive EVA master batch for shielding is prepared from the following components in parts by weight: 70 parts of ethylene-vinyl acetate copolymer, 23 parts of conductive carbon black, 20 parts of modified ethylene propylene diene monomer, 2 parts of zinc oxide, 1 part of coupling agent, 8 parts of hydroxyapatite, 1 part of dicumyl peroxide, 2 parts of chlorinated paraffin, 1.5 parts of antioxidant and 3 parts of dispersant.
The vinyl acetate content of the ethylene-vinyl acetate copolymer is 12 percent.
The preparation method of the modified ethylene propylene diene monomer rubber comprises the following steps:
(1) adding tetramethyl orthosilicate into an ethanol solution, and uniformly stirring to obtain a premixed solution;
(2) sequentially adding graphene and kaolin into a stirrer, and stirring and mixing at a high speed to obtain a solid mixture;
(3) adding the obtained fixed mixture into a premixed solution, stirring at the rotating speed of 500r/min for 2 hours, and then performing ultrasonic dispersion treatment for 10 minutes to obtain a dispersion solution;
(4) heating and drying the dispersion liquid, and then crushing to obtain an intercalation material;
(5) and sequentially adding the intercalation material and the ethylene propylene diene monomer rubber into a mixing roll to be mixed for 30min, then discharging and cooling to obtain the ethylene propylene diene monomer.
The mixing mass ratio of the tetramethyl orthosilicate to the ethanol solution is 1: 3;
the mass fraction of the ethanol solution is 60%.
The mixing mass ratio of the graphene to the kaolin is 1: 5;
the kaolin is obtained by treating with an acidic solution:
adding kaolin into a nitric acid solution according to the mass ratio of 1:6, adjusting the temperature to 80 ℃, preserving heat, stirring for 40min, then filtering, washing with water to be neutral, and drying to constant weight;
the mass fraction of the nitric acid solution is 3.5%.
The mixing mass ratio of the fixed mixture to the premixed liquid is 1: 6;
the ultrasonic frequency is 40 kHz.
The mixing mass ratio of the interlayer material to the ethylene propylene diene monomer is 1: 10;
the mixing temperature was 138 ℃.
The coupling agent is an organic silane coupling agent;
the antioxidant is zinc dialkyl dithiophosphate;
the dispersing agent is zinc stearate.
A preparation method of a semiconductive EVA master batch for shielding comprises the following steps:
(1) weighing ethylene-vinyl acetate copolymer, conductive carbon black, modified ethylene propylene diene monomer, zinc oxide, coupling agent, hydroxyapatite, dicumyl peroxide, chlorinated paraffin, antioxidant and dispersant according to the weight parts;
(2) putting ethylene-vinyl acetate copolymer, conductive carbon black, modified ethylene propylene diene monomer, zinc oxide, a coupling agent, hydroxyapatite, chlorinated paraffin, an antioxidant and a dispersing agent into a dryer for drying treatment, wherein the drying temperature is 60 ℃, and the drying time is 1 hour, so as to obtain a dried material;
(3) adding the obtained dry materials into a mixer for uniform mixing, and then adding into a mixing roll for mixing treatment to obtain mixed materials, wherein the mixing temperature is 138 ℃, and the mixing time is 30 min;
(4) and (3) adding the mixing materials and dicumyl peroxide into an internal mixer in sequence for internal mixing treatment, and then discharging, wherein the internal mixing temperature is 125 ℃, and the internal mixing time is 35 min.
Example 2
The semiconductive EVA master batch for shielding is prepared from the following components in parts by weight: 74 parts of ethylene-vinyl acetate copolymer, 24 parts of conductive carbon black, 22 parts of modified ethylene propylene diene monomer, 3 parts of zinc oxide, 2 parts of coupling agent, 10 parts of hydroxyapatite, 1.5 parts of dicumyl peroxide, 3 parts of chlorinated paraffin, 2 parts of antioxidant and 4 parts of dispersant.
The vinyl acetate content of the ethylene-vinyl acetate copolymer is 12%.
The preparation method of the modified ethylene propylene diene monomer rubber comprises the following steps:
(1) adding tetramethyl orthosilicate into an ethanol solution, and uniformly stirring to obtain a premixed solution;
(2) sequentially adding graphene and kaolin into a stirrer, and stirring and mixing at a high speed to obtain a solid mixture;
(3) adding the obtained fixed mixture into a premixed solution, stirring at the rotating speed of 500r/min for 2 hours, and then performing ultrasonic dispersion treatment for 10 minutes to obtain a dispersion solution;
(4) heating and drying the dispersion liquid, and then crushing to obtain an intercalation material;
(5) and sequentially adding the intercalation material and the ethylene propylene diene monomer rubber into a mixing roll to be mixed for 30min, then discharging and cooling to obtain the ethylene propylene diene monomer.
The mixing mass ratio of the tetramethyl orthosilicate to the ethanol solution is 1: 3;
the mass fraction of the ethanol solution is 60%.
The mixing mass ratio of the graphene to the kaolin is 1: 5;
the kaolin is obtained by treating with an acidic solution:
adding kaolin into a nitric acid solution according to the mass ratio of 1:6, adjusting the temperature to 80 ℃, preserving heat, stirring for 40min, then filtering, washing with water to be neutral, and drying to constant weight;
the mass fraction of the nitric acid solution is 3.5%.
The mixing mass ratio of the fixed mixture to the premixed liquid is 1: 6;
the ultrasonic frequency is 40 kHz.
The mixing mass ratio of the interlayer material to the ethylene propylene diene monomer is 1: 10;
the mixing temperature was 138 ℃.
The coupling agent is an organic silane coupling agent;
the antioxidant is zinc dialkyl dithiophosphate;
the dispersing agent is zinc stearate.
A preparation method of a semiconductive EVA master batch for shielding comprises the following steps:
(1) weighing ethylene-vinyl acetate copolymer, conductive carbon black, modified ethylene propylene diene monomer, zinc oxide, coupling agent, hydroxyapatite, dicumyl peroxide, chlorinated paraffin, antioxidant and dispersant according to the weight parts;
(2) putting ethylene-vinyl acetate copolymer, conductive carbon black, modified ethylene propylene diene monomer, zinc oxide, a coupling agent, hydroxyapatite, chlorinated paraffin, an antioxidant and a dispersing agent into a dryer for drying treatment, wherein the drying temperature is 60 ℃, and the drying time is 1 hour, so as to obtain a dried material;
(3) adding the obtained dry materials into a mixer for uniform mixing, and then adding into a mixing roll for mixing treatment to obtain mixed materials, wherein the mixing temperature is 138 ℃, and the mixing time is 30 min;
(4) and (3) adding the mixing materials and dicumyl peroxide into an internal mixer in sequence for internal mixing treatment, and then discharging, wherein the internal mixing temperature is 125 ℃, and the internal mixing time is 35 min.
Example 3
The semiconductive EVA master batch for shielding is prepared from the following components in parts by weight: 78 parts of ethylene-vinyl acetate copolymer, 25 parts of conductive carbon black, 23 parts of modified ethylene propylene diene monomer, 4 parts of zinc oxide, 2 parts of coupling agent, 12 parts of hydroxyapatite, 1.5 parts of dicumyl peroxide, 3 parts of chlorinated paraffin, 1.8 parts of antioxidant and 4 parts of dispersing agent.
The vinyl acetate content of the ethylene-vinyl acetate copolymer is 12 percent.
The preparation method of the modified ethylene propylene diene monomer rubber comprises the following steps:
(1) adding tetramethyl orthosilicate into an ethanol solution, and uniformly stirring to obtain a premixed solution;
(2) sequentially adding graphene and kaolin into a stirrer, and stirring and mixing at a high speed to obtain a solid mixture;
(3) adding the obtained fixed mixture into a premixed solution, stirring at the rotating speed of 500r/min for 2 hours, and then performing ultrasonic dispersion treatment for 10 minutes to obtain a dispersion solution;
(4) heating and drying the dispersion liquid, and then crushing to obtain an intercalation material;
(5) and sequentially adding the intercalation material and the ethylene propylene diene monomer rubber into a mixing roll to be mixed for 30min, then discharging and cooling to obtain the ethylene propylene diene monomer.
The mixing mass ratio of the tetramethyl orthosilicate to the ethanol solution is 1: 3;
the mass fraction of the ethanol solution is 60%.
The mixing mass ratio of the graphene to the kaolin is 1: 5;
the kaolin is obtained by treating with an acidic solution:
adding kaolin into a nitric acid solution according to the mass ratio of 1:6, adjusting the temperature to 80 ℃, preserving heat, stirring for 40min, then filtering, washing with water to be neutral, and drying to constant weight;
the mass fraction of the nitric acid solution is 3.5%.
The mixing mass ratio of the fixed mixture to the premixed liquid is 1: 6;
the ultrasonic frequency is 40 kHz.
The mixing mass ratio of the interlayer material to the ethylene propylene diene monomer is 1: 10;
the mixing temperature was 138 ℃.
The coupling agent is an organic silane coupling agent;
the antioxidant is zinc dialkyl dithiophosphate;
the dispersing agent is zinc stearate.
A preparation method of a semiconductive EVA master batch for shielding comprises the following steps:
(1) weighing ethylene-vinyl acetate copolymer, conductive carbon black, modified ethylene propylene diene monomer, zinc oxide, coupling agent, hydroxyapatite, dicumyl peroxide, chlorinated paraffin, antioxidant and dispersant according to the weight parts;
(2) putting ethylene-vinyl acetate copolymer, conductive carbon black, modified ethylene propylene diene monomer, zinc oxide, a coupling agent, hydroxyapatite, chlorinated paraffin, an antioxidant and a dispersing agent into a dryer for drying treatment, wherein the drying temperature is 60 ℃, and the drying time is 1 hour, so as to obtain a dried material;
(3) adding the obtained dry materials into a mixer for uniform mixing, and then adding into a mixing roll for mixing treatment to obtain mixed materials, wherein the mixing temperature is 138 ℃, and the mixing time is 30 min;
(4) and (3) adding the mixing materials and dicumyl peroxide into an internal mixer in sequence for internal mixing treatment, and then discharging, wherein the internal mixing temperature is 125 ℃, and the internal mixing time is 35 min.
Example 4
The semiconductive EVA master batch for shielding is prepared from the following components in parts by weight: 80 parts of ethylene-vinyl acetate copolymer, 26 parts of conductive carbon black, 25 parts of modified ethylene propylene diene monomer, 5 parts of zinc oxide, 3 parts of coupling agent, 15 parts of hydroxyapatite, 2 parts of dicumyl peroxide, 4 parts of chlorinated paraffin, 2.5 parts of antioxidant and 5 parts of dispersant.
The vinyl acetate content of the ethylene-vinyl acetate copolymer is 12 percent.
The preparation method of the modified ethylene propylene diene monomer rubber comprises the following steps:
(1) adding tetramethyl orthosilicate into an ethanol solution, and uniformly stirring to obtain a premixed solution;
(2) sequentially adding graphene and kaolin into a stirrer, and stirring and mixing at a high speed to obtain a solid mixture;
(3) adding the obtained fixed mixture into a premixed solution, stirring at the rotating speed of 500r/min for 2 hours, and then performing ultrasonic dispersion treatment for 10 minutes to obtain a dispersion solution;
(4) heating and drying the dispersion liquid, and then crushing to obtain an intercalation material;
(5) and sequentially adding the intercalation material and the ethylene propylene diene monomer rubber into a mixing roll to be mixed for 30min, then discharging and cooling to obtain the ethylene propylene diene monomer.
The mixing mass ratio of the tetramethyl orthosilicate to the ethanol solution is 1: 3;
the mass fraction of the ethanol solution is 60%.
The mixing mass ratio of the graphene to the kaolin is 1: 5;
the kaolin is obtained by treating with an acidic solution:
adding kaolin into a nitric acid solution according to the mass ratio of 1:6, adjusting the temperature to 80 ℃, preserving heat, stirring for 40min, then filtering, washing with water to be neutral, and drying to constant weight;
the mass fraction of the nitric acid solution is 3.5%.
The mixing mass ratio of the fixed mixture to the premixed liquid is 1: 6;
the ultrasonic frequency is 40 kHz.
The mixing mass ratio of the interlayer material to the ethylene propylene diene monomer is 1: 10;
the mixing temperature was 138 ℃.
The coupling agent is an organic silane coupling agent;
the antioxidant is zinc dialkyl dithiophosphate;
the dispersing agent is zinc stearate.
A preparation method of a semiconductive EVA master batch for shielding comprises the following steps:
(1) weighing ethylene-vinyl acetate copolymer, conductive carbon black, modified ethylene propylene diene monomer, zinc oxide, coupling agent, hydroxyapatite, dicumyl peroxide, chlorinated paraffin, antioxidant and dispersant according to the weight parts;
(2) putting ethylene-vinyl acetate copolymer, conductive carbon black, modified ethylene propylene diene monomer, zinc oxide, a coupling agent, hydroxyapatite, chlorinated paraffin, an antioxidant and a dispersing agent into a dryer for drying treatment, wherein the drying temperature is 60 ℃, and the drying time is 1 hour, so as to obtain a dried material;
(3) adding the obtained dry materials into a mixer for uniform mixing, and then adding into a mixing roll for mixing treatment to obtain mixed materials, wherein the mixing temperature is 138 ℃, and the mixing time is 30 min;
(4) and (3) adding the mixing materials and dicumyl peroxide into an internal mixer in sequence for internal mixing treatment, and then discharging, wherein the internal mixing temperature is 125 ℃, and the internal mixing time is 35 min.
Comparative example 1: the difference from the example 1 is that no modified ethylene propylene diene monomer is added.
Comparative example 2: the difference from example 1 is that the modified ethylene propylene diene monomer rubber is replaced by untreated ethylene propylene diene monomer rubber.
Test of
The tensile strength test of the samples of the examples and the comparative examples is carried out according to GB/T1040-2018, the samples are II type standard dumbbell sheets, the thickness is (1.0 +/-0.1) mm, and the tensile speed is (250 +/-50) mm/min;
TABLE 1
| Tensile strength MPa | |
| Example 1 | 19.92 |
| Example 2 | 20.54 |
| Example 3 | 20.41 |
| Example 4 | 20.25 |
| Comparative example 1 | 16.52 |
| Comparative example 2 | 18.32 |
As can be seen from Table 1, the semiconductive EVA master batch for shielding prepared by the invention has excellent mechanical properties, and the tensile property of the semiconductive EVA master batch for shielding can be effectively improved by introducing the modified ethylene propylene diene monomer prepared by the invention.
An air heat aging test, which is to perform a test according to the requirements of section 6.4 in JB/T10738-2007 semiconductive shielding material for extruded insulated cables with rated voltage of 35kV and below, wherein after 240h at (100 +/-2) DEG C, a sample is adjusted for 18h in an environment with (23 +/-3) DEG C and relative humidity of 44% -45%;
the test results are shown in table 2;
TABLE 2
| Tensile strength after aging MPa | |
| Example 1 | 14.12 |
| Example 2 | 14.58 |
| Example 3 | 14.33 |
| Example 4 | 14.21 |
| Comparative example 1 | 10.25 |
| Comparative example 2 | 13.37 |
As can be seen from Table 2, the semiconductive EVA master batch for shielding prepared by the invention has excellent aging resistance, and can be tightly combined with matrix polymer molecules by introducing the modified ethylene propylene diene monomer, so that the combination property is improved, and the aging resistance of the prepared semiconductive EVA master batch for shielding is improved.
Measuring the volume resistivity at 20 ℃, wherein the test is carried out according to the regulation of GB/T3048.3-2007 method for testing the electrical property of the cable, and the sample is regulated for 25 hours in the environment with the temperature of (23 +/-3) DEG C and the relative humidity of 44-45%;
TABLE 3
As can be seen from Table 3, the semiconductive EVA master batch for shielding prepared by the invention can be used for homogenizing the electric field distribution in the cable insulating layer, preventing partial discharge, improving the electrical strength of the cable and finally prolonging the service life of the cable.
Based on example 2, the effect of the addition of different amounts of modified EPDM on the tensile strength of the material is compared, as shown in FIG. 1.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention, and the present invention is not limited to the illustrated embodiments, and all the modifications and equivalents of the embodiments may be made without departing from the spirit of the present invention.
Claims (10)
1. The semiconductive EVA master batch for shielding is characterized by being prepared from the following components in parts by weight: 70-80 parts of ethylene-vinyl acetate copolymer, 23-26 parts of conductive carbon black, 20-25 parts of modified ethylene propylene diene monomer, 2-5 parts of zinc oxide, 1-3 parts of coupling agent, 8-15 parts of hydroxyapatite, 1-2 parts of dicumyl peroxide, 2-4 parts of chlorinated paraffin, 1.5-2.5 parts of antioxidant and 3-5 parts of dispersant.
2. The semiconductive EVA masterbatch for shielding according to claim 1, wherein: the content of vinyl acetate in the ethylene-vinyl acetate copolymer is 12 percent.
3. The semiconductive EVA masterbatch for shielding according to claim 1, wherein: the preparation method of the modified ethylene propylene diene monomer rubber comprises the following steps:
(1) adding tetramethyl orthosilicate into an ethanol solution, and uniformly stirring to obtain a premixed solution;
(2) sequentially adding graphene and kaolin into a stirrer, and stirring and mixing at a high speed to obtain a solid mixture;
(3) adding the obtained fixed mixture into a premixed solution, stirring at the rotating speed of 500r/min for 2 hours, and then performing ultrasonic dispersion treatment for 10 minutes to obtain a dispersion solution;
(4) heating and drying the dispersion liquid, and then crushing to obtain an intercalation material;
(5) and sequentially adding the intercalation material and the ethylene propylene diene monomer rubber into a mixing roll to be mixed for 30min, then discharging and cooling to obtain the ethylene propylene diene monomer.
4. The semiconductive EVA masterbatch for shielding according to claim 3, wherein: the mixing mass ratio of the tetramethyl orthosilicate to the ethanol solution is 1: 3;
the mass fraction of the ethanol solution is 60%.
5. The semiconductive EVA masterbatch for shielding according to claim 3, wherein: the mixing mass ratio of the graphene to the kaolin is 1: 5;
the kaolin is obtained by treating with an acid solution:
adding kaolin into a nitric acid solution according to the mass ratio of 1:6, adjusting the temperature to 80 ℃, preserving heat, stirring for 40min, then filtering, washing with water to be neutral, and drying to constant weight;
the mass fraction of the nitric acid solution is 3.5%.
6. The semiconductive EVA masterbatch for shielding according to claim 3, wherein: the mixing mass ratio of the fixed mixture to the premixed liquid is 1: 6;
the ultrasonic frequency is 40 kHz.
7. The semiconductive EVA masterbatch for shielding according to claim 3, wherein: the mixing mass ratio of the interlayer material to the ethylene propylene diene monomer is 1: 10;
the mixing temperature was 138 ℃.
8. The semiconductive EVA masterbatch for shielding according to claim 1, wherein: the coupling agent is an organosilane coupling agent.
9. The semiconductive EVA masterbatch for shielding according to claim 1, wherein: the antioxidant is zinc dialkyl dithiophosphate;
the dispersing agent is zinc stearate.
10. The process for preparing a semiconductive EVA masterbatch for shielding according to any one of claims 1 or 9, characterized in that: the method comprises the following steps:
(1) weighing ethylene-vinyl acetate copolymer, conductive carbon black, modified ethylene propylene diene monomer, zinc oxide, coupling agent, hydroxyapatite, dicumyl peroxide, chlorinated paraffin, antioxidant and dispersant according to the weight parts;
(2) putting ethylene-vinyl acetate copolymer, conductive carbon black, modified ethylene propylene diene monomer, zinc oxide, a coupling agent, hydroxyapatite, chlorinated paraffin, an antioxidant and a dispersing agent into a dryer for drying treatment, wherein the drying temperature is 60 ℃, and the drying time is 1 hour, so as to obtain a dried material;
(3) adding the obtained dry materials into a mixer for uniform mixing, and then adding into a mixing roll for mixing treatment to obtain mixed materials, wherein the mixing temperature is 138 ℃, and the mixing time is 30 min;
(4) and (3) adding the mixing materials and dicumyl peroxide into an internal mixer in sequence for internal mixing treatment, and then discharging, wherein the internal mixing temperature is 125 ℃, and the internal mixing time is 35 min.
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