CN110628119A - Modified graphene composite polyethylene material and preparation method thereof - Google Patents
Modified graphene composite polyethylene material and preparation method thereof Download PDFInfo
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Abstract
The invention provides a modified graphene composite polyethylene material which comprises the following components in parts by weight: 75-100 parts of polyethylene, 0.5-2 parts of graphene, 1-4 parts of a coupling agent, 4-10 parts of a compatilizer, 0.8-2 parts of a dispersing agent, 2-5 parts of a flocculating agent and 3-5 parts of a stabilizing agent. Compared with the prior art, the preparation method adopts the graphene as the antistatic agent and the reinforcing agent, the graphene is organically modified through the coupling agent, the maleic anhydride grafted EVA is adopted as the toughening compatilizer to form an antistatic toughening reinforcing system of the polyethylene material, and finally the polyethylene material obtains stable physical and chemical properties through the flocculating agent and the stabilizing agent.
Description
Technical Field
The invention relates to a high polymer material and a preparation method thereof, in particular to a modified graphene composite polyethylene material and a preparation method thereof.
Background
The polyethylene material has the advantages of excellent mechanical property and processability, and good comprehensive properties such as corrosion resistance, insulativity, sanitation, barrier property and the like, so that the polyethylene material is widely applied to the fields of industry, agriculture, medicine, sanitation, daily necessities and the like.
Since polyethylene is an insulating material and is a poor electrical conductor, it is a source of electrostatic accumulation and electrostatic damage. Therefore, the polyethylene material is easy to generate and accumulate static electricity under the conditions of friction, extrusion and the like, the static voltage can reach 1000-2000V, static induction, electric shock and product production obstacles can be caused, even fire and explosion accidents can be caused in serious conditions, and the production and use safety is directly influenced. Therefore, antistatic treatment is required to be carried out on polyethylene materials applied to printing workshops, computer rooms, electronic component maintenance rooms, petroleum, natural gas and some flammable and explosive production scenes.
At present, polyethylene is modified mainly by adding antistatic agent to improve its antistatic performance. Specific antistatic agents are various, and graphite, carbon black, amines, glycerol monostearyl ester compounds and the like are commonly used. The amine has stronger adhesive force to polyethylene and good antistatic property; however, due to the corrosiveness of amine structures, the application of amine structures gradually exits the market along with the increasingly strict requirements of electronic packaging materials in recent years. After the glycerol monostearyl ester compound is doped into polyethylene, because of incompatibility with the polyethylene, the glycerol monostearyl ester compound can migrate to the surface of the polyethylene to form a uniform layer of hydrophilic substance, absorb moisture in the air to form a conductive channel, so as to improve the conductivity of the surface of the polyethylene; but has the problem of serious moisture absorption and can not meet the requirements of some occasions. Graphite and carbon black are carbon-series conductive materials with the widest application range at present, have stable and permanent conductivity, and have wide sources, low cost and simple use; but the disadvantages are that the compatibility of graphite and carbon black with polyethylene is poor, the polyethylene conductivity is easy to be low, and the phenomena of yarn breakage and the like occur in the spinning process. The consumption of the conductive carbon black and the graphite in the modified polyethylene is up to 5-20%, and the surface resistance of the modified polyethylene can reach 10%9The mechanical properties of the alloy are greatly reduced below omega.
The appearance of graphene brings hope to the solution of the problem, and the graphene is the nano material which is the most conductive (the resistivity is 10-6 omega-cm and is slightly lower than the most conductive metal silver) and the most conductive (the thermal conductivity reaches 5000W/m-k at room temperature and exceeds the diamond with the highest thermal conductivity known at present) known in the world at present. Due to the excellent properties of the graphene, the graphene is very likely to be a material for improving the antistatic property of the polyethylene. The process for directly compounding the graphene and the polyethylene base material is simple in step, but the combination of the surface of the graphene and the polyethylene is poor, and the surface atoms of the graphene have high surface energy and surface combination energy, so that the graphene is poor in dispersibility and is easy to form large aggregates, and the graphene is easy to agglomerate when being used as a reinforcing material of the polyethylene base body, so that the dispersion degree of the graphene in the polyethylene base body is low, the application performance of the composite material is influenced, and the stable modified polyethylene material with good antistatic performance is not easy to obtain.
Disclosure of Invention
Based on the above, in order to overcome the defects and shortcomings of the prior art, the invention provides a modified graphene composite polyethylene material which has stable physical properties and good antistatic performance.
The modified graphene composite polyethylene material comprises the following components in parts by weight: 75-100 parts of polyethylene, 0.5-2 parts of graphene, 1-4 parts of a coupling agent, 4-10 parts of a compatilizer, 0.8-2 parts of a dispersing agent, 2-5 parts of a flocculating agent and 3-5 parts of a stabilizing agent.
Compared with the prior art, the molecular chains of the coupling agent and the compatilizer are introduced into the surface of the graphene, so that the lipophilicity of the surface of the graphene is greatly improved, and the compatibility of the graphene and a polyethylene matrix is improved, so that the interface bonding force of the graphene and polyethylene is increased, and the mechanical strength of the modified graphene composite polyethylene material is improved; and adding a flocculating agent and a stabilizing agent into the blend to obtain the blend which is stable, good in compatibility, free of migration and good in dispersibility, so that the graphene is uniformly dispersed into the polyethylene to form a stable rib or mesh passage for conducting and resisting static electricity. Through the graphene modified polyethylene material, the mechanical properties such as tensile strength, bending strength and bending modulus and the like, and the thermal properties such as thermal deformation resistance, heat conduction and electric conduction of the final product modified graphene composite polyethylene material can be effectively improved. The surface resistance of the modified graphene composite polyethylene material can be reduced to 10 by only 2% of the graphene7Omega. According to the invention, the graphene is adopted as the antistatic modifier, the specific surface area of the graphene is large, the contact surface of the graphene and polyethylene is large, compared with other materials, the excellent antistatic effect can be obtained by using a small amount of graphene, and the blocking effect of high content on the arrangement of polyethylene molecular chains can be avoided.
Further, the flocculant is selected from at least one of polymeric aluminum ferric sulfate, polyamine, sodium hydroxide or polyethylene oxide. The polymeric aluminum ferric sulfate has high basicity, high polymerization degree, dense molecular chain network and large structure, and has the effect of promoting polymer aggregation and precipitation; polyamines are a class of compounds containing two or more amino groups and have the effect of promoting the growth of polymer structures; the sodium hydroxide also has the function of accelerating the reaction rate by being similar to the catalyst, so that the polymer structure tends to be stable; the polyethylene oxide has flocculation effect on high molecular polymer and good compatibility with other resin. The flocculant can neutralize the charges on the surface of the polymer through grafting or reaction, so that the Z potential of the polymer is reduced, the repulsive energy is reduced, and finally the modified graphene composite polyethylene material has stable physical and chemical properties.
Further, the compatilizer is maleic anhydride grafted EVA with the grafting rate of 1.8-2.5%. Maleic anhydride is an important intermediate for the production of copolymers; the grafted EVA is an ethylene-vinyl acetate copolymer, and has the advantages of good buffering, shock resistance, heat insulation, moisture resistance, chemical corrosion resistance, no toxicity, no water absorption and the like. The modified polyethylene material adopts maleic anhydride grafted EVA as a compatilizer, and introduces a strong-polarity maleic anhydride side group on an EVA molecular main chain to form a bridge for improving the adhesion and compatibility of the organic modified graphene and polyethylene; the dispersibility of the organic modified graphene in the polyethylene material is improved, and the impact resistance of the modified graphene composite polyethylene material can be improved. When the grafting rate of maleic anhydride grafted EVA is too low, the adhesion of the organic modified graphene and the modified polyethylene is not facilitated; when the grafting ratio of maleic anhydride grafted EVA is too high, the original mechanical property and the electric and heat conductivity of the organic modified graphene are reduced.
Further, the graphene needs to be subjected to organic modification treatment, and the specific surface area of the obtained organic modified graphene is 350-400 m2Per g, particle diameter D50The content of carbon is not less than 98%, the content of oxygen is less than 1.0%, and the content of sulfur is less than 0.1%. The specific surface area of the organic modified graphene used in the invention is not too high, otherwise agglomeration is easy to occur; the oxygen mass fraction and the sulfur mass fraction are not too high, otherwise the modified graphene is influencedThe polyethylene material has mechanical property and electric and heat conduction effects.
Further, the polyethylene is linear low density polyethylene or high density polyethylene. Linear low density polyethylene (LLDPE for short, density of 0.918-0.935 g/cm)3) And high density polyethylene (HDPE for short in English) with density of 0.918-0.935 g/cm3) Are all non-toxic, tasteless and odorless milky white particles. And low density polyethylene (abbreviated as LDPE) with the density of 0.910-0.925 g/cm3) Compared with LLDPE, the LLDPE has higher softening temperature and melting temperature, has the advantages of high strength, good toughness, high rigidity, good heat resistance and cold resistance, and also has good environmental stress crack resistance, impact strength, tear strength and other properties; compared with LDPE, HDPE has the advantages of excellent mechanical property and processability, and good comprehensive properties such as corrosion resistance, insulation property, sanitation property, barrier property and the like. LLDPE and HDPE can also resist acid, alkali, organic solvent and the like, so that LLDPE and HDPE are widely used in the fields of industry, agriculture, medicine, sanitation and the like. According to the invention, the LLDPE and the HDPE are subjected to composite modification treatment through the graphene modified by the coupling agent, the flocculating agent and the stabilizing agent, so that the physical stability and the antistatic property of the final product modified graphene composite polyethylene material can be greatly improved.
Further, the coupling agent is selected from at least one of silane coupling agents or titanate coupling agents; the dispersing agent is selected from at least one of polyethylene wax, oxidized polyethylene wax, plasticized polyethylene wax, poly alpha-methyl styrene or white oil; the stabilizer is at least one selected from butyl hydroxy anisole, dibutyl hydroxy toluene, tert-butyl hydroquinone, N-isopropyl-N' -phenyl p-phenylenediamine or 2, 6-di-tert-butyl-p-cresol. The coupling agent has the main function of improving the connectivity of a graphene molecular chain so as to improve the dispersibility of graphene in polyethylene. The dispersing agent is a surfactant which has two opposite properties of lipophilicity and hydrophilicity in a molecule, is beneficial to uniformly dispersing graphene in a liquid solvent, and can prevent the graphene from settling and condensing. Stabilizers can slow down chemical reactions, maintain chemical equilibrium, reduce polymer surface tension, prevent the effects of light, thermal or oxidative decomposition of the polymer.
The invention also provides a preparation method of the modified graphene composite polyethylene material, which is low in production cost and simple in production process, and comprises the following steps:
s1: placing graphene and a coupling agent in an organic solvent for refluxing for 80-120 min, and then removing the organic solvent to obtain organic modified graphene;
s2: dispersing organic modified graphene in deionized water, and uniformly mixing to obtain an organic modified graphene dispersion liquid;
s3: mixing the organic modified graphene dispersion liquid, polyethylene, a compatilizer and a dispersing agent, and discharging to obtain a modified graphene composite polyethylene mixed material;
s4: melting the modified graphene composite polyethylene mixed material obtained in the step S3, sequentially adding a flocculating agent and a stabilizing agent, uniformly mixing, and extruding at the temperature of 160-210 ℃ to obtain a modified graphene composite polyethylene pipe;
s5: and (5) cooling, pelletizing and drying the modified graphene composite polyethylene pipe obtained in the step (S4) to obtain the modified graphene composite polyethylene material.
Compared with the prior art, the method has the advantages that on one hand, the graphene is organically modified through the coupling agent, so that the graphene contains a large number of active functional groups such as carboxyl and hydroxyl, and the like, and a molecular chain of the compatilizer is introduced into the surface of the graphene by utilizing the active functional groups, so that the lipophilicity of the surface of the graphene is greatly improved; on the other hand, the compatilizer is used as a bridge to improve the connectivity between the organic modified graphene and the polyethylene, and is beneficial to improving the dispersibility of the organic modified graphene in the polyethylene material, so that the interface bonding force between the organic modified graphene and the polyethylene is increased, and the mechanical strength of the modified graphene composite polyethylene material is improved. Then, the modified graphene composite polyethylene mixed material is controlled to be melted at the temperature of 160-210 ℃, so that graphene is promoted to be uniformly dispersed into polyethylene; then adding a flocculating agent and a stabilizing agent in sequence to obtain a stable, good-compatibility, non-migration and good-dispersibility blend; the modified graphene composite polyethylene material forms a stable rib or net-shaped passage for conducting and resisting static electricity. The mechanical properties such as tensile strength, bending strength and bending modulus of the modified graphene composite polyethylene, and the electrical properties such as thermal deformation resistance, heat conduction and electric conduction are further effectively improved. The preparation method of the modified graphene composite polyethylene material is simple and flexible, has low production cost, obvious antistatic capability and enhanced conductive effect and obviously improved mechanical property, and can meet the production of products with specific application requirements.
Further, in the step S1, the mass ratio of the coupling agent to the graphene is 1:1 to 2: 1. When the dosage of the coupling agent is too small, the molecular chain of the coupling agent is not favorably grafted on the surface of the organic modified graphene, so that the lipophilic effect of the organic modified graphene is influenced; when the using amount of the coupling agent is too much, the lipophilic effect of the organic modified graphene cannot be obviously increased, and materials are wasted.
Further, in the step S2, the concentration of the organic modified graphene dispersion liquid is 0.3 to 0.8 g/L.
Further, in the step S1, the organic solvent is an alcohol organic solvent selected from at least one of methanol, ethanol, and isopropanol.
Detailed Description
The modified graphene composite polyethylene material comprises the following components in parts by weight: 75-100 parts of polyethylene, 0.5-2 parts of graphene, 1-4 parts of a coupling agent, 4-10 parts of a compatilizer, 0.8-2 parts of a dispersing agent, 2-5 parts of a flocculating agent and 3-5 parts of a stabilizing agent.
Preferably, the polyethylene is a linear low density polyethylene or a high density polyethylene. The graphene needs to be subjected to organic modification treatment, and the specific surface area of the obtained organic modified graphene is 350-400 m2Per g, particle diameter D50The content of carbon is not less than 98%, the content of oxygen is less than 1.0%, and the content of sulfur is less than 0.1%.
Preferably, the coupling agent is selected from at least one of silane coupling agents or titanate coupling agents; the dispersing agent is selected from at least one of polyethylene wax, oxidized polyethylene wax, plasticized polyethylene wax, poly alpha-methyl styrene or white oil; the stabilizer is at least one selected from butyl hydroxy anisole, dibutyl hydroxy toluene, tert-butyl hydroquinone, N-isopropyl-N' -phenyl p-phenylenediamine or 2, 6-di-tert-butyl-p-cresol. The flocculant is at least one of polymeric aluminum ferric sulfate, polyamine, sodium hydroxide or polyethylene oxide.
Preferably, the compatilizer is maleic anhydride grafted EVA with the grafting rate of 1.8-2.5%.
The invention also provides a preparation method of the modified graphene composite polyethylene material, which comprises the following steps:
s1: placing graphene and a coupling agent in an organic solvent for refluxing for 80-120 min, and then removing the organic solvent to obtain organic modified graphene;
preferably, the mass ratio of the coupling agent to the graphene is 1: 1-2: 1. The organic solvent is an alcohol organic solvent and is selected from at least one of methanol, ethanol or isopropanol.
S2: dispersing organic modified graphene in deionized water, and uniformly mixing to obtain an organic modified graphene dispersion liquid;
preferably, the concentration of the organic modified graphene dispersion liquid is 0.3-0.8 g/L.
S3: mixing the organic modified graphene dispersion liquid, polyethylene, a compatilizer and a dispersing agent, and discharging to obtain a modified graphene composite polyethylene mixed material;
s4: melting the modified graphene composite polyethylene mixed material obtained in the step S3, sequentially adding a flocculating agent and a stabilizing agent, uniformly mixing, and extruding at the temperature of 160-210 ℃ to obtain a modified graphene composite polyethylene pipe;
preferably, a twin-screw extruder is used for the extrusion operation, and the temperature of the extrusion process is set in sections: the length of a machine barrel area of the double-screw extruder is divided into 9 sections, and the temperature of each section is as follows: the 1 st section is 165 +/-5 ℃, the 2 nd section is 165 +/-5 ℃, the 3 rd section is 175 +/-5 ℃, the 4 th section is 175 +/-5 ℃, the 5 th section is 185 +/-5 ℃, the 6 th section is 185 +/-5 ℃, the 7 th section is 195 +/-5 ℃, the 8 th section is 205 +/-5 ℃ and the 9 th section is 205 +/-5 ℃; the temperature in the die area of the extruder was 195. + -. 5 ℃.
S5: and (5) cooling, pelletizing and drying the modified graphene composite polyethylene pipe obtained in the step (S4) to obtain the modified graphene composite polyethylene material.
The technical solution of the present invention will be described in detail below with reference to specific examples.
Example 1:
embodiment 1 provides a modified graphene composite polyethylene material, which is prepared from the following components in parts by weight:
75 parts of linear low-density polyethylene, 0.5 part of graphene, 0.5 part of silane coupling agent, 4 parts of maleic anhydride grafted EVA, 0.8 part of polyethylene wax, 2 parts of polymeric aluminum ferric oxide, and 3 parts of butyl hydroxy anisole and tert-butyl hydroquinone.
The preparation method of the modified graphene composite polyethylene material comprises the following steps:
s1: placing graphene and a silane coupling agent in methanol at a mass ratio of 1:1 for refluxing for 80min, and then removing an organic solvent to obtain organic modified graphene;
s2: dispersing organic modified graphene in deionized water, and uniformly mixing to obtain an organic modified graphene dispersion liquid;
s3: mixing the organic modified graphene dispersion liquid, linear low-density polyethylene, maleic anhydride grafted EVA and polyethylene wax, and discharging to obtain a modified graphene composite polyethylene mixed material;
s4: melting the modified graphene composite polyethylene mixed material obtained in the step S3 at 160-190 ℃, sequentially adding polymeric aluminum ferric sulfate, butyl hydroxy anisole and tert-butyl hydroquinone, uniformly mixing, and extruding to obtain a modified graphene composite polyethylene pipe;
the modified graphene composite polyethylene mixed material is fed into a double-screw extruder to be extruded, the length of a machine barrel area of the double-screw extruder is equally divided into 9 sections, and the temperature of each section is as follows: t is1＝160℃，T2＝160℃，T3＝170℃，T4＝170℃，T5＝180℃，T6＝180℃，T7＝190℃，T8＝200℃，T9The temperature is 200 ℃; the temperature in the die area of the twin-screw extruder was: t isDie＝190℃。
S5: and (5) allowing the modified graphene composite polyethylene pipe obtained in the step (S4) to enter a water tank through a die head for cooling, then granulating through a granulator, and finally drying to obtain the modified graphene composite polyethylene material.
Examples 2 to 3:
the preparation steps of the modified graphene composite polyethylene materials in the embodiments 2 to 3 are the same as those of the modified graphene composite polyethylene material in the embodiment 1, and the differences are that the weight ratio and the operation parameters of the components are different, which is detailed in table 1.
TABLE 1 summary of the weight ratios and operating parameters of the components of examples 1-3
EXAMPLES 1 to 3 comparison of Performance
The properties of the modified graphene composite polyethylene materials prepared in examples 1 to 3 are shown in table 2.
Table 2 comparison of properties of modified graphene composite polyethylene materials prepared in examples 1 to 3
| Testing performance | Example 1 | Example 2 | Example 3 |
| Tensile strength/MPa | 23.16 | 23.84 | 24.20 |
| Cantilever beam notch impact strength/kJ.m-2 | 2.83 | 2.84 | 2.95 |
| Flexural Strength/MPa | 18.52 | 19.21 | 18.94 |
| Flexural modulus/MPa | 592.76 | 623.57 | 546.70 |
| Heat distortion temperature/. degree.C | 77.5 | 77.8 | 76.9 |
| Thermal conductivity/W (m.K)-1 | 0.503 | 0.516 | 0.531 |
| Surface resistance/omega | 4.23×107 | 4.05×107 | 3.93×107 |
| Stability of | Superior food | Superior food | Superior food |
| Service life | Is longer | Is longer | Is longer |
As can be seen from table 2, as the reflux time, the mass ratio of the coupling agent to the graphene, and the extrusion temperature increase in step S3 in step S1; the prepared modified graphene composite polyethylene material has better tensile strength, cantilever beam notch impact strength, bending modulus and heat conductivity; the higher the heat distortion temperature and the lower the surface resistance.
Comparative examples 4 to 7:
the preparation steps and the operation parameters of the modified graphene composite polyethylene materials in comparative examples 4-7 and example 2 are the same, and the difference is that the materials and the weight ratio of each component are different. See table 3.
Table 3 shows the material and weight ratio of each component of the modified graphene composite polyethylene material described in examples 2, 4 to 7
The modified graphene composite polyethylene materials prepared in the embodiments 2, 4 to 7 were subjected to injection molding of a standard sample by an injection molding machine, and the force performance test was performed on the standard sample according to the national standard, and the test results are shown in table 4.
As can be seen from table 3, comparative example 4 has no maleic anhydride grafted EVA added; as can be seen from the test results of the modified graphene composite polyethylene in table 4, compared with example 2, the modified graphene composite polyethylene material prepared in comparative example 4 has a slightly reduced izod notched impact strength, and the other comprehensive mechanical properties, such as tensile strength, bending modulus, thermal deformation temperature, thermal conductivity, and electrical conductivity, are all significantly reduced.
Since the coupling agent is not added in comparative example 5 to organically modify the graphene, that is, the graphene is used instead of the organically modified graphene modified polyethylene material, compared with example 2, the modified graphene composite polyethylene material prepared in comparative example 5 has equivalent notched izod impact strength, and the other comprehensive mechanical properties, such as tensile strength, bending modulus, thermal deformation temperature, thermal conductivity, electrical conductivity, and the like, are also significantly reduced.
By combining table 3 and table 4, it can be seen that, when comparative example 4 (without adding a compatibilizer) and comparative example 5 (without adding a coupling agent to modify graphene), the compatibilizer has a greater influence on the comprehensive mechanical properties, thermal conductivity and electrical conductivity of the finally prepared modified graphene composite polyethylene material than when the coupling agent modifies graphene. That is, when the compatibilizer is not added in comparative example 4, the combination of mechanical property parameters (e.g., tensile strength, flexural modulus, heat distortion temperature) and electrical conductivity parameters (thermal conductivity and surface resistance) are reduced to a greater extent than those of comparative example 5.
Table 4 test results of modified graphene composite polyethylene prepared according to the weight ratio of each component of examples 2, 4 to 7
As can be seen from table 3, comparative example 6 and comparative example 7 have no flocculant and stabilizer added, respectively; as can be seen from the test results of the modified graphene composite polyethylene in table 4, the stability and the service life of the modified graphene composite polyethylene materials prepared in comparative examples 6 and 7 are significantly reduced compared to those of example 2. Furthermore, as can be seen from the comparative analysis between comparative example 6 (without adding a flocculant) and comparative example 7 (without adding a stabilizer), the flocculant has a greater influence on the stability and the service life of the finally prepared modified graphene composite polyethylene material than the stabilizer. That is, when comparative example 6 was not added with a flocculant, the stability and service life of the product were reduced to a greater extent than those of comparative example 7.
Compared with the prior art, the modified graphene composite polyethylene material and the preparation method thereof have the following characteristics:
(1) on one hand, the graphene is organically modified by the coupling agent, so that the graphene contains a large number of active functional groups such as carboxyl, hydroxyl and the like, and a molecular chain of a compatilizer is introduced to the surface of the graphene by utilizing the active functional groups, so that the lipophilicity of the surface of the graphene is greatly improved; on the other hand, the compatilizer is used as a bridge to improve the connectivity between the organic modified graphene and the polyethylene, and is beneficial to improving the dispersibility of the organic modified graphene in the polyethylene material, so that the interface bonding force between the organic modified graphene and the polyethylene is increased, and the mechanical strength of the modified graphene composite polyethylene material is improved.
(2) The modified graphene composite polyethylene mixed material is controlled to be melted at the temperature of 160-210 ℃, so that graphene is promoted to be uniformly dispersed into polyethylene; then adding a flocculating agent and a stabilizing agent in sequence to obtain a stable, good-compatibility, non-migration and good-dispersibility blend; therefore, the modified graphene composite polyethylene material forms a stable rib or net-shaped path for conducting and resisting static electricity.
(3) The preparation method of the modified graphene composite polyethylene material is simple and flexible, and can meet the production requirements of specific applications. Through the organic modified graphene composite polyethylene material, the mechanical properties such as tensile strength, bending strength and bending modulus and the like, and the thermal properties such as thermal deformation resistance, heat conduction and electric conduction and the like of the final product modified graphene composite polyethylene material can be effectively improved.
(4) Compared with the traditional conductive carbon black and graphite, the invention only needs 2% of the graphene dosage, and the modified graphene composite polyethylene material can be preparedSurface resistance as low as 107Ω。
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention.
Claims (10)
1. A modified graphene composite polyethylene material is characterized in that: the paint comprises the following components in parts by weight:
2. the modified graphene composite polyethylene material according to claim 1, wherein: the flocculant is at least one of polymeric aluminum ferric sulfate, polyamine, sodium hydroxide or polyethylene oxide.
3. The modified graphene composite polyethylene material according to claim 2, wherein: the compatilizer is maleic anhydride grafted EVA with the grafting rate of 1.8-2.5%.
4. The modified graphene composite polyethylene material according to claim 3, wherein: the graphene needs to be subjected to organic modification treatment, and the specific surface area of the obtained organic modified graphene is 350-400 m2Per g, particle diameter D50The content of carbon is not less than 98%, the content of oxygen is less than 1.0%, and the content of sulfur is less than 0.1%.
5. The modified graphene composite polyethylene material according to claim 4, wherein: the polyethylene is linear low density polyethylene or high density polyethylene.
6. The modified graphene composite polyethylene material according to claim 5, wherein: the coupling agent is selected from at least one of silane coupling agents or titanate coupling agents; the dispersing agent is selected from at least one of polyethylene wax, oxidized polyethylene wax, plasticized polyethylene wax, poly alpha-methyl styrene or white oil; the stabilizer is at least one selected from butyl hydroxy anisole, dibutyl hydroxy toluene, tert-butyl hydroquinone, N-isopropyl-N' -phenyl p-phenylenediamine or 2, 6-di-tert-butyl-p-cresol.
7. A preparation method for preparing the modified graphene composite polyethylene material of any one of claims 1 to 6 is characterized by comprising the following steps:
s1: placing graphene and a coupling agent in an organic solvent for refluxing for 80-120 min, and then removing the organic solvent to obtain organic modified graphene;
s2: dispersing organic modified graphene in deionized water, and uniformly mixing to obtain an organic modified graphene dispersion liquid;
s3: mixing the organic modified graphene dispersion liquid, polyethylene, a compatilizer and a dispersing agent, and discharging to obtain a modified graphene composite polyethylene mixed material;
s4: melting the modified graphene composite polyethylene mixed material obtained in the step S3 at 160-210 ℃, sequentially adding a flocculating agent and a stabilizing agent, uniformly mixing, and extruding to obtain a modified graphene composite polyethylene pipe;
s5: and (5) cooling, pelletizing and drying the modified graphene composite polyethylene pipe obtained in the step (S4) to obtain the modified graphene composite polyethylene material.
8. The method for preparing the modified graphene composite polyethylene material according to claim 7, wherein the method comprises the following steps: in the step S1, the mass ratio of the coupling agent to the graphene is 1: 1-2: 1.
9. The method for preparing the modified graphene composite polyethylene material according to claim 8, wherein the method comprises the following steps: in the step S2, the concentration of the organic modified graphene dispersion liquid is 0.3-0.8 g/L.
10. The method for preparing the modified graphene composite polyethylene material according to claim 9, wherein the method comprises the following steps: in step S1, the organic solvent is an alcohol organic solvent selected from at least one of methanol, ethanol, and isopropanol.
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