CN113444310A - Conductive polyolefin composite material and preparation method thereof - Google Patents
Conductive polyolefin composite material and preparation method thereof Download PDFInfo
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Abstract
The application relates to a conductive polyolefin composite material and a preparation method thereof. The conductive polyolefin composite material comprises: ferric trichloride modified graphite, and polyolefin resin; wherein the amount of the ferric trichloride modified graphite is 2.0-20.0 mass% of the polyolefin resin. By modifying graphite, modified graphite which is easier to strip and has good conductivity is obtained, and the compatibility of the graphite material and polyolefin resin is further improved; the modified graphite and the polyolefin resin are ground and compounded, so that the graphite material is easier to strip, the surfaces of polyolefin resin particles are wrapped, a conductive network is formed, and the carbon/polyolefin composite material with good conductivity is obtained.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a conductive polyolefin composite material and a preparation method thereof.
Background
The material is characterized by abundant raw materials, low price, easy processing and forming, good chemical resistance, good water resistance, good mechanical strength and the like, and is a high-quality material for films, pipes, plates, various formed products, wires and cables and the like. Polyolefin resins are widely used in the fields of agriculture, packaging, electronics, electrical, automotive, machinery, daily sundry goods, and the like. However, because the polyolefin resin has good insulating property, it also limits its application in the electrical industry, especially in the field of conductive materials, so the development and application of conductive polyolefin resin has become a very active research field in the world in recent years, and it has been developed from the initial pure laboratory research to the application research stage, and is widely applied in the fields of semiconductors, antistatic materials, conductive materials, etc.
Conductive polyolefins can be classified into structural types and filled types. The structural conductive polyolefin is a high polymer or a material which has conductivity after being doped, while the filling type conductive polyolefin is a material which has no conductivity but becomes conductive by adding a conductive filler (conductive filler), and is prepared by mixing and granulating a plastic with better electrical insulating property, a filler with excellent conductivity and other additives, and adopting the methods of injection molding, compression molding, extrusion molding and the like.
The conductive filler is classified into carbon black filled type, graphite filled type, carbon fiber filled type, carbon nanotube filled type, and metal matrix conductive network filled type. Among them, carbon black-filled conductive polymers are most common. At present, research and development in the field of carbon black filled conductive plastics mainly focus on the aspects of carbon black modification, novel conductive carbon black development, nano carbon black application and the like. With the development of nano materials, the preparation of conductive composite materials by compounding nano carbon materials such as nano graphite, carbon nanotubes, graphene and the like with matrix materials becomes a new trend in research and development of filled conductive polymer materials in recent years.
The preparation method for compounding carbon materials such as graphite and the like with polyolefin materials mainly comprises two methods: physical blending methods and in situ polymerization methods. The physical blending method can be divided into a solution blending method and a melt blending method. The modified carbon material is well compatible with a matrix by mechanical means (such as shearing force, magnetic stirring, ultrasound and the like) and fully utilizing the affinity or steric hindrance effect between the modified carbon material and a polymer. The blending method is simple and easy to implement, and is convenient for controlling factors such as volume fraction of the carbon material in the polyolefin matrix. In the in-situ polymerization method, an olefin polymerization catalyst is loaded on a carbon material, and the composite material is prepared by in-situ polymerization.
Chinese patent CN 108117684A prepares polyolefin conductive composite material from high-density polyethylene, polypropylene, modified carbon nanotube, graphene and other carbon materials in the presence of lubricant, compatilizer and antioxidant, and the volume resistivity of the composite material reaches 102 omega cm. According to the process, cobalt chloride, nickel chloride, sodium borohydride and the like are adopted to modify a carbon material, the process flow is complex, and the prepared composite material of polyethylene, polypropylene and carbon is used for eliminating the electrostatic influence of a polyolefin material.
Chinese patent CN 109535529A4 mixes polyethylene, ethylene propylene copolymer, conductive carbon black and graphene, and then carries out melt extrusion to obtain conductive polyethylene, which is used for chemical raw material barrel inner containers to reduce static electricity and pollution. The surface resistivity of the conductive polyethylene can reach 103 omega cm, and the surface resistivity of the prepared liner section can reach 105 omega cm.
Chinese patent 109192539A adopts mechanochemical polymerization to prepare conductive polymer electrode material, and the invention prepares graphene conductive polymer composite material as high-performance super capacitor electrode material by in-situ polymerization of graphene and conductive polymer.
Chinese patent CN1252416A provides a method for preparing conductive polyolefin composite material by filling method, which adopts pretreated high-dispersibility conductive filler graphite or superconducting carbon black activated by ziegler-natta catalyst, then olefin monomer polymerization is carried out on the surface to prepare conductive filler/polymer composite material with adjustable conductive range. The composite material comprises 5-90 wt% of conductive filler and 10-95 wt% of polyolefin polymer. But the content of the conductive filler is high, so that the comprehensive performance of the resin is influenced.
Disclosure of Invention
The invention aims to provide a conductive polyolefin composite material and a preparation method thereof.
The present application provides an electrically conductive polyolefin composite comprising:
iron trichloride modified graphite, and
a polyolefin resin;
wherein the amount of the ferric trichloride modified graphite is 2.0-20.0 mass% of the polyolefin resin.
In one embodiment, the volume resistivity of the conductive polyolefin composite is 1 to 10000 Ω · cm.
In one embodiment, the carbon content of the iron trichloride modified graphite is 95.0 to 99.0 mass%, the oxygen content is 0.1 to 5.0 mass%, and the iron content is 0.1 to 3.0 mass%, based on the total mass of the modified graphite.
In one embodiment, the carbon content of the iron trichloride modified graphite is 95.0 to 99.0 mass%, the oxygen content is 0.1 to 2.0 mass%, and the iron content is 0.2 to 2.0 mass%, based on the total mass of the modified graphite.
In one embodiment, the iron trichloride-modified graphite is obtained by:
pretreating graphite at 200-400 ℃ in a vacuum state,
carrying out composite modification on the pretreated graphite and anhydrous ferric trichloride at the temperature of 200-500 ℃ to obtain the ferric trichloride modified graphite.
In one embodiment, the pretreated graphite has an oxygen content of 0.1 to 5.0 mass% and a carbon content of 95.0 to 99.9 mass% based on the total mass of the pretreated graphite.
In one embodiment, the pretreated graphite and the anhydrous ferric chloride are used in amounts such that the carbon content of the ferric chloride modified graphite is 95.0 to 99.0 mass%, the oxygen content is 0.1 to 5.0 mass%, and the iron content is 0.1 to 3.0 mass%, based on the total mass of the modified graphite.
In one embodiment, the graphite is selected from one or more of natural graphite, expanded graphite, flake graphite, and graphite oxide, preferably expanded graphite.
In one embodiment, the polyolefin resin is selected from one or more of Low Density Polyethylene (LDPE), Linear Low Density Polyethylene (LLDPE), High Density Polyethylene (HDPE), Medium Density Polyethylene (MDPE), High Density Polyethylene (HDPE), Ultra High Molecular Weight Polyethylene (UHMWPE), polypropylene (PP), ethylene-propylene copolymers, ethylene-butene copolymers, and ethylene-other olefin copolymers.
In another aspect, the present application provides a method for preparing a conductive polyolefin composite, comprising the steps of:
grinding and compounding the ferric trichloride modified graphite and the polyolefin resin to obtain the conductive polyolefin composite material;
wherein the amount of the ferric trichloride modified graphite is 2.0-20.0% by mass of the polyolefin resin.
In one embodiment, the iron trichloride-modified graphite is obtained by:
pretreating graphite at 200-400 ℃ in a vacuum state,
carrying out composite modification on the pretreated graphite and anhydrous ferric trichloride at the temperature of 200-500 ℃ to obtain the ferric trichloride modified graphite.
In one embodiment, the pretreated graphite has an oxygen content of 0.1 to 5.0 mass% and a carbon content of 95.0 to 99.9 mass% based on the total mass of the pretreated graphite.
In one embodiment, the pretreated graphite and the anhydrous ferric chloride are used in amounts such that the carbon content of the ferric chloride modified graphite is 95.0 to 99.0 mass%, the oxygen content is 0.1 to 5.0 mass%, and the iron content is 0.1 to 3.0 mass%, based on the total mass of the modified graphite.
In one embodiment, the milling is performed in a ball mill.
In one embodiment, in the ball mill, the weight ratio of the stainless steel balls to the polyolefin resin in the ball mill is 2-50: 1, the rotation speed is 150-2000 r/min, and the ball milling time is 30 minutes-12 hours.
The method of the invention has the following advantages:
by modifying graphite, modified graphite which is easier to strip and has good conductivity is obtained, and the compatibility of the graphite material and polyolefin resin is further improved; the modified graphite and the polyolefin resin are ground and compounded, so that the graphite material is easier to strip, the surfaces of polyolefin resin particles are wrapped, a conductive network is formed, and the carbon/polyolefin composite material with good conductivity is obtained.
Drawings
FIG. 1 is an X-ray diffraction pattern (XRD pattern) of the expanded graphite used in example 1 before and after modification;
fig. 2A and 2B show transmission electron micrographs (TEM pictures) of the expanded graphite used in example 1 and the modified expanded graphite, respectively.
Detailed Description
The technical solution of the present invention is further explained below according to specific embodiments. The scope of protection of the invention is not limited to the following examples, which are set forth for illustrative purposes only and are not intended to limit the invention in any way.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In one aspect, the present application provides an electrically conductive polyolefin composite comprising:
ferric trichloride modified graphite, and polyolefin resin.
The conductive polyolefin composite material takes ferric trichloride modified graphite as a conductive medium. The modified graphite which is easier to strip and has good conductivity is obtained by modifying the graphite with ferric trichloride, and the modified graphite and the polyolefin resin are compounded by ball milling to obtain the carbon/polyolefin composite material with good conductivity, wherein the composite material keeps the good performance of the polyolefin resin, has good conductivity and can be applied to conductive, antistatic and electromagnetic shielding products.
In one embodiment, the conductive polyolefin composite of the present application has good electrical conductivity and a volume resistivity of 1.0 to 10000 Ω · cm, preferably 10.0 to 1000 Ω · cm.
In one embodiment, in the conductive polyolefin composite material, the amount of the iron trichloride-modified graphite is 2.0 to 20.0 mass%, preferably 2.0 to 10.0 mass% of the polyolefin resin. The amount of the ferric trichloride modified graphite is important for the conductive polyolefin composite material, and is less than 2.0 mass% of the polyolefin resin, so that the function of the ferric trichloride modified graphite as a conductive medium cannot be embodied, and the conductivity of the obtained composite material is poor. However, if the amount of the iron trichloride-modified graphite is more than 20.0 mass% of the polyolefin resin, mechanical properties of the composite material, such as yield strength and breaking strength of the resin, are significantly reduced.
In one embodiment, the carbon content of the iron trichloride modified graphite is 95.0 to 99.0 mass%, the oxygen content is 0.1 to 5.0 mass%, and the iron content is 0.1 to 3.0 mass%, based on the total mass of the modified graphite. Preferably, the carbon content of the iron trichloride modified graphite is 95.0-99.0 mass%, the oxygen content is 0.1-3.0 mass%, and the iron content is 0.1-2.0 mass%, based on the total mass of the modified graphite. In one embodiment, the carbon content of the iron trichloride modified graphite is 98.0 to 99.8 mass%, the oxygen content is 0.1 to 5.0 mass%, and the iron content is 0.1 to 3.0 mass%, based on the total mass of the modified graphite. In another embodiment, the carbon content of the iron trichloride modified graphite is 95.0 to 99.0 mass%, the oxygen content is 0.1 to 5.0 mass%, and the iron content is 0.1 to 2.0 mass%, based on the total mass of the modified graphite.
In one embodiment, the iron trichloride modified graphite of the present application can be obtained by:
pretreating graphite at 200-400 ℃ in a vacuum state,
carrying out composite modification on the pretreated graphite and anhydrous ferric trichloride at the temperature of 200-500 ℃ to obtain the ferric trichloride modified graphite.
In the process of preparing the ferric trichloride modified graphite, the graphite is pretreated at the temperature of 200-400 ℃ in a vacuum state, so that the influence of impurities and bound water on the surface of the graphite can be removed. The pretreated graphite contains 0.1 to 5.0 mass% of oxygen and 95.0 to 99.9 mass% of carbon, and can be determined by photoelectron spectroscopy.
In the process of preparing the ferric trichloride modified graphite, the pretreated graphite and anhydrous ferric trichloride can be compositely modified in a high-temperature high-pressure reaction kettle, the vacuum degree is reduced to be below 0.09MPa, the reaction temperature is 200-500 ℃, and the reaction time is 0.5-4 h. The properties of the resulting iron trichloride-modified graphite can be controlled by adjusting the amounts of the pretreated graphite and the anhydrous iron trichloride. In one embodiment, the pretreated graphite and the anhydrous ferric chloride are used in amounts such that the carbon content of the ferric chloride modified graphite is 95.0 to 99.0 mass%, the oxygen content is 0.1 to 5.0 mass%, and the iron content is 0.1 to 3.0% by weight, based on the total mass of the modified graphite; preferably, the carbon content of the iron trichloride modified graphite is 95.0-99.0 mass%, the oxygen content is 0.1-2.0 mass%, and the iron content is 0.2-2.0 mass%, based on the total mass of the modified graphite. In one embodiment, the pretreated graphite and the anhydrous ferric chloride are used in amounts such that the carbon content of the ferric chloride modified graphite is 95.0 to 99.0 mass%, the oxygen content is 0.1 to 5.0 mass%, and the iron content is 0.1 to 3.0 mass%, based on the total mass of the modified graphite. In another embodiment, the pretreated graphite and the anhydrous ferric chloride are used in amounts such that the carbon content of the ferric chloride modified graphite is 95.0 to 99.0 mass%, the oxygen content is 2.0 to 5.0 mass%, and the iron content is 0.2 to 2.0 mass%, based on the total mass of the modified graphite.
In the present application, the graphite may be selected from one or more of natural graphite, expanded graphite, flake graphite, and graphite oxide. Preferably, the graphite is expanded graphite, because the expanded graphite is a vermicular product obtained by oxidizing, acidifying intercalation, washing, drying and expanding natural crystalline flake graphite, the vermicular graphite reserves the lamellar structure of the natural graphite, has the characteristics of high temperature resistance, corrosion resistance, electric conduction, heat conduction, self lubrication and the like, has the characteristics of reduced specific gravity, enlarged specific surface, enlarged compression shape, easy rebound and the like caused by expansion, and is an ideal functional material such as a lubricant, an adsorbent, an additive and the like. In addition, because the expanded graphite is prepared from natural graphite through processes of oxidation, acidification intercalation and the like in the preparation process, compared with the natural graphite, the oxygen content in the graphite is increased, so that the conductivity of the graphite is reduced, and the application of the expanded graphite in conductive materials is limited. In one embodiment, the expanded graphite is selected from the group consisting of flake expanded graphite having a multiple expansion of 300 or more and a particle size of 1 μm or more, and has a volume resistivity of less than 1 Ω · cm. The expanded graphite with small volume resistivity is beneficial to obtaining the conductive composite material with more excellent conductivity.
Compared with an intercalated graphite compound, the ferric trichloride modified graphite obtained by the method has the advantages that the reaction temperature is low, the reaction time is short, the ferric trichloride is almost free of intercalated graphite interlayers, the ferric trichloride is combined with the oxygen functional groups at the edge of the graphite or fills partial graphite structure defects, so that the material resistance caused by partial oxygen functional groups or defects is increased, the combination ability of the graphite modified graphite with a resin material is improved due to the change of the graphite edge functional groups and the influence of iron elements, the sheets are easier to strip in the mixed grinding process of the graphite and can be mutually lapped and meshed in the material to form a conductive network, and therefore the composite material with higher conductivity can be obtained under the condition that less expanded graphite material is added.
In one embodiment, the polyolefin resin is selected from one or more of Low Density Polyethylene (LDPE), Linear Low Density Polyethylene (LLDPE), High Density Polyethylene (HDPE), Medium Density Polyethylene (MDPE), High Density Polyethylene (HDPE), Ultra High Molecular Weight Polyethylene (UHMWPE), polypropylene (PP), ethylene-propylene copolymers, ethylene-butene copolymers, and ethylene-other olefin copolymers. Here, the other olefin means an alpha-olefin having 5 to 10 carbon atoms.
In another aspect, the present application also provides a method for preparing a conductive polyolefin composite, comprising the steps of:
grinding and compounding the ferric trichloride modified graphite and the polyolefin resin to obtain the conductive polyolefin composite material, wherein the amount of the ferric trichloride modified graphite is 3-20 mass% of that of the polyolefin resin.
The iron trichloride modified graphite used in the above method can be obtained by referring to the preparation process of the iron trichloride modified graphite in the first aspect of the present application in the following manner: pretreating graphite at 200-400 ℃ in a vacuum state; carrying out composite modification on the pretreated graphite and anhydrous ferric trichloride at the temperature of 200-500 ℃ to obtain the ferric trichloride modified graphite.
The method for preparing the conductive polyolefin composite material also comprises grinding and compounding the ferric trichloride modified graphite and the polyolefin resin. The grinding compounding can ensure that the ferric trichloride modified graphite is fully dispersed in the polyolefin resin and can form a conductive network in the obtained composite material, so that the obtained composite material has conductivity. The grinding may be performed by ball milling, roll milling or the like. Preferably, the grinding compounding is performed in a ball mill. The compatibility of the graphite material and the polyolefin resin can be further improved by modifying the graphite, the graphite material can be more easily peeled off by ball milling, the surfaces of polyolefin resin particles are wrapped, a conductive network is formed, and meanwhile, the prepared conductive polyolefin composite material keeps the resin performance of the polyolefin resin. In the ball mill, the weight ratio of the stainless steel balls of the ball mill to the polyolefin resin is 2-50: 1, preferably 2-10: 1; the rotating speed is 150-2000 r/min, preferably 150-800 r/min; the ball milling time is 30 minutes to 12 hours, or 30 minutes to 4 hours.
The present invention will be described in detail below by way of examples for illustrating the conductive polyolefin composite material of the present invention and the method for preparing the same.
Example 1
(1) Adding 20.0g of expanded graphite (the expansion multiple is 300-400 times, the purity is 99.9%, the average particle size is 1 mu m, and the resistivity is 1.78m omega cm) into a 500mL high-temperature high-pressure reaction kettle, vacuumizing to below 0.09MPa, raising the temperature to 300 ℃ at the heating rate of 10 ℃/min, keeping the temperature for 2 hours, and then reducing to the normal temperature, wherein the oxygen content and the carbon content in the treated expanded graphite are 2.08 mass% and 97.92 mass%.
(2) Adding 4.0g of anhydrous ferric trichloride into the pretreated expanded graphite, continuously carrying out reaction modification in a high-temperature high-pressure reaction kettle, vacuumizing to be below 0.09MPa, raising the temperature to 320 ℃ at the heating rate of 10 ℃/min, keeping the temperature for 2h, then reducing the temperature to the normal temperature, introducing nitrogen for protection for later use, wherein the iron content, the oxygen content and the carbon content in the modified expanded graphite are respectively 1.01 mass%, 2.06 mass% and 96.93 mass%.
(3) After 1.0g of modified expanded graphite and 20.0g of Linear Low Density Polyethylene (LLDPE) are added into a 500mL planetary ball mill pot, 100.0g of stainless steel matched balls are added at 500 r/min, and ball milling is carried out for 8 hours, black brown carbon polymer powder is obtained, wherein the carbon content in the composite material is 5.0 mass percent. The volume resistivity of the prepared carbon polymer can be measured to be 54 omega cm by using a four-probe resistivity tester.
FIG. 1 is an X-ray diffraction pattern (XRD pattern) of the expanded graphite used in the present example before and after modification; fig. 2A and 2B show transmission electron micrographs (TEM images) of the expanded graphite used in this example and the modified expanded graphite, respectively.
Example 2
According to the method of example 1, except that,
in the step (2), the addition of anhydrous ferric trichloride is 2.0g, and the temperature is raised to 350 ℃; the modified expanded graphite had an iron content of 1.13 mass%, an oxygen content of 1.98 mass%, and a carbon content of 96.89 mass%;
and (3) adding 0.5g of the obtained modified expanded graphite, adding 20.0g of high-density polyethylene (HDPE), performing ball milling for 8 hours to obtain black brown carbon polyethylene powder, and measuring the volume resistivity of the prepared carbon polymer to be 23 omega cm by using a four-probe resistivity tester.
Comparative example 1
The process of example 1 was followed except that the carbon material used was expanded graphite and was modified without adding anhydrous ferric chloride, i.e., without the step (2) process. The carbon polymer composite material obtained is subjected to ball milling to obtain the carbon polymer composite material with the volume resistivity of 172 omega cm.
Comparative example 2
According to the method described in example 1, except that the carbon material used was natural graphite (resistivity of 9.0m Ω. cm), and was modified without adding anhydrous ferric chloride, a carbon polymer composite material was prepared, and the resistivity of the material could not be measured after ball milling, and the material could not conduct electricity.
The properties of the composite resin prepared are shown in Table 1.
TABLE 1
| Test items | Standard number | LLDPE | HDPE | Example 1 | Example 2 | Comparative example 1 |
| MI2.16，g/10min | GB3682 | 2.00 | 0.9510 | 1.98 | 0.9508 | 1.99 |
| Density, g/cm3 | GB1033 | 0.9195 | 1.09 | 0.9195 | 1.09 | 0.9194 |
| Yield strength, MPa | GB1040 | 10.4 | 24.8 | 10.1 | 24.6 | 10.3 |
| Breaking strength, Mpa | GB1040 | 18.2 | 15.9 | 18.7 | 15.9 | 18.4 |
| Elongation at break,% | GB1040 | 800 | 898 | 804 | 900 | 801 |
| Resistivity, Ω · cm | GB/T24521 | / | / | 54 | 23 | 172 |
The experimental results show that the carbon/polyolefin composite material with better conductivity can be obtained after graphite modification and polyolefin resin ball milling compounding. As can be seen from Table 1, after the polyolefin resin carbon is compounded, the resin material performance is not obviously changed, but the conductivity is obviously improved, so that the material can be used as a conductive material to be applied to conductive, antistatic and electromagnetic shielding products.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (15)
1. An electrically conductive polyolefin composite comprising:
ferric trichloride modified graphite, and polyolefin resin;
wherein the amount of the ferric trichloride modified graphite is 2.0-20.0 mass% of the polyolefin resin.
2. The conductive polyolefin composite according to claim 1, wherein the volume resistivity of the conductive polyolefin composite is 10 to 10000 Ω -cm.
3. The conductive polyolefin composite material according to claim 1, wherein the carbon content of the iron trichloride modified graphite is 95.0 to 99.0 mass%, the oxygen content is 0.1 to 5.0 mass%, and the iron content is 0.1 to 3.0 mass%, based on the total mass of the modified graphite.
4. The conductive polyolefin composite material according to claim 1, wherein the carbon content of the iron trichloride modified graphite is 95.0 to 99.0 mass%, the oxygen content is 0.1 to 2.0 mass%, and the iron content is 0.2 to 2.0 mass%, based on the total mass of the modified graphite.
5. The conductive polyolefin composite of any of claims 1-4, wherein the iron trichloride-modified graphite is obtained by:
pretreating graphite at 200-400 ℃ in a vacuum state,
carrying out composite modification on the pretreated graphite and anhydrous ferric trichloride at the temperature of 200-500 ℃ to obtain the ferric trichloride modified graphite.
6. The conductive polyolefin composite according to claim 5, wherein the pretreated graphite has an oxygen content of 0.1 to 5.0 mass% and a carbon content of 94.0 to 99.0 mass% based on the total mass of the pretreated graphite.
7. The conductive polyolefin composite material according to claim 5, wherein the pretreated graphite and the anhydrous ferric trichloride are used in amounts such that the carbon content in the ferric trichloride-modified graphite is 95.0 to 99.0 mass%, the oxygen content is 0.1 to 2.0 mass%, and the iron content is 0.2 to 2.0 mass%, based on the total mass of the modified graphite.
8. The electrically conductive polyolefin composite of claim 5, wherein the graphite is selected from one or more of natural graphite, expanded graphite, flake graphite, and graphite oxide, preferably expanded graphite.
9. The conductive polyolefin composite of claim 1, wherein the polyolefin resin is selected from one or more of Low Density Polyethylene (LDPE), Linear Low Density Polyethylene (LLDPE), High Density Polyethylene (HDPE), Medium Density Polyethylene (MDPE), High Density Polyethylene (HDPE), Ultra High Molecular Weight Polyethylene (UHMWPE), polypropylene (PP), ethylene-propylene copolymers, ethylene-butene copolymers, and ethylene-other olefin copolymers.
10. A preparation method of a conductive polyolefin composite material comprises the following steps:
grinding and compounding the ferric trichloride modified graphite and the polyolefin resin to obtain the conductive polyolefin composite material;
wherein the amount of the ferric trichloride modified graphite is 2.0-20.0% by mass of the polyolefin resin.
11. The production method according to claim 10, wherein the iron trichloride-modified graphite is obtained by:
pretreating graphite at 200-400 ℃ in a vacuum state, and carrying out composite modification on the pretreated graphite and anhydrous ferric trichloride at 200-500 ℃ to obtain the ferric trichloride modified graphite.
12. The production method according to claim 11, wherein the pretreated graphite has an oxygen content of 0.1 to 5.0 mass% and a carbon content of 95.0 to 99.9 mass% based on the total mass of the pretreated graphite.
13. The production method according to claim 11, wherein the pretreated graphite and the anhydrous ferric trichloride are used in amounts such that the carbon content in the ferric trichloride-modified graphite is 95.0 to 99.0% by mass, the oxygen content is 0.1 to 5.0% by mass, and the iron content is 0.1 to 3.0% by mass, based on the total mass of the modified graphite.
14. The production method according to claim 10, wherein the grinding compounding is performed in a ball mill.
15. The method according to claim 14, wherein the ball mill has a weight ratio of stainless steel balls to the polyolefin resin of 2 to 50: 1, a rotation speed of 150 to 2000 rpm, and a ball milling time of 30 minutes to 12 hours.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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