Polypropylene-based antistatic functional master batch and preparation method thereof

Abstract

The invention relates to the field of plastic master batches, and provides a polypropylene-based antistatic functional master batch and a preparation method thereof, the polypropylene-based antistatic functional master batch comprises the following raw materials by weight: 60-80 parts of polypropylene, 3-7 parts of modified graphene oxide, 1-5 parts of an antioxidant, 0.5-2 parts of a flame retardant, and 1-3 parts of a dispersant. The polypropylene-based antistatic functional master batch provided by the invention has the characteristics of good antistatic property and oxidation resistance.

Description

Technical Field

[0001] The present invention relates to the field of plastic masterbatches, and particularly to a polypropylene-based antistatic functional masterbatch and a preparation method thereof. Background Art

[0002] Polypropylene is a general-purpose plastic with a wide range of raw material sources, low price, and easy molding and processing. It has excellent mechanical properties, heat resistance, and chemical resistance, and can be widely used in the fields of the automotive industry, household appliances, industrial materials, medical supplies, etc.

[0003] Although polypropylene has many excellent characteristics mentioned above, during the plastic material processing, it is prone to the accumulation of static charges due to friction, which may further lead to quality problems and even pose safety hazards. Moreover, polypropylene itself does not have antistatic properties and even has high electrical insulation, making it more likely to generate static electricity during processing or use. Therefore, antistatic agents need to be added to endow polyolefin materials with antistatic properties. In addition, the tertiary hydrogen atoms in the polypropylene molecule are easily affected by heat or light and undergo aging, resulting in color change and performance degradation of the polypropylene resin.

[0004] Patent CN 112759848B discloses an antibacterial and antistatic polypropylene composite material and a preparation method thereof. The antibacterial and antistatic polypropylene composite material disclosed in this application includes polypropylene resin, toughening agent, and talcum powder. The total mass fraction of polypropylene resin, toughening agent, and talcum powder is 100 parts, and it also includes 2 - 10 parts of antibacterial and antistatic masterbatch, 0.2 - 0.6 parts of antioxidant, 0.05 - 0.3 parts of lubricant, and 0.2 - 0.5 parts of weathering agent. The antibacterial and antistatic masterbatch is prepared from an antibacterial and antistatic prefabricated composite and polypropylene as raw materials; the antibacterial and antistatic prefabricated composite is prepared from nano-silver, graphene oxide, and coupling agent as raw materials, making the antibacterial and antistatic polypropylene composite material have both good antibacterial effect and antistatic function. However, the graphene oxide component in the antibacterial and antistatic prefabricated composite has problems of easy agglomeration and poor dispersibility, which will lead to a decrease in the overall antistatic performance of the polypropylene composite material.

[0005] Therefore, there is an urgent need in the market for a polypropylene-based functional masterbatch with good antistatic and antioxidant properties. Summary of the Invention

[0006] Aiming at the problems existing in the prior art, the present invention uses polypropylene as the main component of the functional masterbatch, and synthesizes a polypropylene-based antistatic functional masterbatch by adding modified graphene oxide, antioxidant, flame retardant, and dispersant, which has good antistatic and antioxidant characteristics.

[0007] In order to achieve the above object, the technical solution adopted by the present invention is as follows:

[0008] On the one hand, the present invention provides a polypropylene-based antistatic functional masterbatch. By weight, the polypropylene-based antistatic functional masterbatch comprises the following raw materials: 60 - 80 parts of polypropylene, 3 - 7 parts of modified graphene oxide, 1 - 5 parts of antioxidant, 0.5 - 2 parts of flame retardant, and 1 - 3 parts of dispersant.

[0009] Among them, the flame retardant is antimony trioxide.

[0010] In some embodiments of the present invention, the preparation method of the modified graphene oxide comprises the following steps:

[0011] 1) Mix tetraethylammonium hydroxide, acetonitrile, propanol and deionized water, stir, add γ-aminopropyltriethoxysilane, stir at 45 - 55 °C for 23 - 25 h, perform rotary evaporation, wash, and freeze-dry to obtain POSS material for standby;

[0012] 2) Add antimony tin oxide to a reaction vessel, introduce an inert gas, add deionized water, perform ultrasonic treatment, add an ethanol aqueous solution and the POSS material obtained in step 1), stir at 35 - 45 °C for 8 - 10 h, filter, wash, and dry to obtain a product for standby;

[0013] 3) Add graphene oxide to deionized water, stir, add the product obtained in step 2), add an aqueous sodium hydroxide solution to adjust the pH to 9 - 10, stir at 75 - 85 °C for 23 - 25 h, centrifuge, take the upper suspension, centrifuge, wash until neutral, take the lower colloid, and dry to obtain the modified graphene oxide.

[0014] Among them, in step 1), the ratio of γ-aminopropyltriethoxysilane, tetraethylammonium hydroxide, acetonitrile, propanol and deionized water is 1 g : (0.008 - 0.01) ml : (0.03 - 0.05) ml : (0.16 - 0.20) ml : (0.35 - 0.45) ml.

[0015] In some embodiments of the present invention, in step 2), the mass ratio of antimony tin oxide to the POSS material is 1 : (12 - 13).

[0016] Preferably, in step 2), the mass ratio of antimony tin oxide to the POSS material is 1 : 12.5.

[0017] In some embodiments of the present invention, in step 3), the mass ratio of graphene oxide to the product is 1 : (0.3 - 0.5).

[0018] Preferably, in step 3), the mass ratio of graphene oxide to the product is 1 : 0.4.

[0019] Graphene oxide has good electrical conductivity. Adding it to polypropylene materials can improve the electrical conductivity of polypropylene to reduce static charge accumulation, and thus achieve a good antistatic effect. However, graphene oxide has the problem of easy agglomeration, which leads to poor dispersibility, and will cause the antistatic performance of polypropylene to not be well improved.

[0020] The applicant prepared an organic-inorganic hybrid POSS material by hydrolyzing and condensing the organosilicon compound γ-aminopropyltriethoxysilane, and further modified tin antimonate oxide with the POSS material to obtain a product. Finally, the product was anchored on the graphene oxide sheets to obtain modified graphene oxide. On the one hand, tin antimonate oxide has high electrical conductivity and chemical stability, and can cooperate with graphene oxide to improve the antistatic property of polypropylene; on the other hand, the applicant synthesized a POSS material with a complete cage structure and amino groups by controlling the conditions of the hydrolysis and condensation reaction of γ-aminopropyltriethoxysilane, and used the covalent bond connection between amino and carboxyl groups to anchor the POSS material on the graphene oxide sheets. The cage structure of the POSS material produced a steric effect between the graphene oxide sheets, thereby effectively improving the dispersibility of graphene oxide.

[0021] In some embodiments of the present invention, the preparation method of the antioxidant includes the following steps:

[0022] (1) Add quercetin to absolute ethanol, stir, add an aqueous sodium acetate solution to adjust the pH = 5 - 7, add an absolute ethanol solution of zinc acetate, heat to 50 - 70 °C, stir until precipitation occurs, stop the reaction, centrifuge, wash, and dry to obtain product 1 for standby;

[0023] (2) Add chitosan to an aqueous acetic acid solution, stir to obtain solution 1 for standby, add sodium tripolyphosphate to deionized water, stir to obtain solution 2 for standby, add tea polyphenols to solution 1 under ultrasonic conditions, stir, add solution 2, stir, centrifuge, wash, and dry to obtain product 2 for standby;

[0024] (3) Mix product 1 from step (1) and product 2 from step (2), and ball mill to obtain the antioxidant.

[0025] In some embodiments of the present invention, in step (1), the mass ratio of zinc acetate in the absolute ethanol solution of quercetin and zinc acetate is 1:(0.3 - 0.5).

[0026] Preferably, in step (1), the mass ratio of zinc acetate in the absolute ethanol solution of quercetin and zinc acetate is 1:0.4.

[0027] In some embodiments of the present invention, in step (2), the mass ratio of chitosan, sodium tripolyphosphate, and tea polyphenols is 1:(0.2 - 0.3):(0.05 - 0.15).

[0028] Preferably, in step (2), the mass ratio of chitosan, sodium tripolyphosphate, and tea polyphenols is 1:0.25:0.1.

[0029] In some embodiments of the present invention, in step (3), the mass ratio of product 1 and product 2 is 1:(1.5 - 2.5).

[0030] Preferably, in step (3), the mass ratio of product 1 and product 2 is 1:2.

[0031] Quercetin is a natural flavonoid compound with good biological activity and is a natural antioxidant. However, the structural characteristics of quercetin itself make it sensitive to temperature and easily lose its biological activity due to environmental factors. Especially in a high-temperature environment, the antioxidant property of quercetin cannot play a lasting role.

[0032] On the one hand, the applicant introduced zinc acetate to modify quercetin, and by controlling the pH of the reaction between zinc acetate and quercetin within the range of 5 - 7, the strong coordinating oxygen atoms in the quercetin molecule were in a suitable spatial configuration to form a stable complex with Zn 2+ Thereby effectively enhancing the thermal stability of quercetin and endowing quercetin with certain antibacterial properties; on the other hand, the applicant synthesized a carrier particle (product 2) using tea polyphenols, chitosan, and sodium tripolyphosphate as raw materials. Chitosan is a natural and environmentally friendly carrier material, and sodium polyphosphate has excellent thermal stability. The amino group of chitosan and the phosphate group of sodium tripolyphosphate interacted with each other, enhancing the intermolecular interaction and thermal stability of the carrier particle molecules. Tea polyphenols were combined with chitosan and sodium tripolyphosphate through hydrogen bonds, thereby improving the antioxidant property of the carrier particle. Further, the applicant combined the zinc acetate-modified quercetin with the carrier particle by ball milling. The carrier particle played a good protective role for quercetin, thereby effectively improving the thermal stability of quercetin, and the various active ingredients in quercetin and tea polyphenols could play a synergistic effect, which could further improve the antioxidant performance of quercetin.

[0033] In some embodiments of the present invention, the dispersant is polyethylene wax or ethylene bisstearamide.

[0034] On the other hand, the present invention also provides a method for preparing the polypropylene-based antistatic masterbatch described in the above technical solution, including the following steps:

[0035] Polypropylene, modified graphene oxide, antioxidant, flame retardant and dispersant are respectively crushed and then mixed, stirred, melt-kneaded, extruded, cooled, air-dried and granulated to obtain a polypropylene-based antistatic masterbatch.

[0036] Compared with the prior art, the present invention has the following beneficial effects:

[0037] (1) In the present invention, polypropylene is used as the main component of the masterbatch, and a polypropylene-based antistatic masterbatch is synthesized by adding modified graphene oxide, antioxidant, flame retardant and dispersant. Through the synergistic effect among the components, the polypropylene-based antistatic masterbatch has good antistatic and antioxidant characteristics.

[0038] (2) In the present invention, an organic-inorganic hybrid POSS material is prepared by hydrolytic condensation of an organosilicon compound γ-aminopropyltriethoxysilane, and further, the tin antimonate oxide is modified by using the POSS material to obtain a product. Finally, the product is anchored onto the graphene oxide sheet layer to obtain modified graphene oxide, which greatly improves the dispersibility of graphene oxide and further significantly enhances the antistatic performance of graphene oxide.

[0039] (3) In the present invention, quercetin is modified with zinc acetate, and then a carrier particle is synthesized by using tea polyphenols, chitosan and sodium tripolyphosphate as raw materials. Finally, the zinc acetate-modified quercetin is combined with the carrier particle by ball milling. The carrier particle plays a good protective role on quercetin, thereby effectively improving the thermal stability and antioxidant performance of quercetin.

[0040] (4) The polypropylene-based masterbatch prepared in the present invention has good antistatic and antioxidant characteristics and can be widely applied to the antistatic field, having good commercial application value. Specific Embodiments

[0041] The present invention will be described below in conjunction with specific implementation embodiments. It should be noted that the following examples are examples of the present invention and are only used to illustrate the present invention, rather than to limit the present invention. Other combinations and various improvements within the concept of the present invention can be made without departing from the gist or scope of the present invention.

[0042] In the following examples and comparative examples, except for modified graphene oxide and antioxidant, the compound monomers and related reagents used can be purchased from the market. Among them, polypropylene is purchased from Jiuju International Trade (Shanghai) Co., Ltd.; chitosan is purchased from Qingdao Bozhihuilai Biotechnology Co., Ltd.; polyethylene wax is purchased from Shanghai Zhenlishi Network Technology Co., Ltd.

[0043] Preparation Example 1

[0044] The synthesis method of modified graphene oxide A includes the following steps:

[0045] 1) Mix 1 ml of tetraethylammonium hydroxide, 5 ml of acetonitrile, 20 ml of propanol, and 45 ml of deionized water, stir for 10 min, add 110.5 g of γ-aminopropyltriethoxysilane, stir at 50 °C for 24 h, perform rotary evaporation, wash successively with deionized water and cyclohexane, and freeze-dry at -40 °C for 12 h to obtain the POSS material for standby;

[0046] 2) Add 3.2 g of antimony tin oxide to the reaction vessel, introduce nitrogen, add 300 ml of deionized water, sonicate for 1 h, add 50 wt% ethanol aqueous solution and 40 g of the POSS material obtained in step 1), stir at 40 °C for 9 h, filter, wash successively with absolute ethanol and deionized water 3 times, and dry at 60 °C for 12 h to obtain the product for standby;

[0047] 3) Add 1 g of graphene oxide to 100 ml of deionized water, stir for 20 min, add 0.4 g of the product obtained in step 2), add 10 wt% sodium hydroxide aqueous solution to adjust the pH to 9.5, stir at 80 °C for 24 h, centrifuge, take the upper suspension, centrifuge, wash with deionized water until neutral, centrifuge, take the lower colloid, and dry at 35 °C for 72 h to obtain the modified graphene oxide A.

[0048] Preparation Example 2

[0049] For the modified graphene oxide B, the specific implementation method is the same as that of the modified graphene oxide A, except that in step 2), the mass of the POSS material is replaced with 37.5 g.

[0050] Preparation Example 3

[0051] For the modified graphene oxide C, the specific implementation method is the same as that of the modified graphene oxide A, except that in step 3), the mass of the product is replaced with 0.2 g.

[0052] Preparation Example 4

[0053] The synthesis method of antioxidant A includes the following steps:

[0054] (1) Add 10 g of quercetin to 100 ml of absolute ethanol, stir for 15 min, add 0.2 mol / L sodium acetate aqueous solution to adjust the pH to 6, add 20 ml of 0.2 g / ml zinc acetate absolute ethanol solution, heat to 60 °C, stir until precipitation occurs, stop the reaction, centrifuge, wash successively with absolute ethanol and deionized water 3 times, and dry at -40 °C for 24 h to obtain the product 1 for standby;

[0055] (2) Add 10 g of chitosan to 60 ml of 1 wt% acetic acid aqueous solution, stir for 30 min to obtain Solution 1 for standby. Add 2.5 g of sodium tripolyphosphate to 100 ml of deionized water, stir for 30 min to obtain Solution 2 for standby. Under ultrasonic conditions, add 1 g of tea polyphenols to Solution 1, stir for 30 min, add Solution 2, stir for 30 min, centrifuge, wash with deionized water three times, and dry at 60 °C for 24 h to obtain Product 2 for standby;

[0056] (3) Mix 5 g of Product 1 from step (1) and 10 g of Product 2 from step (2), and ball mill to obtain antioxidant A.

[0057] Preparation Example 5

[0058] Antioxidant B, the specific implementation method is the same as that of antioxidant A, the difference is that: in step (1), the volume of the anhydrous ethanol solution of zinc acetate is replaced with 12 ml.

[0059] Preparation Example 6

[0060] Antioxidant C, the specific implementation method is the same as that of antioxidant A, the difference is that: in step (2), the mass of sodium tripolyphosphate is replaced with 1.5 g.

[0061] Preparation Example 7

[0062] Antioxidant D, the specific implementation method is the same as that of antioxidant A, the difference is that: in step (2), the mass of tea polyphenols is replaced with 0.3 g.

[0063] Preparation Example 8

[0064] Antioxidant E, the specific implementation method is the same as that of antioxidant A, the difference is that: in step (3), the mass of Product 2 is replaced with 6.5 g.

[0065] Example 1

[0066] A polypropylene-based antistatic masterbatch, by weight, the polypropylene-based antistatic masterbatch includes the following raw materials: 70 parts of polypropylene, 5 parts of modified graphene oxide A, 3 parts of antioxidant A, 1.5 parts of antimony trioxide, and 2 parts of polyethylene wax.

[0067] The preparation method of the polypropylene-based antistatic masterbatch in this example includes the following steps:

[0068] The polypropylene, modified graphene oxide A, antioxidant A, antimony trioxide, and polyethylene wax are respectively pulverized and then mixed, stirred at 90 °C and 1000 rpm for 1.5 h, melt-kneaded and extruded at 200 °C in a twin-screw extruder, cooled to room temperature, air-dried at room temperature, and pelletized to obtain the polypropylene-based antistatic masterbatch.

[0069] Example 2

[0070] A polypropylene-based antistatic masterbatch, by weight, the polypropylene-based antistatic masterbatch comprises the following raw materials: 60 parts of polypropylene, 5 parts of modified graphene oxide A, 1 part of antioxidant A, 0.5 part of antimony trioxide, and 1 part of vinyl bisstearamide.

[0071] The preparation method of the polypropylene-based antistatic masterbatch in this example comprises the following steps:

[0072] The polypropylene, modified graphene oxide A, antioxidant A, antimony trioxide, and vinyl bisstearamide are respectively pulverized and then mixed, stirred at 80 °C and 1000 rpm for 2 h, melt-kneaded and extruded at 200 °C in a twin-screw extruder, cooled to room temperature, air-dried at room temperature, and pelletized to obtain the polypropylene-based antistatic masterbatch.

[0073] Example 3

[0074] A polypropylene-based antistatic masterbatch, by weight, the polypropylene-based antistatic masterbatch comprises the following raw materials: 80 parts of polypropylene, 5 parts of modified graphene oxide A, 5 parts of antioxidant A, 2 parts of antimony trioxide, and 3 parts of vinyl bisstearamide.

[0075] The preparation method of the polypropylene-based antistatic masterbatch in this example comprises the following steps:

[0076] The polypropylene, modified graphene oxide A, antioxidant A, antimony trioxide, and vinyl bisstearamide are respectively pulverized and then mixed, stirred at 100 °C and 1000 rpm for 1 h, melt-kneaded and extruded at 200 °C in a twin-screw extruder, cooled to room temperature, air-dried at room temperature, and pelletized to obtain the polypropylene-based antistatic masterbatch.

[0077] Example 4

[0078] A polypropylene-based antistatic masterbatch, by weight, the polypropylene-based antistatic masterbatch comprises the following raw materials: 65 parts of polypropylene, 3 parts of modified graphene oxide A, 3 parts of antioxidant A, 1 part of antimony trioxide, and 1.5 parts of polyethylene wax.

[0079] The preparation method of the polypropylene-based antistatic masterbatch in this example is the same as that in Example 1.

[0080] Example 5

[0081] A polypropylene-based antistatic masterbatch. By weight, the polypropylene-based antistatic masterbatch comprises the following raw materials: 75 parts of polypropylene, 7 parts of modified graphene oxide A, 3 parts of antioxidant A, 1.8 parts of antimony trioxide, and 2.5 parts of polyethylene wax.

[0082] In this embodiment, the preparation method of the polypropylene-based antistatic masterbatch is the same as that in Example 1.

[0083] Example 6

[0084] This embodiment provides a polypropylene-based antistatic masterbatch and its preparation method. The specific implementation manner is the same as that in Example 1, except that modified graphene oxide B is used to replace modified graphene oxide A in equal amounts.

[0085] Example 7

[0086] This embodiment provides a polypropylene-based antistatic masterbatch and its preparation method. The specific implementation manner is the same as that in Example 1, except that modified graphene oxide C is used to replace modified graphene oxide A in equal amounts.

[0087] Example 8

[0088] This embodiment provides a polypropylene-based antistatic masterbatch and its preparation method. The specific implementation manner is the same as that in Example 1, except that antioxidant B is used to replace antioxidant A in equal amounts.

[0089] Example 9

[0090] This embodiment provides a polypropylene-based antistatic masterbatch and its preparation method. The specific implementation manner is the same as that in Example 1, except that antioxidant C is used to replace antioxidant A in equal amounts.

[0091] Example 10

[0092] This embodiment provides a polypropylene-based antistatic masterbatch and its preparation method. The specific implementation manner is the same as that in Example 1, except that antioxidant D is used to replace antioxidant A in equal amounts.

[0093] Example 11

[0094] This embodiment provides a polypropylene-based antistatic masterbatch and its preparation method. The specific implementation manner is the same as that in Example 1, except that antioxidant E is used to replace antioxidant A in equal amounts.

[0095] Example 12

[0096] This embodiment provides a polypropylene-based antistatic masterbatch and its preparation method. The specific implementation is the same as that of Example 1, except that quercetin is used to replace antioxidant A in equal amounts.

[0097] Comparative Example 1

[0098] This comparative example provides a polypropylene-based antistatic masterbatch and its preparation method. The specific implementation is the same as that of Example 1, except that graphene oxide is used to replace modified graphene oxide A.

[0099] Performance Test

[0100] The antistatic property and antioxidant property of the polypropylene-based antistatic masterbatches of the above Examples 1 - 12 and Comparative Example 1 were tested, and the test results are shown in Table 1.

[0101] (1) Antistatic Property

[0102] By testing the volume resistivity of the polypropylene-based antistatic masterbatches prepared in the examples and comparative examples, the smaller the volume resistivity, the better the conductivity, that is, the better the antistatic property, referring to the standard GB / T 15662 - 1995.

[0103] (2) Antioxidant Property

[0104] The antioxidant property is judged by the degree of yellowing. After irradiating with a carbon rod lamp-type sunlight irradiator in an atmospheric climate tester for 30 hours, the degree of yellowing of the polypropylene-based antistatic masterbatch is measured with a colorimeter, and the yellowing value (Y I ) is used to represent. The larger the yellowing value, the worse the anti-aging property.

[0105] Table 1

[0106]

[0107]

[0108] As can be seen from the data in Table 1, the polypropylene-based antistatic masterbatch in Examples 1-5 of the present invention as a whole has the characteristics of low volume resistivity and low yellowing value, that is, good antistatic property and antioxidant property. Among them, in Examples 6-7, the addition ratio of POSS material in the synthesis process of modified graphene oxide and the modification ratio of graphene oxide were changed, so that the dispersibility and antistatic property of modified graphene oxide were not well improved, which in turn led to a significant decrease in the antistatic property of modified graphene oxide, but had little effect on the antioxidant property; in Examples 8-11, the addition ratio of key components in the antioxidant was changed, resulting in a decrease in the thermal stability and antioxidant property of the antioxidant. Since the polypropylene-based antistatic masterbatch needs to be heated at high temperature during the preparation process, the poor thermal stability of the antioxidant will seriously affect its antioxidant improvement effect on the masterbatch, and then the phenomenon that the yellowing value of the polypropylene-based antistatic masterbatch increases significantly is reflected, but has little effect on the antistatic property; in Example 12 and Comparative Example 1, quercetin and graphene oxide were respectively selected to replace antioxidant A and modified graphene oxide A in equal amounts. It was found that the antioxidant property of Example 12 showed poor results, but had little effect on the antistatic property, while the antistatic property of Comparative Example 1 showed poor results, but had little effect on the antioxidant property.

[0109] The above embodiments are only for illustrating the technical concept and characteristics of the present invention, and the purpose is to enable those who are familiar with this technology to understand the content of the present invention and implement it. It should not be used to limit the protection scope of the present invention. Any equivalent changes or modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.

Claims

1. A polypropylene-based antistatic functional masterbatch, characterized in that: The polypropylene-based antistatic functional masterbatch comprises the following raw materials by weight: 60-80 parts of polypropylene, 3-7 parts of modified graphene oxide, 1-5 parts of antioxidant, 0.5-2 parts of flame retardant and 1-3 parts of dispersant.

2. The polypropylene-based antistatic functional masterbatch according to claim 1, characterized in that: The preparation method of the modified graphene oxide comprises the following steps: 1) Tetraethylammonium hydroxide, acetonitrile, propanol and deionized water are mixed, stirred, γ-aminopropyltriethoxysilane is added, stirred at 45-55° C. for 23-25 ​​h, rotary evaporated, washed, freeze-dried to obtain POSS material for use; 2) adding antimony tin oxide to a reaction vessel, introducing an inert gas, adding deionized water, ultrasonicating, adding an ethanol aqueous solution and the POSS material of step 1), stirring at 35-45° C. for 8-10 h, filtering, washing, and drying to obtain a product for later use; 3) Add graphene oxide to deionized water, stir, add the product of step 2), add sodium hydroxide aqueous solution to adjust pH to 9-10, stir at 75-85° C. for 23-25 ​​h, centrifuge, take the upper suspension, centrifuge, wash to neutrality, take the lower colloid, and dry to obtain modified graphene oxide.

3. The polypropylene-based antistatic functional masterbatch according to claim 2, characterized in that: In the step 2), the mass ratio of antimony tin oxide to POSS material is 1:(12-13).

4. The polypropylene-based antistatic functional masterbatch according to claim 2, characterized in that: In the step 3), the mass ratio of graphene oxide to product is 1:(0.3-0.5).

5. The polypropylene-based antistatic functional masterbatch according to claim 1, characterized in that: The preparation method of the antioxidant comprises the following steps: (1) adding quercetin to anhydrous ethanol, stirring, adding sodium acetate aqueous solution to adjust the pH to 5-7, adding anhydrous ethanol solution of zinc acetate, heating to 50-70° C., stirring until precipitation occurs, stopping the reaction, centrifuging, washing, and drying to obtain product 1 for later use; (2) adding chitosan to an acetic acid aqueous solution and stirring to obtain a solution 1 for later use, adding sodium tripolyphosphate to a deionized water solution and stirring to obtain a solution 2 for later use, adding tea polyphenols to the solution 1 under ultrasonic conditions and stirring, adding the solution 2, stirring, centrifuging, washing, and drying to obtain a product 2 for later use; (3) The product 1 of step (1) and the product 2 of step (2) are mixed and ball-milled to obtain an antioxidant.

6. The polypropylene-based antistatic functional masterbatch according to claim 5, characterized in that: In the step (1), the mass ratio of quercetin to zinc acetate in the anhydrous ethanol solution of zinc acetate is 1:(0.3-0.5).

7. The polypropylene-based antistatic functional masterbatch according to claim 5, characterized in that: In the step (2), the mass ratio of chitosan, sodium tripolyphosphate and tea polyphenols is 1:(0.2-0.3):(0.05-0.15).

8. The polypropylene-based antistatic functional masterbatch according to claim 5, characterized in that: In the step (3), the mass ratio of product 1 to product 2 is 1:(1.5-2.5).

9. The polypropylene-based antistatic functional masterbatch according to claim 1, characterized in that: The dispersant is polyethylene wax or vinyl bisstearamide.

10. A method for preparing the polypropylene-based antistatic functional masterbatch according to any one of claims 1 to 9, characterized in that: The following steps are involved: The polypropylene, modified graphene oxide, antioxidant, flame retardant and dispersant are crushed and mixed respectively, stirred, melt-kneaded, extruded, cooled, air-dried and granulated to obtain the polypropylene-based antistatic functional masterbatch.

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