CN104356487A - Preparation method of graphene semiconductive shielding material for cables - Google Patents

Abstract

The invention relates to a method for preparing a graphene semiconductive shielding material for cables. By mixing graphene and resin with an organic solution respectively, a graphene mixed solution and a resin mixed solution are obtained, and then the graphene solution is mixed with the resin mixed solution, Obtain a mixed solution of graphene and resin, and then obtain the semiconductive shielding material for cables by spray drying and granulating under the protection of an inert gas; this method can obtain a uniformly dispersed semiconductive shielding material, which is safe, environmentally friendly, easy to characteristics of mass production.

Description

A kind of preparation method of graphene semi-conductive shielding material for cable

technical field

The invention relates to a graphene semiconductive shielding material for cables and a preparation method thereof, belonging to the field of cable materials.

Background technique

Polymer semi-conductive shielding materials are widely used in the field of cable shielding. The preparation method is usually by adding a large amount of conductive carbon black to the polymer matrix to improve the conductivity of the polymer. The mass fraction of carbon black added is generally 30~ 50%, the resistivity of the prepared semi-conductive shielding material is generally around 100Ω·cm. However, adding a large amount of carbon black not only reduces the mechanical properties of the polymer matrix, but also makes the surface of the shielding material rough, and the convexity of the shielding material surface Stress concentration is easy to occur under the condition of high-voltage electric field, which leads to the breakdown of the cable insulation layer, and also affects the processing performance of the conductive shielding material during cable extrusion; in addition, the rated working temperature of the cable is usually 90 ° C, polymer semi-conductive shielding material The resistivity of the shielding material will increase with the increase of temperature. In order to offset the influence of the positive temperature coefficient effect and ensure that the shielding material can maintain a certain volume resistivity at the rated working temperature of the cable, it is necessary to further increase the amount of carbon black used. How to improve the processing performance of the semi-conductive shielding material under the premise of ensuring its conductivity is a problem that needs to be solved at present.

Graphene is a two-dimensional new material with excellent electrical conductivity. Its resistivity is 10 ^-8 Ω·m, which is lower than that of silver and copper. Graphene is used as a conductive filler for polymer semiconductive shielding materials. It maintains good electrical conductivity in the case of a large amount, thereby improving its processing performance in cable preparation. In the patent CN201410012969.0, Wen Peng et al prepared graphene semi-conductive shielding material for cables by mixing graphene with resin, plasticizing and granulating, but graphene, as a nano material, is very easy to agglomerate , it is difficult to uniformly disperse graphene in the resin matrix by the method of melt mixing and extrusion. The graphene agglomerated in the resin matrix is not only easy to form a tip discharge under the action of a high-voltage electric field, but also this uneven distribution is difficult to develop graphite. High conductivity of alkenes at low loadings. In the patent CN201110419323.0, Xing Yan et al. provided a method for uniformly dispersing graphene in the resin by means of solution blending, but this method is not efficient in removing solvents and is easy to cause pollution to the environment, so This method is limited to the laboratory level and cannot be applied to large-scale production.

Contents of the invention

The object of the invention is to overcome the defective of prior art, provide a kind of preparation method of graphene semiconductive shielding material for cable, by graphene and resin are mixed with organic solution respectively, obtain graphene mixed solution and resin mixed solution, then The graphene solution is mixed with the resin mixed solution to obtain a graphene-resin mixed solution, and then spray-dried and granulated under the protection of an inert gas to obtain the semi-conductive shielding material for cables.

Its preparation method of described a kind of graphene semi-conductive shielding material for cable specifically comprises the following steps:

(1) Graphene is mixed with an organic solvent, and after ultrasonic dispersion for a period of time, it is placed in a high-speed dispersant machine and stirred and mixed to form a mixed solution of graphene;

(2) mixing the resin with an organic solvent, heating and stirring to mix evenly and then cooling to room temperature to obtain a mixed solution of the resin;

(3) the mixed solution of the graphene of step (1) is mixed with the resin mixed solution of step (2), stir evenly, obtain the mixed solution of graphene and resin;

(4) Under the protection of an inert gas, the mixed solution of the graphene and the resin is dried and granulated by a spray drying granulator to obtain the graphene semiconductive shielding material for cables.

in,

Preferably, in step (1), the organic solvent is selected from tetrahydrofuran, xylene, chloroform and petroleum ether.

Preferably, in step (2), the organic solvent is selected from tetrahydrofuran, xylene, chloroform and petroleum ether.

More preferably, step (1) and step (2) use the same organic solvent.

Preferably, in step (1), the mass ratio of the graphene to the organic solvent is 1:100-1000.

Preferably, in step (1), the ultrasonic dispersion time is 0.5-2 hours.

Preferably, in step (1), the speed of the high-speed dispersant machine is 100-1000 r/min, and the stirring is performed for 0.5-2 hours.

Preferably, in step (2), the resin is selected from polyethylene (polymerization degree 400-1600) or ethylene-vinyl acetate (vinyl acetate content 14.6-28%).

Preferably, in step (2), the mass ratio of the resin to the organic solvent is 1-3:20.

Preferably, in step (2), the heating and stirring is heating and stirring at 40-130° C. for 2-10 hours.

Preferably, in step (3), the mixing mass ratio of the graphene mixed solution to the resin mixed solution is 0.5˜6:1.

Preferably, in step (3), stirring at room temperature at a rotational speed of 200-600 r/min for 1-5 hours to obtain a mixed solution of graphene and resin.

Preferably, in step (4), the inert gas is selected from nitrogen or argon.

Preferably, in step (4), the inlet temperature of the spray drying granulator is 100-300°C, the outlet temperature is 100-300°C, and the spray interval is 5-30s.

Preferably, the exhaust gas of the spray drying granulator is used to recover the organic solvent through a condensing device.

Preferably, the condensing temperature of the condensing device is 0-5°C.

The resistivity of the semi-conductive shielding material for cables prepared by the above preparation method is 3.1-5000Ω·cm.

The beneficial effects of the present invention are:

Mix graphene and resin evenly in an organic solvent, improve the method of spray drying and granulation, use inert gas instead of compressed air for protection, and avoid the danger of organic solvents in the high temperature drying process. The tail is introduced into a condensation device to recover organic solvents and avoid direct discharge into the atmosphere to cause environmental pollution. Using this method, a large amount of semi-conductive shielding materials for cables composed of graphene and resin can be prepared, which can be applied to large-scale production; graphene can be uniformly dispersed in the resin by spray drying and granulation, and prepared A semi-conductive shielding material with excellent conductivity. The semi-conductive shielding material prepared by this method can achieve a resistivity of 100Ω cm by adding 5% graphene in mass fraction, and the resistivity can be reduced to 20Ω cm by adding 10% graphene in mass fraction. cm below, greatly improving the conductivity and processing performance of the semi-conductive shielding material.

Detailed ways

The technical solutions of the present invention are illustrated below through specific examples. It should be understood that one or more method steps mentioned in the present invention do not exclude that there are other method steps before and after the combined steps or other method steps can be inserted between these explicitly mentioned steps; it should also be understood that these The examples are only for illustrating the present invention and are not intended to limit the scope of the present invention. Moreover, unless otherwise stated, the numbering of each method step is only a convenient tool for identifying each method step, and is not intended to limit the sequence of each method step or limit the scope of the present invention. The change or adjustment of its relative relationship is in In the case of no substantive change in technical content, it should also be regarded as the scope of implementation of the present invention.

Example 1:

Add 10 g of graphene into 1000 g of tetrahydrofuran, ultrasonically disperse for 0.5 h, and then use a high-speed disperser to stir at a speed of 100 r/min for 0.5 h to obtain a mixed solution of graphene and tetrahydrofuran. Add 50g of ethylene-vinyl acetate with a vinyl acetate content of 14.6% into 1000g of tetrahydrofuran and mix, heat and stir at 40°C for 2h, and cool to room temperature to obtain a mixed solution of ethylene-vinyl acetate and tetrahydrofuran. Mix 110 g of graphene mixed solution with 189 g of ethylene-vinyl acetate mixed solution, and stir at room temperature for 1 h at a speed of 200 r/min to obtain a mixed solution of graphene and ethylene-vinyl acetate. Under the protection of nitrogen, the mixed solution of graphene and ethylene-vinyl acetate is dried and granulated by a spray drying granulator to obtain a semi-conductive shielding material for cables compounded by graphene and ethylene-vinyl acetate, and the spray drying granulator The inlet temperature is 100°C, the outlet temperature is 100°C, the spraying interval is 5s, the exhaust gas passes through the condensing device to recover the organic solvent, and the condensation temperature is 0°C; the resistivity of the prepared shielding material is 19.7Ω·cm.

Example 2:

Add 5 g of graphene into 1000 g of tetrahydrofuran, ultrasonically disperse for 1 h, and then use a high-speed disperser to stir at a speed of 500 r/min for 1 h to obtain a mixed solution of graphene. Add 100 g of ethylene-vinyl acetate with a vinyl acetate content of 18% to 1000 g of tetrahydrofuran and mix, heat and stir at 80°C for 6 hours, and cool to room temperature to obtain a mixed solution of ethylene-vinyl acetate and tetrahydrofuran. Mix the mixed solution of 100.5g of graphene with the mixed solution of 104.5g of ethylene-vinyl acetate, and stir for 3h at room temperature at a speed of 400r/min to obtain a mixed solution of graphene and ethylene-vinyl acetate. Under the protection of nitrogen, the mixed solution of graphene and ethylene-vinyl acetate is dried and granulated by a spray drying granulator to obtain a semi-conductive shielding material for cables compounded by graphene and ethylene-vinyl acetate, and the spray drying granulator The inlet temperature is 150°C, the outlet temperature is 150°C, the spraying interval is 20s, the waste gas passes through the condensation device to recover the organic solvent, and the condensation temperature is 2.5°C. ; The resistivity of the prepared shielding material is 100Ω·cm.

Example 3:

Add 1 g of graphene to 1000 g of tetrahydrofuran, ultrasonically disperse it for 2 hours, and then use a high-speed disperser to stir at a speed of 1000 r/min for 2 hours to obtain a mixed solution of graphene and tetrahydrofuran. Add 150g of ethylene-vinyl acetate with a vinyl acetate content of 28% to 1000g of tetrahydrofuran and mix, heat and stir at 130°C for 10h, and cool to room temperature to obtain a mixed solution of ethylene-vinyl acetate and tetrahydrofuran. A mixed solution of 100.1 g of graphene and tetrahydrofuran was mixed with a mixed solution of 75.9 g of ethylene-vinyl acetate and tetrahydrofuran, and stirred at room temperature at a speed of 600 r/min for 5 hours to obtain a mixed solution of graphene and ethylene-vinyl acetate. Under the protection of nitrogen, the mixed solution of graphene and ethylene-vinyl acetate is dried and granulated by a spray drying granulator to obtain a semi-conductive shielding material for cables compounded by graphene and ethylene-vinyl acetate, and the spray drying granulator The inlet temperature is 300°C, the outlet temperature is 300°C, the spraying interval is 30s, the exhaust gas passes through the condensing device to recover the organic solvent, and the condensation temperature is 5°C; the resistivity of the prepared shielding material is 5000Ω·cm.

Example 4:

Add 10 g of graphene into 1000 g of chloroform, ultrasonically disperse for 0.5 h, and then use a high-speed disperser to stir at a speed of 100 r/min for 0.5 h to obtain a mixed solution of graphene and chloroform. Add 50g of ethylene-vinyl acetate with a vinyl acetate content of 14.6% into 1000g of chloroform and mix, heat and stir at 40°C for 2h, and cool to room temperature to obtain a mixed solution of ethylene-vinyl acetate and chloroform. Mix the mixed solution of 110g graphene and chloroform with the mixed solution of 119g ethylene-vinyl acetate and chloroform, and stir for 1h at room temperature at a speed of 200r/min to obtain a mixed solution of graphene and ethylene-vinyl acetate. solution. Under the protection of argon, the mixed solution of graphene and ethylene-vinyl acetate is dried and granulated by a spray drying granulator to obtain a semi-conductive shielding material for cables composited by graphene and ethylene-vinyl acetate, which is spray-dried and granulated The inlet temperature of the machine is 100°C, the outlet temperature is 100°C, and the spraying interval is 5s. The exhaust gas passes through the condensing device to recover the organic solvent, and the condensation temperature is 0°C; the resistivity of the prepared shielding material is 15.4Ω·cm.

Example 5:

5 g of graphene was added to 1000 g of chloroform, and after ultrasonic dispersion for 1 h, a high-speed disperser was used to stir at a speed of 500 r/min for 1 h to obtain a mixed solution of graphene and chloroform. Add 100g of ethylene-vinyl acetate with a vinyl acetate content of 18% to 1000g of chloroform and mix, heat and stir at 80°C for 6h, and cool to room temperature to obtain a mixed solution of ethylene-vinyl acetate and chloroform. Mix the mixed solution of 100.5g graphene and chloroform with the mixed solution of 86.17g ethylene-vinyl acetate and chloroform, stir at room temperature at a speed of 400r/min for 3h to obtain graphene and ethylene-vinyl acetate mixed solution. Under the protection of argon, the mixed solution of graphene and ethylene-vinyl acetate is dried and granulated by a spray drying granulator to obtain a semi-conductive shielding material for cables composited by graphene and ethylene-vinyl acetate, which is spray-dried and granulated The inlet temperature of the machine is 150°C, the outlet temperature is 150°C, the spraying interval is 20s, the waste gas passes through the condensing device to recover the organic solvent, and the condensation temperature is 2.5°C; the resistivity of the prepared shielding material is 82.1Ω·cm.

Embodiment 6:

Add 1 g of graphene to 1000 g of chloroform, ultrasonically disperse it for 2 hours, and then use a high-speed disperser to stir at a speed of 1000 r/min for 2 hours to obtain a mixed solution of graphene and chloroform. Add 150g of ethylene-vinyl acetate with a vinyl acetate content of 28% to 1000g of chloroform and mix, heat and stir at 130°C for 10h, and cool to room temperature to obtain a mixed solution of ethylene-vinyl acetate and chloroform. Mix the mixed solution of 100.1g graphene and chloroform with 37.57g ethylene-vinyl acetate and chloroform, and stir for 5h at room temperature at a speed of 600r/min to obtain a mixture of graphene and ethylene-vinyl acetate. solution. Under the protection of argon, the mixed solution of graphene and ethylene-vinyl acetate is dried and granulated by a spray drying granulator to obtain a semi-conductive shielding material for cables composited by graphene and ethylene-vinyl acetate, which is spray-dried and granulated The inlet temperature of the machine is 300°C, the outlet temperature is 300°C, the spraying interval is 30s, and the waste gas passes through the condensing device to recover the organic solvent, and the condensation temperature is 5°C; the resistivity of the prepared shielding material is 3500Ω·cm.

Embodiment 7:

Add 10 g of graphene to 1000 g of xylene, ultrasonically disperse for 0.5 h, and then use a high-speed disperser to stir at a speed of 100 r/min for 0.5 h to obtain a mixed solution of graphene and xylene. Add 50g of polyethylene with a degree of polymerization of 1600 into 1000g of xylene and mix, heat and stir at 40°C for 2h, and cool to room temperature to obtain a mixed solution of polyethylene and xylene. 110g of the mixed solution of graphene and xylene was mixed with 84g of the mixed solution of polyethylene and xylene, and stirred at room temperature at a speed of 200r/min for 1h to obtain a mixed solution of graphene and polyethylene. Under the protection of nitrogen, the mixed solution of graphene and polyethylene is dried and granulated by a spray drying granulator to obtain a semi-conductive shielding material for cables composited by graphene and polyethylene. The inlet temperature of the spray drying granulator is 100°C. The outlet temperature was 100°C, the spraying interval was 5s, and the exhaust gas passed through the condensing device to recover the organic solvent, and the condensation temperature was 0°C; the resistivity of the prepared shielding material was 11.7Ω·cm.

Embodiment 8:

5 g of graphene was added to 1000 g of xylene, and after ultrasonic dispersion for 1 h, a high-speed disperser was used to stir at a speed of 500 r/min for 1 h to obtain a mixed solution of graphene and xylene. Add 100g of polyethylene with a degree of polymerization of 1000 to 1000g of xylene and mix, heat and stir at 80°C for 6h, and cool to room temperature to obtain a mixed solution of polyethylene and xylene. Mix 100.5g of graphene-xylene mixed solution with 73.07g polyethylene-xylene mixed solution, and stir at room temperature at 400r/min for 3h to obtain graphene-polyethylene mixed solution. Under the protection of nitrogen, the mixed solution of graphene and polyethylene is dried and granulated by a spray drying granulator to obtain a semi-conductive shielding material for cables composited by graphene and polyethylene. The inlet temperature of the spray drying granulator is 150°C. The outlet temperature was 150°C, the spraying interval was 20s, and the exhaust gas passed through the condensing device to recover the organic solvent, and the condensation temperature was 2.5°C; the resistivity of the prepared shielding material was 66.3Ω·cm.

Embodiment 9:

Add 1 g of graphene to 1000 g of xylene, ultrasonically disperse for 2 h, then use a high-speed disperser to stir at a speed of 1000 r/min for 2 h to obtain a mixed solution of graphene and xylene. Add 150 g of polyethylene with a degree of polymerization of 400 to 1000 g of xylene and mix, heat and stir at 130° C. for 10 h, and cool to room temperature to obtain a mixed solution of polyethylene and xylene. Mix 100.1g of graphene-xylene mixed solution with 24.79g polyethylene-xylene mixed solution, stir at room temperature at 600r/min for 5h to obtain graphene-polyethylene mixed solution. Under the protection of nitrogen, the mixed solution of graphene and polyethylene is dried and granulated by a spray drying granulator to obtain a semi-conductive shielding material for cables composited by graphene and polyethylene. The inlet temperature of the spray drying granulator is 300°C. The outlet temperature was 300°C, the spraying interval was 30s, and the exhaust gas passed through the condensing device to recover the organic solvent, and the condensation temperature was 5°C; the resistivity of the prepared shielding material was 1121Ω·cm.

Example 10:

10 g of graphene was added to 1000 g of petroleum ether, ultrasonically dispersed for 0.5 h, and stirred at a speed of 100 r/min for 0.5 h using a high-speed disperser to obtain a mixed solution of graphene and petroleum ether. 50 g of polyethylene with a degree of polymerization of 1600 was added to 1000 g of petroleum ether and mixed, heated and stirred at 40° C. for 2 hours, and cooled to room temperature to obtain a mixed solution of polyethylene and petroleum ether. 110g of a mixed solution of graphene and petroleum ether was mixed with a mixed solution of 49g of polyethylene and petroleum ether, and stirred at room temperature at a speed of 200r/min for 1h to obtain a mixed solution of graphene and polyethylene. Under the protection of argon, the mixed solution of graphene and polyethylene is dried and granulated by a spray drying granulator to obtain a semi-conductive shielding material for cables composited by graphene and polyethylene. The inlet temperature of the spray drying granulator is 100°C , the outlet temperature is 100°C, the spraying interval is 5s, the exhaust gas passes through the condensing device to recover the organic solvent, and the condensation temperature is 0°C; the resistivity of the prepared shielding material is 3.1Ω·cm.

Example 11:

5 g of graphene was added to 1000 g of petroleum ether, and after ultrasonic dispersion for 1 h, a high-speed disperser was used to stir at a speed of 500 r/min for 1 h to obtain a mixed solution of graphene and petroleum ether. 100g of polyethylene with a degree of polymerization of 1000 was added to 1000g of petroleum ether and mixed, heated and stirred at 80°C for 6h, and cooled to room temperature to obtain a mixed solution of polyethylene and petroleum ether. 100.5g of the mixed solution of graphene and petroleum ether was mixed with 63.25g of the mixed solution of polyethylene and petroleum ether, and stirred at room temperature at a speed of 400r/min for 3h to obtain a mixed solution of graphene and polyethylene. Under the protection of argon, the mixed solution of graphene and polyethylene is dried and granulated by a spray drying granulator to obtain a semi-conductive shielding material for cables composited by graphene and polyethylene. The inlet temperature of the spray drying granulator is 150°C , the outlet temperature is 150°C, the spraying interval is 20s, the exhaust gas passes through the condensing device to recover the organic solvent, and the condensation temperature is 2.5°C; the resistivity of the prepared shielding material is 48.4Ω·cm.

Example 12:

Add 1 g of graphene to 1000 g of petroleum ether, ultrasonically disperse it for 2 hours, then use a high-speed disperser to stir at a speed of 1000 r/min for 2 hours to obtain a mixed solution of graphene and petroleum ether. 150g of polyethylene with a degree of polymerization of 400 was added to 1000g of petroleum ether and mixed, heated and stirred at 130°C for 10h, and cooled to room temperature to obtain a mixed solution of polyethylene and petroleum ether. 100.1 g of the mixed solution of graphene and petroleum ether was mixed with 18.4 g of the mixed solution of polyethylene and petroleum ether, and stirred at room temperature at a speed of 600 r/min for 5 hours to obtain a mixed solution of graphene and polyethylene. Under the protection of argon, the mixed solution of graphene and polyethylene is dried and granulated by a spray drying granulator to obtain a semi-conductive shielding material for cables composited by graphene and polyethylene. The inlet temperature of the spray drying granulator is 300°C , the outlet temperature is 300°C, the spraying interval is 30s, the exhaust gas passes through the condensing device to recover the organic solvent, and the condensation temperature is 5°C; the resistivity of the prepared shielding material is 397Ω·cm.

Claims (14)

1. a preparation method of graphene semiconducting shielding material for cable, it is characterized in that, by graphene and resin are mixed with organic solution respectively, obtain graphene mixed solution and resin mixed solution, then graphene solution is mixed with resin The solutions are mixed to obtain a mixed solution of graphene and resin, and then spray-dried and granulated under the protection of an inert gas to obtain the semi-conductive shielding material for cables. 2. the preparation method of a kind of graphene semi-conductive shielding material for cables as claimed in claim 1, is characterized in that, the waste gas of described spray drying granulator reclaims organic solvent by condensing unit. 3. its preparation method of a kind of graphene semi-conductive shielding material for cables as claimed in claim 1, is characterized in that, specifically comprises the following steps: (1) Graphene is mixed with an organic solvent, and after ultrasonic dispersion for a period of time, it is placed in a high-speed dispersant machine and stirred and mixed to form a mixed solution of graphene; (2) mixing the resin with an organic solvent, heating and stirring to mix evenly and then cooling to room temperature to obtain a mixed solution of the resin; (3) the mixed solution of the graphene of step (1) is mixed with the resin mixed solution of step (2), stir evenly, obtain the mixed solution of graphene and resin; (4) Under the protection of an inert gas, the mixed solution of the graphene and the resin is dried and granulated by a spray drying granulator to obtain the graphene semiconductive shielding material for cables. 4. the preparation method of a kind of graphene semiconductive shielding compound for cable as claimed in claim 3 is characterized in that, in step (1), described organic solvent is selected from tetrahydrofuran (THF), dimethylbenzene, chloroform and Petroleum ether; In step (3), the organic solvent is selected from tetrahydrofuran, xylene, chloroform and petroleum ether. 5. the preparation method of a kind of graphene semiconductive shielding material for cables as claimed in claim 3, is characterized in that, in step (1), the mass ratio of described graphene and organic solvent is 1:100～1000. 6. the preparation method of a kind of graphene semiconductive shielding material for cables as claimed in claim 3, is characterized in that, in step (1), the time of described ultrasonic dispersion is 0.5～2 hours; The rotating speed of the machine is 100-1000r/min, stirring for 0.5-2 hours. 7. the preparation method of a kind of graphene semiconductive shielding material for cables as claimed in claim 3, is characterized in that, in step (2), described resin is selected from polyethylene and ethylene-vinyl acetate. 8. the preparation method of a kind of graphene semiconductive shielding material for cables as claimed in claim 3, is characterized in that, in step (2), the mass ratio of described resin and organic solvent is 1～3:20. 9 . The method for preparing a graphene semiconductive shielding material for cables according to claim 3 , wherein in step (2), the heating and stirring is heating and stirring at 40 to 130° C. for 2 to 10 hours. 10. the preparation method of a kind of graphene semi-conductive shielding material for cable as claimed in claim 3, is characterized in that, in step (3), the ratio of the mixing quality of the mixed solution of described graphene and the mixed solution of resin It is 0.5～6:1. 11. the preparation method of a kind of graphene semi-conductive shielding material for cables as claimed in claim 3, is characterized in that, in step (3), stir 1～5h at room temperature, the rotating speed of 200～600r/min, obtain Mixed solution of graphene and resin. 12. the preparation method of a kind of graphene semi-conductive shielding material for cables as claimed in claim 3, is characterized in that, in step (4), the inlet temperature of described spray drying granulator is 100～300 ℃, and outlet temperature 100～300℃, spray interval 5～30s. 13. the preparation method of a kind of graphene semi-conductive shielding material for cables as claimed in claim 3, is characterized in that, in step (4), the waste gas of described spray drying granulator reclaims organic solvent by condensing device, condenses The temperature is 0-5°C. 14. the graphene semiconductive shielding material for cable that the preparation method of a kind of graphene semiconductive shielding material for cable as described in any one of claim 1-13 makes.