CN112226021A - Preparation method of graphene/polyvinyl chloride composite material - Google Patents
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Abstract
The invention discloses a preparation method of a graphene/polyvinyl chloride composite material. The method comprises the following steps: firstly, preparing modified graphene; secondly, preparing aqueous emulsion; thirdly, preparing modified polyvinyl chloride resin; and fourthly, preparing the graphene/polyvinyl chloride composite material. The method disclosed by the invention is low in cost, simple in preparation and easy for industrial batch production, solves the problem that the traditional waterproof material is easy to crack, and prepares the waterproof and corrosion-resistant composite material by uniformly dispersing graphene in polyvinyl chloride resin and under the synergistic action of the graphene and the polyvinyl chloride resin.
Description
Technical Field
The invention relates to the field of composite material preparation, and particularly relates to a preparation method of a graphene/polyvinyl chloride composite material.
Background
The problems of bridge collapse, ship wrecking, factory equipment damage and the like caused by metal corrosion bring huge loss to daily life of people. Although people cannot avoid the occurrence of metal corrosion, people can search for an effective means to protect the metal by researching the mechanism of the metal corrosion so as to delay the corrosion rate of the metal and reduce the harm caused by the corrosion. The graphene is a two-dimensional carbon nano material, has a special lamellar structure, has good stability and barrier property on water, oxygen and ions, can be applied to anticorrosive coatings as fillers such as flaky mica powder, aluminum powder and glass sheets, plays a role of physical barrier to block the permeation of oxygen and anticorrosive media, reduces the permeability of anticorrosive coatings, and improves the corrosion resistance of the coatings. And the graphene is a chemical inert substance, the oxidation resistance and the oxygen diffusion resistance of the graphene are gradually concerned, and the graphene is applied to the fields of metal corrosion prevention, antifouling, electric conduction and other functional coatings and achieves some results. The polyvinyl chloride waterproof coiled material is one of main polymer coiled materials, and has excellent performances such as corrosion resistance, aging resistance, long service life and the like. Meanwhile, the polyvinyl chloride resin is one of synthetic resins which realize industrialization in the world at the earliest time, has certain corrosion resistance and insulativity, and has excellent performance, low price and wide raw material sources.
The graphene and the polyvinyl chloride resin are compounded, so that the excellent thermal, electrical and shielding properties of the graphene can be kept, and the characteristics of strong adhesive force, high mechanical property and the like of the polyvinyl chloride resin are also achieved, and the functional waterproof and anticorrosive material can be obtained after the graphene and the polyvinyl chloride resin are compounded. The common metal protection technologies mainly include cathodic protection, corrosion inhibitor protection, metal plating, surface organic coating and the like. The first three protection methods have the problems of high cost, environmental pollution, limited application environment and the like. The surface organic coating method is the most common and effective metal protection method, and is to cover a layer of organic protective film on the metal surface to prevent the metal from directly contacting with corrosive media in the environment, so as to reduce the probability of chemical or electrochemical reaction of the metal. However, a considerable part of the traditional organic coatings contain heavy metal toxic substances such as chromate, lead, zinc and the like, certain potential safety hazards and environmental pollution risks exist, a large amount of waste is consumed, and the organic coatings are not renewable, and are extremely not beneficial to the sustainable development of society and economy. Therefore, the search for a metal surface coating material with good shielding performance and environmental friendliness is a research hotspot in the field of metal corrosion prevention at present.
Disclosure of Invention
The invention aims to provide a preparation method of a graphene/polyvinyl chloride composite material, which is prepared from a polyvinyl chloride resin modified by graphene, is easy to process, has an electrostatic elimination effect, can prevent water and resist corrosion, and has a function of delaying metal corrosion.
The invention is realized by the following technical scheme:
a preparation method of a graphene/polyvinyl chloride composite material is characterized by comprising the following steps:
firstly, preparing modified graphene:
(1) under the ice bath condition (namely at 0-5 ℃), uniformly mixing nitrate and sulfurous acid, then adding graphene and uniformly stirring to obtain a mixed solution A;
(2) adding an oxidant into the mixed solution A under the condition of water bath, stirring for reaction, adding deionized water after reaction, heating, carrying out heat preservation treatment, and then terminating the reaction (adding a large amount of deionized water to terminate the reaction);
(3) after the reaction is ended, adding hydrogen peroxide into the reaction system, stirring, filtering, washing and drying to obtain modified graphene;
secondly, preparing the aqueous emulsion:
(1) adding polyvinyl alcohol with sulfydryl at the tail end into deionized water for dissolving, and then adjusting the pH value to be acidic to obtain a mixed solution B;
(2) adding acrylic ester into the mixed solution B in an inert atmosphere, heating, and then adding a potassium bromide solution for reaction to obtain an aqueous emulsion;
thirdly, preparing the modified polyvinyl chloride resin:
adding polyvinyl chloride resin into the obtained aqueous emulsion to obtain modified polyvinyl chloride resin;
fourthly, preparing the graphene/polyvinyl chloride composite material:
(1) mixing n-octyl phthalate and a calcium-zinc liquid stabilizer, adding modified polyvinyl chloride resin, stirring to obtain a mixed material A, drying the mixed material A, and taking out for later use;
(2) adding the modified graphene and the processing aid into the mixed material A to be used, and continuously stirring to obtain a mixed material B;
(3) and adding the obtained mixed material B into an open mill for mixing to obtain the graphene/polyvinyl chloride composite material.
Further, firstly, preparing modified graphene: in the step (1), the nitrate is sodium nitrate; the mass volume ratio of the nitrate to the sulfurous acid is 0.02-0.025 g/mL; the mass ratio of the nitrate to the graphene is 1: (1-3).
Further, firstly, preparing modified graphene: in the step (2), the oxidant is potassium permanganate; under the condition of 35-45 ℃ water bath, adding potassium permanganate into the mixed solution A, magnetically stirring and reacting for 2-5 hours, adding deionized water after reaction, heating to 90-100 ℃, preserving heat for 10-20 minutes, and then stopping reaction; the mass ratio of the potassium permanganate to the graphene is (2-4): 1; the mass volume ratio of the potassium permanganate to the deionized water is 0.05-0.1 g/mL.
Further, firstly, preparing modified graphene: after the reaction in the step (3) is ended, adding hydrogen peroxide into a reaction system, stirring, filtering while the reaction system is hot, washing filter residues with hydrochloric acid, washing the filter residues with deionized water to be neutral, and drying the filter residues for 1-3 hours at the temperature of 60-70 ℃ to obtain modified graphene; the volume ratio of the hydrogen peroxide to the sulfurous acid is 1: (8-10).
Further, preparing an aqueous emulsion: adding polyvinyl alcohol with sulfydryl at the tail end into deionized water, heating to 85-95 ℃ for dissolution, and then adjusting the pH to 2-3 by using sulfuric acid to obtain a mixed solution B; the end beltThe mass volume ratio of the sulfhydryl polyvinyl alcohol to the deionized water is 1-5 g/mL; the polyvinyl alcohol having a mercapto group at the terminal has a polymerization degree of 500, a saponification degree of 88% (mole fraction), and a mercapto group content of 3.2X 10-5mol/g。
Further, preparing an aqueous emulsion: the mass ratio of the acrylate to the polyvinyl alcohol with the mercapto group at the tail end in the step (2) is 14: 1; the heating temperature is 60-70 ℃; the volume ratio of the potassium bromide solution to the mixed solution B is 1: (40-50); the mass fraction of potassium bromide in the potassium bromide solution is 2-5%; the reaction time is 2-5 hours.
Further, preparing the graphene/polyvinyl chloride composite material: the mass ratio of the n-octyl phthalate, the calcium-zinc liquid stabilizer and the modified polyvinyl chloride resin in the step (1) is 1: 1: 3; the drying temperature is 80-90 ℃, and the drying time is 1-3 hours.
Further, preparing the graphene/polyvinyl chloride composite material: in the step (2), the mass ratio of the modified graphene to the processing aid is 1: (2-5); the mass of the modified graphene in the mixed material B accounts for 1-2%.
Further, the processing aid is any one of a quaternary ammonium salt cationic active agent, a methacrylate polymer type cationic active agent, a methacrylate amide polymer type cationic active agent, a fatty amide and a mixture of silver sulfide.
Further, preparing the graphene/polyvinyl chloride composite material: the mixing time in the step (3) is 5-10 minutes; the temperature during mixing is 160-180 ℃.
The invention has the beneficial effects that:
the method disclosed by the invention is low in cost, simple in preparation and easy for industrial batch production, solves the problem that the traditional waterproof material is easy to crack, and prepares the waterproof and corrosion-resistant composite material by uniformly dispersing graphene in polyvinyl chloride resin and under the synergistic action of the graphene and the polyvinyl chloride resin.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 is a Tafel polarization curve of metals coated with materials obtained in examples 1-3 of the present invention and comparative example 1;
FIG. 2 is an optical diagram showing the adhesion between the metal and the coating layers formed after the metal is coated with the materials obtained in examples 1 to 3 of the present invention and comparative example 1.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in 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 of the embodiments. The following description of at least one exemplary embodiment is merely illustrative in nature and is in no way intended to limit the invention, its application, or uses. 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
A preparation method of a graphene/polyvinyl chloride composite material comprises the following steps:
firstly, preparing modified graphene:
(1) 1.0g of sodium nitrate (NaNO) was added to the dried beaker under ice-bath conditions (0-5 ℃ C.)3) And 46.0mL of sulfurous acid (H)2SO3) Uniformly mixing, then adding 2.0g of graphene, and uniformly stirring to obtain a mixed solution A;
(2) 6.0g of potassium permanganate (KMnO) was added to the mixture A in a water bath at 35 deg.C4) Magnetically stirring to react for 2 hours, adding 92.0mL of deionized water after the reaction, rapidly heating to 98 ℃, preserving the heat for 15 minutes at the temperature, and then adding 280.0mL (a large amount) of deionized water to stop the reaction;
(3) after the reaction was terminated, 5.0mL of hydrogen peroxide (H) was added to the reaction system2O2) Stirring uniformly by using a glass rod, changing the reaction system from brown black to bright yellow, filtering while the reaction system is hot, washing filter residues by using hydrochloric acid, washing the filter residues to be neutral by using deionized water, and drying the filter residues for 3 hours in a drying box at the temperature of 65 ℃ to obtain modified graphene;
secondly, preparing the aqueous emulsion:
(1) adding deionized water and polyvinyl alcohol with sulfydryl at the tail end into a polymerization kettle with a stirrer, heating to 95 ℃ to completely dissolve, and then regulating the pH value of the system to be 3 by using sulfuric acid to obtain a mixed solution B; wherein the polyvinyl alcohol with sulfhydryl at the end has polymerization degree of 500, saponification degree of 88% (mol fraction), and sulfhydryl content of 3.2 × 10-5mol/g; the mass-volume ratio of the polyvinyl alcohol with the mercapto group at the tail end to the deionized water is 1 g/mL;
(2) adding acrylic ester into the mixed solution B under an inert atmosphere, heating to 65 ℃, and then adding a potassium bromide solution with the mass fraction of 2% for reacting for 2 hours to obtain a water-based emulsion; the mass ratio of the acrylic ester to the polyvinyl alcohol with the mercapto group at the tail end is 14: 1; the volume ratio of the potassium bromide solution to the mixed solution B is 1: 49;
thirdly, preparing the modified polyvinyl chloride resin:
adding polyvinyl chloride resin into the obtained aqueous emulsion to obtain modified polyvinyl chloride resin;
fourthly, preparing the graphene/polyvinyl chloride composite material:
(1) weighing n-octyl phthalate and a calcium-zinc liquid stabilizer, uniformly mixing, adding modified polyvinyl chloride resin, uniformly stirring to obtain a mixed material A, putting the mixed material A into an oven at 80 ℃, drying and curing for 1 hour, and taking out for later use; the mass ratio of the n-octyl phthalate to the calcium-zinc liquid stabilizer to the modified polyvinyl chloride resin is 1: 1: 3;
(2) adding the modified graphene and the processing aid into the mixed material A to be used, and continuously stirring to obtain a mixed material B; the mass ratio of the modified graphene to the processing aid is 1: 2; the mass of the modified graphene in the mixed material B accounts for 1.0%; the processing aid is a quaternary ammonium salt cationic active agent;
(3) adding the obtained mixture B into a double roller of a small-sized precise double-roller open mill, wherein the temperature of the front roller and the temperature of the rear roller are respectively 170 ℃ and 168 ℃, and the rotation speed ratio is 1: and (3) mixing for 5 minutes under the condition of 1.1, forming a film by mixing, taking down and cooling to obtain the graphene/polyvinyl chloride composite material.
Example 2
A preparation method of a graphene/polyvinyl chloride composite material comprises the following steps:
firstly, preparing modified graphene:
(1) 1.0g of sodium nitrate (NaNO) was added to the dried beaker under ice-bath conditions (0-5 ℃ C.)3) And 40.0mL of sulfurous acid (H)2SO3) Uniformly mixing, then adding 3.0g of graphene, and uniformly stirring to obtain a mixed solution A;
(2) to the above-mentioned mixed solution A was added 7.5g of potassium permanganate (KMnO) in a water bath at 40 deg.C4) Magnetically stirring to react for 4 hours, adding 100.0mL of deionized water after reaction, rapidly heating to 90 ℃, preserving heat at the temperature for 20 minutes, and then adding 300.0mL (large amount) of deionized water to stop the reaction;
(3) after the reaction was terminated, 5.0mL of hydrogen peroxide (H) was added to the reaction system2O2) Stirring uniformly by using a glass rod, changing the reaction system from brown black to bright yellow, filtering while the reaction system is hot, washing filter residues by using hydrochloric acid, washing the filter residues to be neutral by using deionized water, and drying the filter residues for 2 hours in a drying box at the temperature of 70 ℃ to obtain modified graphene;
secondly, preparing the aqueous emulsion:
(1) adding deionized water and polyvinyl alcohol with sulfydryl at the tail end into a polymerization kettle with a stirrer, heating to 85 ℃ to completely dissolve, and then regulating the pH value of the system to 2.5 by using sulfuric acid to obtain a mixed solution B; wherein the polyvinyl alcohol with sulfhydryl at the end has polymerization degree of 500, saponification degree of 88% (mol fraction), and sulfhydryl content of 3.2 × 10-5mol/g; the mass-volume ratio of the polyvinyl alcohol with the mercapto group at the tail end to the deionized water is 3 g/mL;
(2) adding acrylic ester into the mixed solution B under an inert atmosphere, heating to 70 ℃, and then adding a potassium bromide solution with the mass fraction of 5% for reacting for 5 hours to obtain a water-based emulsion; the mass ratio of the acrylic ester to the polyvinyl alcohol with the mercapto group at the tail end is 14: 1; the volume ratio of the potassium bromide solution to the mixed solution B is 1: 45, a first step of;
thirdly, preparing the modified polyvinyl chloride resin:
adding polyvinyl chloride resin into the obtained aqueous emulsion to obtain modified polyvinyl chloride resin;
fourthly, preparing the graphene/polyvinyl chloride composite material:
(1) weighing n-octyl phthalate and a calcium-zinc liquid stabilizer, uniformly mixing, adding modified polyvinyl chloride resin, uniformly stirring to obtain a mixed material A, putting the mixed material A into a drying oven at 90 ℃, drying and curing for 2 hours, and taking out for later use; the mass ratio of the n-octyl phthalate to the calcium-zinc liquid stabilizer to the modified polyvinyl chloride resin is 1: 1: 3;
(2) adding the modified graphene and the processing aid into the mixed material A to be used, and continuously stirring to obtain a mixed material B; the mass ratio of the modified graphene to the processing aid is 1: 3; the mass of the modified graphene in the mixed material B accounts for 1.5%; the processing aid is a methacrylate polymer type cationic active agent;
(3) adding the obtained mixture B into a double roller of a small-sized precise double-roller open mill, wherein the temperature of the front roller and the temperature of the rear roller are respectively 170 ℃ and 168 ℃, and the rotation speed ratio is 1: and (3) mixing for 8 minutes under the condition of 1.1, forming a film by mixing, taking down and cooling to obtain the graphene/polyvinyl chloride composite material.
Example 3
A preparation method of a graphene/polyvinyl chloride composite material comprises the following steps:
firstly, preparing modified graphene:
(1) under the condition of ice bath (0-5 ℃), underTo a dry beaker was added 1.0g of sodium nitrate (NaNO)3) And 50.0mL of sulfurous acid (H)2SO3) Uniformly mixing, then adding 1.0g of graphene, and uniformly stirring to obtain a mixed solution A;
(2) 4.0g of potassium permanganate (KMnO) was added to the mixture A in a water bath at 45 deg.C4) Magnetically stirring to react for 5 hours, adding 50.0mL of deionized water after the reaction, rapidly heating to 95 ℃, preserving the heat for 10 minutes at the temperature, and then adding 250.0mL (large amount) of deionized water to stop the reaction;
(3) after the reaction was terminated, 6.0mL of hydrogen peroxide (H) was added to the reaction system2O2) Stirring uniformly by using a glass rod, changing the reaction system from brown black to bright yellow, filtering while the reaction system is hot, washing filter residues by using hydrochloric acid, washing the filter residues to be neutral by using deionized water, and drying the filter residues for 3 hours in a drying box at the temperature of 60 ℃ to obtain modified graphene;
secondly, preparing the aqueous emulsion:
(1) adding deionized water and polyvinyl alcohol with sulfydryl at the tail end into a polymerization kettle with a stirrer, heating to 90 ℃ to completely dissolve, and then regulating the pH value of the system to be 2 by using sulfuric acid to obtain a mixed solution B; wherein the polyvinyl alcohol with sulfhydryl at the end has polymerization degree of 500, saponification degree of 88% (mol fraction), and sulfhydryl content of 3.2 × 10-5mol/g; the mass-volume ratio of the polyvinyl alcohol with the mercapto group at the tail end to the deionized water is 5 g/mL;
(2) adding acrylic ester into the mixed solution B under an inert atmosphere, heating to 60 ℃, and then adding a potassium bromide solution with the mass fraction of 3% for reacting for 3 hours to obtain a water-based emulsion; the mass ratio of the acrylic ester to the polyvinyl alcohol with the mercapto group at the tail end is 14: 1; the volume ratio of the potassium bromide solution to the mixed solution B is 1: 40;
thirdly, preparing the modified polyvinyl chloride resin:
adding polyvinyl chloride resin into the obtained aqueous emulsion to obtain modified polyvinyl chloride resin;
fourthly, preparing the graphene/polyvinyl chloride composite material:
(1) weighing n-octyl phthalate and a calcium-zinc liquid stabilizer, uniformly mixing, adding modified polyvinyl chloride resin, uniformly stirring to obtain a mixed material A, putting the mixed material A into an oven at 85 ℃, drying and curing for 3 hours, and taking out for later use; the mass ratio of the n-octyl phthalate to the calcium-zinc liquid stabilizer to the modified polyvinyl chloride resin is 1: 1: 3;
(2) adding the modified graphene and the processing aid into the mixed material A to be used, and continuously stirring to obtain a mixed material B; the mass ratio of the modified graphene to the processing aid is 1: 5; the mass of the modified graphene in the mixed material B accounts for 2.0%;
(3) adding the obtained mixture B into a double roller of a small-sized precise double-roller open mill, wherein the temperature of the front roller and the temperature of the rear roller are respectively 170 ℃ and 168 ℃, and the rotation speed ratio is 1: and (3) mixing for 10 minutes under the condition of 1.1, forming a film by mixing, taking down and cooling to obtain the graphene/polyvinyl chloride composite material.
Comparative example 1
A modified polyvinyl chloride resin was prepared with reference to the preparation method of example 1, except that no graphene was added in comparative example 1.
Comparative example 2
Referring to the preparation method of example 3, the graphene/polyvinyl chloride composite material is prepared, and comparative example 2 is different from example 3 in that the mass ratio of graphene in comparative example 2 is 2.5%.
Test example 1
The graphene/polyvinyl chloride composite materials prepared in the above examples 1 to 3, the modified polyvinyl chloride resin obtained in the comparative example 1, and the graphene/polyvinyl chloride composite material prepared in the comparative example 2 were respectively coated on a metal (the thickness of the coating was maintained at 90 to 100 μm), and since the specific surface area of graphene is large and the oil absorption is large, when the addition of graphene reaches 2.5%, the viscosity of the coating is too large, which affects the atomization of air spraying, resulting in failure of spraying.
The metal coated with the materials obtained in examples 1 to 3 and comparative example 1 was then tested using an electrochemical workstation for the Tafel polarization curve, the results of which are shown in FIG. 1 (and the numbers in FIG. 1)Plotted as table 1), it can be seen from fig. 1 or table 1 that the corrosion current density of the coating reaches 0.058 mua/cm at the lowest when the addition amount of graphene is 1.5%2The corrosion resistance of the coating is greatly improved; when the graphene content is 2.0%, the corrosion current density is very high at 0.424. mu.A/cm although the potential is highest2. The high self-corrosion potential and the low self-corrosion current density are the characteristics that the coating has good corrosion resistance, so that the corrosion resistance is optimal when the addition amount of the graphene is 1.5 percent, and the corrosion resistance of the graphene/polyvinyl chloride composite material prepared by the invention is good.
The adhesion of the coatings formed by the materials prepared in the above examples 1-3 and comparative example 1 after coating metal (i.e. different addition amounts of graphene) was tested, and the optical photographs after the adhesion test are shown in fig. 2 (in the figures, a is the material obtained in comparative example 1, b is the material prepared in example 1, c is the material prepared in example 2, and d is the material prepared in example 3). as shown in fig. 2, it can be seen that the mechanical properties of the coating gradually increase with the increase of the content of graphene, so the paint film still can maintain very good adhesion, and when the content of graphene is too high, the mechanical properties of the paint film per se decrease due to the increase of the viscosity of the paint and the agglomeration of graphene, so the adhesion is reduced.
TABLE 1
The above-mentioned preferred embodiments of the present invention are provided for illustration only and not for the purpose of limiting the invention. Obvious variations or modifications of the present invention are within the scope of the present invention.
Claims (10)
1. A preparation method of a graphene/polyvinyl chloride composite material is characterized by comprising the following steps:
firstly, preparing modified graphene:
(1) under the ice bath condition, uniformly mixing nitrate and sulfurous acid, then adding graphene and uniformly stirring to obtain a mixed solution A;
(2) under the condition of water bath, adding an oxidant into the mixed solution A, stirring for reaction, adding deionized water after reaction, heating, carrying out heat preservation treatment, and then terminating the reaction;
(3) after the reaction is ended, adding hydrogen peroxide into the reaction system, stirring, filtering, washing and drying to obtain modified graphene;
secondly, preparing the aqueous emulsion:
(1) adding polyvinyl alcohol with sulfydryl at the tail end into deionized water for dissolving, and then adjusting the pH value to be acidic to obtain a mixed solution B;
(2) adding acrylic ester into the mixed solution B in an inert atmosphere, heating, and then adding a potassium bromide solution for reaction to obtain an aqueous emulsion;
thirdly, preparing the modified polyvinyl chloride resin:
adding polyvinyl chloride resin into the obtained aqueous emulsion to obtain modified polyvinyl chloride resin;
fourthly, preparing the graphene/polyvinyl chloride composite material:
(1) mixing n-octyl phthalate and a calcium-zinc liquid stabilizer, adding modified polyvinyl chloride resin, stirring to obtain a mixed material A, drying the mixed material A, and taking out for later use;
(2) adding the modified graphene and the processing aid into the mixed material A to be used, and continuously stirring to obtain a mixed material B;
(3) and adding the obtained mixed material B into an open mill for mixing to obtain the graphene/polyvinyl chloride composite material.
2. The preparation method of the graphene/polyvinyl chloride composite material according to claim 1, wherein the preparation of the modified graphene comprises the following steps: in the step (1), the nitrate is sodium nitrate; the mass volume ratio of the nitrate to the sulfurous acid is 0.02-0.025 g/mL; the mass ratio of the nitrate to the graphene is 1: (1-3).
3. The preparation method of the graphene/polyvinyl chloride composite material according to claim 1, wherein the preparation of the modified graphene comprises the following steps: in the step (2), the oxidant is potassium permanganate; under the condition of 35-45 ℃ water bath, adding potassium permanganate into the mixed solution A, magnetically stirring and reacting for 2-5 hours, adding deionized water after reaction, heating to 90-100 ℃, preserving heat for 10-20 minutes, and then stopping reaction; the mass ratio of the potassium permanganate to the graphene is (2-4): 1; the mass volume ratio of the potassium permanganate to the deionized water is 0.05-0.1 g/mL.
4. The preparation method of the graphene/polyvinyl chloride composite material according to claim 1, wherein the preparation of the modified graphene comprises the following steps: after the reaction in the step (3) is ended, adding hydrogen peroxide into a reaction system, stirring, filtering while the reaction system is hot, washing filter residues with hydrochloric acid, washing the filter residues with deionized water to be neutral, and drying the filter residues for 1-3 hours at the temperature of 60-70 ℃ to obtain modified graphene; the volume ratio of the hydrogen peroxide to the sulfurous acid is 1: (8-10).
5. The preparation method of the graphene/polyvinyl chloride composite material according to claim 1, wherein the preparation of the aqueous emulsion comprises the following steps: adding polyvinyl alcohol with sulfydryl at the tail end into deionized water, heating to 85-95 ℃ for dissolution, and then adjusting the pH to 2-3 by using sulfuric acid to obtain a mixed solution B; the mass-volume ratio of the polyvinyl alcohol with the mercapto group at the tail end to the deionized water is 1-5 g/mL; the polyvinyl alcohol with the mercapto group at the end has the polymerization degree of 500, the saponification degree of 88 percent and the mercapto group content of 3.2 multiplied by 10-5mol/g。
6. The preparation method of the graphene/polyvinyl chloride composite material according to claim 1, wherein the preparation of the aqueous emulsion comprises the following steps: the mass ratio of the acrylate to the polyvinyl alcohol with the mercapto group at the tail end in the step (2) is 14: 1; the heating temperature is 60-70 ℃; the volume ratio of the potassium bromide solution to the mixed solution B is 1: (40-50); the mass fraction of potassium bromide in the potassium bromide solution is 2-5%; the reaction time is 2-5 hours.
7. The preparation method of the graphene/polyvinyl chloride composite material according to claim 1, characterized by comprising the following steps: the mass ratio of the n-octyl phthalate, the calcium-zinc liquid stabilizer and the modified polyvinyl chloride resin in the step (1) is 1: 1: 3; the drying temperature is 80-90 ℃, and the drying time is 1-3 hours.
8. The preparation method of the graphene/polyvinyl chloride composite material according to claim 1, characterized by comprising the following steps: in the step (2), the mass ratio of the modified graphene to the processing aid is 1: (2-5); the mass of the modified graphene in the mixed material B accounts for 1-2%.
9. The method for preparing a graphene/polyvinyl chloride composite material according to claim 8, wherein the processing aid is any one of a quaternary ammonium salt cationic active agent, a methacrylate polymer cationic active agent, a methacrylate amide polymer cationic active agent, a fatty amide and a mixture of silver sulfide.
10. The preparation method of the graphene/polyvinyl chloride composite material according to claim 1, characterized by comprising the following steps: the mixing time in the step (3) is 5-10 minutes; the temperature during mixing is 160-180 ℃.
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