A slip antistatic composite masterbatch and a preparation method thereof

Abstract

The application discloses a kind of smooth antistatic composite master batch and preparation method thereof, the smooth antistatic composite master batch includes the following weight fraction components: polypropylene 60-80 parts, antistatic agent 10-20 parts, slip agent 5-15 parts, dispersing agent 1-3 parts, antioxidant 0.1-1 part.The smooth antistatic composite master batch provided by the application realizes the efficient fusion of antistatic performance and smoothness through the scientific proportioning and synergistic effect of each component, not only can significantly improve the surface performance of BOPP film, but also can guarantee the comprehensive mechanical properties and processing adaptability of film, suitable for a variety of packaging scenarios with higher requirements on surface performance.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of functional masterbatch for plastic processing, and particularly relates to a smooth and antistatic composite masterbatch and a preparation method thereof. BACKGROUND

[0002] In the modern plastic processing industry, various plastic products are widely used in food packaging, electronic appliances, medical and health care, daily necessities and many other fields due to their lightweight, durability, easy processing and other characteristics, which have a profound impact on people's production and life. Among them, packaging film as an important branch of plastic products has strict requirements on its performance in many aspects due to its direct connection with product protection, storage and display, such as mechanical strength, barrier property, optical performance, weather resistance and use convenience, etc.

[0003] Taking polypropylene film (especially BOPP film) as an example, it occupies a core position in the packaging of food, beverage, cigarette, clothing, book and other industries due to its high gloss, excellent stiffness, excellent gas and moisture barrier property, high impact strength and good heat resistance, and the market demand continues to rise. The annual output in China has reached millions of tons. However, polypropylene film still faces many performance shortcomings in actual production and use, among which the lack of smoothness and antistatic property is particularly prominent, which becomes a key bottleneck restricting its efficient processing and high-quality application.

[0004] Specifically, in the high-speed automatic production line, the high friction coefficient between the films will cause insufficient smoothness, resulting in film adhesion, difficult unwinding and other problems, which seriously reduces the production efficiency; and the static generated by friction in processing and use will cause the film surface to adsorb dust and impurities, affecting the appearance and cleanliness of the product, and even posing a safety hazard in specific scenarios (such as electronic component packaging, contact with flammable and explosive materials).

[0005] To improve these defects, the industry generally solves by adding functional additives: antistatic agents eliminate static electricity by adjusting the surface charge distribution of the film, and slip agents improve the slip performance by reducing the surface friction coefficient. At present, the commonly used antistatic agents for polypropylene film mainly include cationic, anionic, non-ionic and high molecular conductive types. Among them, non-ionic antistatic agents are relatively ideal because of their stable chemical properties, which are not easy to cause plastic aging and degradation, and can form a conductive layer by adsorbing water molecules in the air through low molecular substances. Silicone is the main slip agent for slip agents, which has a significant effect, but it is difficult to popularize on a large scale in China due to its liquid state, inconvenience of addition and high price.

[0006] More concerning is that current antistatic agents and slip agents are often added separately as independent masterbatches: antistatic agents need to be formulated into antistatic masterbatches, and slip agents into slip masterbatches, before being added separately to the film production process. This approach not only increases the complexity of raw material procurement but also extends the production process chain (such as two batching and two mixing steps), leading to increased processing costs. Furthermore, the uniform dispersion of the two masterbatches in the film matrix is ​​difficult to control simultaneously, potentially resulting in localized excessively high or insufficient concentrations of additives, affecting the final performance stability.

[0007] Therefore, developing composite masterbatches with both antistatic and slip properties has become a pressing technical challenge for the industry. These composite masterbatches can simplify production processes, reduce overall costs, and improve performance stability through the synergistic effect of additives, which is of great significance for promoting the development of polypropylene films towards high efficiency, high quality, and low cost. Summary of the Invention

[0008] The main objective of this invention is to propose a slip-resistant and antistatic composite masterbatch and its preparation method, aiming to solve the problem of poor antistatic properties and slip-resistant properties of masterbatches in existing plastic products such as films.

[0009] To achieve the above objectives, the present invention proposes a smooth and antistatic composite masterbatch, comprising the following components in parts by weight:

[0010] Polypropylene 60-80 parts, antistatic agent 10-20 parts, slip agent 5-15 parts, dispersant 1-3 parts, antioxidant 0.1-1 parts.

[0011] Preferably, the dispersant includes at least one of polyethylene wax and oxidized polyethylene wax;

[0012] The antioxidant comprises 2,6-di-tert-butyl-p-cresol and (2,4-di-tert-butylphenyl) phosphite, wherein the mass ratio of 2,6-di-tert-butyl-p-cresol to (2,4-di-tert-butylphenyl) phosphite is (4-6):(1-3).

[0013] The dispersant is used to promote the uniform dispersion of each component in the carrier polypropylene resin, thereby improving the stability and performance consistency of the masterbatch.

[0014] The antioxidant prevents the masterbatch from aging due to oxidation during processing and use, thus extending its service life.

[0015] Preferably, the slip agent comprises behenamide and polyether-modified silicone oil, wherein the mass ratio of behenamide to polyether-modified silicone oil is 1:(1.2-2.5).

[0016] Preferably, the method for preparing the antistatic agent includes the following steps:

[0017] S1. Graphene oxide is added to N-methylpyrrolidone and ultrasonically dispersed to obtain a graphene oxide dispersion. Maleic anhydride and pyridine are added to the graphene oxide dispersion. Under nitrogen protection, the temperature is raised to 80-90°C and the mixture is stirred to react. After the reaction is completed, the mixture is centrifuged, washed, and vacuum dried to obtain carboxylated graphene oxide.

[0018] S2. The carboxylated graphene oxide is dispersed in cyclohexanone and ultrasonically dispersed. Then, vinyl silicone oil is added dropwise, followed by 2,2'-azobisisobutyronitrile. Under nitrogen protection, the mixture is heated and stirred. After the reaction is completed, hydroquinone is added to terminate the reaction. Then, ethanol is added to precipitate the mixture. After centrifugation, washing, and drying, silicone oil-modified graphene oxide is obtained.

[0019] S3. Dissolve the hydroxyl-terminated polyoxyethylene-polyoxypropylene block copolymer in cyclohexanone, then add the silicone oil-modified graphene oxide and p-toluenesulfonic acid. Under nitrogen protection, heat to 90-100°C and stir the reaction. After the reaction is completed, distill under reduced pressure, wash, and dry under vacuum to obtain modified graphene.

[0020] S4. Ethyl acetate is added to the modified graphene, and the mixture is stirred under heating conditions. Ascorbic acid is then added, and the reaction is continued with stirring. After the reaction is completed, the mixture is cooled, centrifuged and washed, and then vacuum dried to obtain the antistatic agent.

[0021] Preferably, in step S1, the ratio of graphene oxide, N-methylpyrrolidone, maleic anhydride, and pyridine is (4-8 mg): (8-12 mL): (25-35 mg): (0.1-1 mg).

[0022] The vacuum drying temperature is 55–65°C, and the vacuum drying time is 5–7 hours.

[0023] Preferably, in step S2, the mass ratio of carboxylated graphene oxide, vinyl silicone oil, 2,2'-azobisisobutyronitrile, and hydroquinone is (8-12):(2-4):(0.02-0.04):(0.02-0.03).

[0024] The temperature is raised to 60-65°C, and the stirring reaction time is 6-8 hours.

[0025] Preferably, in step S3, the hydroxyl-terminated polyoxyethylene-polyoxypropylene block copolymer has a hydroxyl value of 0.4 to 0.6 eq / 100g, and the polyoxyethylene segment content of the hydroxyl-terminated polyoxyethylene-polyoxypropylene block copolymer is 55 to 65%.

[0026] The mass ratio of the hydroxyl-terminated polyoxyethylene-polyoxypropylene block copolymer, the silicone oil-modified graphene oxide, and the p-toluenesulfonic acid is (8-10):(1-2):(0.03-0.04).

[0027] The vacuum drying temperature is 75–85°C, and the vacuum drying time is 3–5 hours.

[0028] Preferably, in step S4, the mass ratio of the modified graphene, ethyl acetate, and ascorbic acid is (1-2):(10-30):(0.1-0.3).

[0029] The temperature is then raised to 60–65°C;

[0030] The vacuum drying temperature is 65–75°C, and the vacuum drying time is 7.5–8.5 h.

[0031] This invention also proposes a method for preparing the slippery antistatic composite masterbatch as described above, comprising the following steps:

[0032] S10. Weigh each component raw material according to the weight percentage;

[0033] S20. Add the antistatic agent, slip agent, dispersant and antioxidant to the mixer and mix evenly to obtain the premix;

[0034] S30. Add the premixed material and polypropylene together into a twin-screw extruder for melt blending;

[0035] S40. The melt-blended material is extruded through the extruder head, water-cooled and stretched, then pelletized using a pelletizer and dried to obtain a smooth and antistatic composite masterbatch.

[0036] The preparation process flow chart of the smooth and antistatic composite masterbatch is shown below. Figure 1 .

[0037] Preferably, in step S20, the speed of the mixer is 500-1500 r / min, and the mixing time is 3-5 min;

[0038] In step S30, the production temperature of the twin-screw extruder is controlled at 225-235°C, and the screw speed is 400-430 r / min.

[0039] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0040] (1) The slippery antistatic composite masterbatch provided by the present invention achieves efficient integration of antistatic performance and slippery performance through the scientific ratio and synergistic effect of each component. It can not only significantly improve the surface performance of BOPP film, but also ensure the comprehensive mechanical properties and processing adaptability of film, and is suitable for a variety of packaging scenarios with high surface performance requirements.

[0041] (2) In the preparation process of the antistatic agent provided by the present invention, after the graphene is modified by maleic anhydride to introduce carboxyl groups and double bonds, it is reacted with vinyl silicone oil to introduce silicone oil segments. The silicone oil segments have low surface energy and form a "lubricating film" on the material surface, which significantly reduces the coefficient of friction. At the same time, the introduced silicon-oxygen bonds have low rotational resistance and weak inter-chain forces, making them easy to slide under external force and enhancing the slip performance. The graphene oxide with introduced silicone oil segments is then covalently bonded with the hydroxyl-terminated polyoxyethylene-polyoxypropylene block copolymer through esterification reaction to form modified graphene with both conductivity and compatibility. The introduced polyoxyethylene segments improve the hydrophilicity of the material, thereby improving its antistatic properties. At the same time, the introduced polyoxypropylene segments are similar to the non-polar structure of polypropylene, enhancing its compatibility. Then, the modified graphene is dispersed by ethyl acetate and reduced by ascorbic acid to reduce the oxygen-containing functional groups in the graphene oxide, thereby improving the conductivity and dispersibility of the graphene.

[0042] (3) The behenic acid amide in the slip agent provided by the present invention can migrate to the surface of the film to form a lubricating molecular layer, and the polyether modified silicone oil can fill the micro-unevenness of the film and significantly reduce the adhesion between films; the silicone oil segments introduced in the antistatic agent have low surface energy, and work synergistically with behenic acid amide and polyether modified silicone oil to further reduce the friction coefficient of the material surface, improve the slip performance of the overall system, avoid excessive static electricity generated by friction, and indirectly assist in maintaining the antistatic effect. Attached Figure Description

[0043] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other related drawings can be obtained based on these drawings without creative effort.

[0044] Figure 1 The process flow diagram for preparing the smooth and antistatic composite masterbatch provided by the present invention is shown.

[0045] The realization of the objective, functional features and advantages of the present invention will be further explained in conjunction with the embodiments and with reference to the accompanying drawings. Detailed Implementation

[0046] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents or instruments whose manufacturers are not specified are all conventional products that can be purchased commercially. Furthermore, the technical solutions of the various embodiments can be combined with each other, but this must be based on the ability of those skilled in the art to implement them. When the combination of technical solutions is contradictory or cannot be implemented, it should be considered that such a combination of technical solutions does not exist and is not within the scope of protection claimed by the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0047] The technical solution of the present invention will be further described in detail below with reference to specific embodiments and accompanying drawings. It should be understood that the following embodiments are only used to explain the present invention and are not intended to limit the present invention.

[0048] Polypropylene: Purchased from Pingxiang Shengfeng Packing Co., Ltd., specification 51*19mm;

[0049] Polyether-modified silicone oil: purchased from Jinan Jiaxu Chemical Technology Co., Ltd., industrial grade;

[0050] Polyethylene wax: purchased from Jiangsu Tianwen New Material Technology Co., Ltd., average particle size D50: 4-5, average particle size D90: 8-10;

[0051] Graphene oxide: purchased from Zhongke Leiming (Beijing) Technology Co., Ltd., specification: 0.5~3μm>99wt%1g.

[0052] Example 1

[0053] A smooth and antistatic composite masterbatch comprises the following components in parts by weight:

[0054] 70 parts polypropylene, 15 parts antistatic agent, 4 parts behenamide, 6 parts polyether modified silicone oil, 2 parts polyethylene wax, 0.4 parts 2,6-di-tert-butyl-p-cresol and 0.1 parts (2,4-di-tert-butylphenyl) phosphite;

[0055] The preparation method of the slippery antistatic composite masterbatch includes the following steps:

[0056] S10. Weigh each component raw material according to the weight percentage;

[0057] S20. Add the antistatic agent, slip agent, polyethylene wax and antioxidant to the mixer. The mixer speed is 1000 r / min and the mixing time is 4 min. Mix evenly to obtain the premix.

[0058] S30. Add the premixed material and polypropylene together into a twin-screw extruder. The production temperature of the twin-screw extruder is controlled at 230℃ and the screw speed is 415r / min for melt blending.

[0059] S40. The melt-blended material is extruded through the extruder head, and after being water-cooled and stretched, it is pelletized using a pelletizer and dried to obtain a smooth and antistatic composite masterbatch.

[0060] The method for preparing the antistatic agent includes the following steps:

[0061] S1. 12 mg of graphene oxide was added to 20 mL of N-methylpyrrolidone and ultrasonically dispersed to obtain a graphene oxide dispersion. 60 mg of maleic anhydride and 1 mg of pyridine were added to the graphene oxide dispersion. Under nitrogen protection, the temperature was raised to 85 °C and the mixture was stirred to react. After the reaction was completed, the mixture was centrifuged and washed, and then vacuum dried at 60 °C to obtain carboxylated graphene oxide.

[0062] S2. 10 mg of carboxylated graphene oxide was dispersed in 100 mL of cyclohexanone and ultrasonically dispersed. Then, 3 mg of vinyl silicone oil was added dropwise, followed by 0.03 mg of 2,2'-azobisisobutyronitrile. Under nitrogen protection, the mixture was heated to 63 °C and stirred for 7 h. After the reaction was completed, 0.025 mg of hydroquinone was added to terminate the reaction. Then, ethanol was added to precipitate the product. The product was centrifuged, washed, and dried to obtain silicone oil-modified graphene oxide.

[0063] S3. Dissolve 80 mg of hydroxyl-terminated polyoxyethylene-polyoxypropylene block copolymer in 100 mL of cyclohexanone, then add 10 mg of silicone oil-modified graphene oxide and 0.3 mg of p-toluenesulfonic acid. Under nitrogen protection, heat to 95 °C and stir to react. After the reaction is completed, distill under reduced pressure, wash, and vacuum dry to obtain modified graphene.

[0064] S4. Add 150 mg of ethyl acetate to 10 mg of modified graphene, stir and mix under heating conditions, then add 2 mg of ascorbic acid, continue stirring and reacting. After the reaction is complete, cool, centrifuge and wash, and vacuum dry to obtain the antistatic agent.

[0065] Example 2

[0066] A smooth and antistatic composite masterbatch comprises the following components in parts by weight:

[0067] 60 parts polypropylene, 10 parts antistatic agent, 4 parts behenamide, 6 parts polyether modified silicone oil, 1 part polyethylene wax, 0.4 parts 2,6-di-tert-butyl-p-cresol, and 0.1 parts (2,4-di-tert-butylphenyl) phosphite.

[0068] The preparation method of the slippery antistatic composite masterbatch includes the following steps:

[0069] S10. Weigh each component raw material according to the weight percentage;

[0070] S20. Add the antistatic agent, slip agent, polyethylene wax and antioxidant to the mixer. The mixer speed is 1000 r / min and the mixing time is 3 min. Mix evenly to obtain the premix.

[0071] S30. Add the premixed material and polypropylene together into a twin-screw extruder. The production temperature of the twin-screw extruder is controlled at 225℃ and the screw speed is 415r / min for melt blending.

[0072] S40. The melt-blended material is extruded through the extruder head, and after being water-cooled and stretched, it is pelletized using a pelletizer and dried to obtain a smooth and antistatic composite masterbatch.

[0073] The method for preparing the antistatic agent includes the following steps:

[0074] S1. Add 8 mg of graphene oxide to 20 mL of N-methylpyrrolidone and disperse by ultrasonication to obtain a graphene oxide dispersion. Add 50 mg of maleic anhydride and 0.2 mg of pyridine to the graphene oxide dispersion. Under nitrogen protection, heat to 80 °C and stir to react. After the reaction is complete, centrifuge and wash, and dry under vacuum at 60 °C to obtain carboxylated graphene oxide.

[0075] S2. Disperse 8 mg of carboxylated graphene oxide in 80 mL of cyclohexanone and sonicate. Then add 2 mg of vinyl silicone oil and 0.02 mg of 2,2'-azobisisobutyronitrile. Under nitrogen protection, heat to 60 °C and stir for 6 h. After the reaction is complete, add 0.02 mg of hydroquinone to terminate the reaction. Then add ethanol to precipitate, centrifuge, wash, and dry to obtain silicone oil modified graphene oxide.

[0076] S3. Dissolve 40 mg of hydroxyl-terminated polyoxyethylene-polyoxypropylene block copolymer in 100 mL of cyclohexanone, then add 8 mg of silicone oil-modified graphene oxide and 0.16 mg of p-toluenesulfonic acid. Under nitrogen protection, heat to 100 °C and stir to react. After the reaction is complete, distill under reduced pressure, wash, and dry under vacuum to obtain modified graphene.

[0077] S4. Add 120 mg of ethyl acetate to 8 mg of modified graphene, stir and mix under heating conditions, then add 1.2 mg of ascorbic acid, continue stirring and reacting. After the reaction is complete, cool, centrifuge and wash, and vacuum dry to obtain the antistatic agent.

[0078] Example 3

[0079] A smooth and antistatic composite masterbatch comprises the following components in parts by weight:

[0080] 80 parts polypropylene, 20 parts antistatic agent, 4 parts behenamide, 6 parts polyether modified silicone oil, 3 parts polyethylene wax, 0.4 parts 2,6-di-tert-butyl-p-cresol, and 0.1 parts (2,4-di-tert-butylphenyl) phosphite.

[0081] The preparation method of the slippery antistatic composite masterbatch includes the following steps:

[0082] S10. Weigh each component raw material according to the weight percentage;

[0083] S20. Add the antistatic agent, slip agent, polyethylene wax and antioxidant to the mixer. The mixer speed is 1000 r / min and the mixing time is 5 min. Mix evenly to obtain the premix.

[0084] S30. Add the premixed material and polypropylene together into a twin-screw extruder. The production temperature of the twin-screw extruder is controlled at 235℃ and the screw speed is 415r / min for melt blending.

[0085] S40. The melt-blended material is extruded through the extruder head, and after being water-cooled and stretched, it is pelletized using a pelletizer and dried to obtain a smooth and antistatic composite masterbatch.

[0086] The method for preparing the antistatic agent includes the following steps:

[0087] S1. 16 mg of graphene oxide was added to 24 mL of N-methylpyrrolidone and ultrasonically dispersed to obtain a graphene oxide dispersion. 70 mg of maleic anhydride and 2 mg of pyridine were added to the graphene oxide dispersion. Under nitrogen protection, the temperature was raised to 90 °C and the mixture was stirred. After the reaction was completed, the mixture was centrifuged and washed, and then vacuum dried at 60 °C to obtain carboxylated graphene oxide.

[0088] S2. 12 mg of carboxylated graphene oxide was dispersed in 100 mL of cyclohexanone and ultrasonically dispersed. Then, 4 mg of vinyl silicone oil was added dropwise, followed by 0.04 mg of 2,2'-azobisisobutyronitrile. Under nitrogen protection, the mixture was heated to 65 °C and stirred for 8 h. After the reaction was completed, 0.03 mg of hydroquinone was added to terminate the reaction. Then, ethanol was added to precipitate the product. The product was centrifuged, washed, and dried to obtain silicone oil-modified graphene oxide.

[0089] S3. Dissolve 60 mg of hydroxyl-terminated polyoxyethylene-polyoxypropylene block copolymer in 100 mL of cyclohexanone, then add 12 mg of silicone oil-modified graphene oxide and 0.24 mg of p-toluenesulfonic acid. Under nitrogen protection, heat to 90 °C and stir to react. After the reaction is completed, distill under reduced pressure, wash, and dry under vacuum to obtain modified graphene.

[0090] S4. Add 180 mg of ethyl acetate to 12 mg of modified graphene, stir and mix under heating conditions, then add 1.8 mg of ascorbic acid, continue stirring and reacting. After the reaction is complete, cool, centrifuge and wash, and vacuum dry to obtain the antistatic agent.

[0091] Comparative Example 1

[0092] A smooth and antistatic composite masterbatch comprises the following components in parts by weight:

[0093] 70 parts polypropylene, 4 parts behenamide, 6 parts polyether modified silicone oil, 2 parts polyethylene wax, 0.4 parts 2,6-di-tert-butyl-p-cresol, and 0.1 parts (2,4-di-tert-butylphenyl) phosphite.

[0094] The preparation method of the slippery antistatic composite masterbatch includes the following steps:

[0095] S10. Weigh each component raw material according to the weight percentage;

[0096] S20. Add the slip agent, polyethylene wax and antioxidant to the mixer. The mixer speed is 1000 r / min and the mixing time is 4 min. Mix evenly to obtain the premix.

[0097] S30. Add the premixed material and polypropylene together into a twin-screw extruder. The production temperature of the twin-screw extruder is controlled at 230℃ and the screw speed is 415r / min for melt blending.

[0098] S40. The melt-blended material is extruded through the extruder head, water-cooled and stretched, then pelletized using a pelletizer and dried to obtain a smooth and antistatic composite masterbatch.

[0099] Compared with Example 1, Comparative Example 1 did not contain an antistatic agent in the composite masterbatch.

[0100] Comparative Example 2

[0101] A smooth and antistatic composite masterbatch comprises the following components in parts by weight:

[0102] 70 parts polypropylene, 15 parts antistatic agent, 4 parts behenamide, 6 parts polyether modified silicone oil, 2 parts polyethylene wax, 0.4 parts 2,6-di-tert-butyl-p-cresol and 0.1 parts (2,4-di-tert-butylphenyl) phosphite;

[0103] The preparation method of the slippery antistatic composite masterbatch includes the following steps:

[0104] S10. Weigh each component raw material according to the weight percentage;

[0105] S20. Add the antistatic agent, slip agent, polyethylene wax and antioxidant to the mixer. The mixer speed is 1000 r / min and the mixing time is 4 min. Mix evenly to obtain the premix.

[0106] S30. Add the premixed material and polypropylene together into a twin-screw extruder. The production temperature of the twin-screw extruder is controlled at 230℃ and the screw speed is 415r / min for melt blending.

[0107] S40. The melt-blended material is extruded through the extruder head, and after being water-cooled and stretched, it is pelletized using a pelletizer and dried to obtain a smooth and antistatic composite masterbatch.

[0108] The method for preparing the antistatic agent includes the following steps:

[0109] S1. 12 mg of graphene oxide was added to 20 mL of N-methylpyrrolidone and ultrasonically dispersed to obtain a graphene oxide dispersion. 60 mg of maleic anhydride and 1 mg of pyridine were added to the graphene oxide dispersion. Under nitrogen protection, the temperature was raised to 85 °C and the mixture was stirred to react. After the reaction was completed, the mixture was centrifuged and washed, and then vacuum dried at 60 °C to obtain carboxylated graphene oxide.

[0110] S2. Dissolve 80 mg of hydroxyl-terminated polyoxyethylene-polyoxypropylene block copolymer in 100 mL of cyclohexanone, then add 10 mg of carboxylated graphene oxide and 0.3 mg of p-toluenesulfonic acid. Under nitrogen protection, heat to 95 °C and stir to react. After the reaction is complete, distill under reduced pressure, wash, and dry under vacuum to obtain modified graphene.

[0111] S3. Add 150 mg of ethyl acetate to 10 mg of modified graphene, stir and mix under heating conditions, then add 2 mg of ascorbic acid, continue stirring and reacting. After the reaction is complete, cool, centrifuge and wash, and vacuum dry to obtain the antistatic agent.

[0112] Compared with Example 1, the carboxylated graphene oxide in Comparative Example 2 did not react with vinyl silicone oil.

[0113] Comparative Example 3

[0114] A smooth and antistatic composite masterbatch comprises the following components in parts by weight:

[0115] 70 parts polypropylene, 15 parts antistatic agent, 4 parts behenamide, 6 parts polyether modified silicone oil, 2 parts polyethylene wax, 0.4 parts 2,6-di-tert-butyl-p-cresol and 0.1 parts (2,4-di-tert-butylphenyl) phosphite;

[0116] The preparation method of the slippery antistatic composite masterbatch includes the following steps:

[0117] S10. Weigh each component raw material according to the weight percentage;

[0118] S20. Add the antistatic agent, slip agent, polyethylene wax and antioxidant to the mixer. The mixer speed is 1000 r / min and the mixing time is 4 min. Mix evenly to obtain the premix.

[0119] S30. Add the premixed material and polypropylene together into a twin-screw extruder. The production temperature of the twin-screw extruder is controlled at 230℃ and the screw speed is 415r / min for melt blending.

[0120] S40. The melt-blended material is extruded through the extruder head, and after being water-cooled and stretched, it is pelletized using a pelletizer and dried to obtain a smooth and antistatic composite masterbatch.

[0121] The method for preparing the antistatic agent includes the following steps:

[0122] S1. 12 mg of graphene oxide was added to 20 mL of N-methylpyrrolidone and ultrasonically dispersed to obtain a graphene oxide dispersion. 60 mg of maleic anhydride and 1 mg of pyridine were added to the graphene oxide dispersion. Under nitrogen protection, the temperature was raised to 85 °C and the mixture was stirred to react. After the reaction was completed, the mixture was centrifuged and washed, and then vacuum dried at 60 °C to obtain carboxylated graphene oxide.

[0123] S2. 10 mg of carboxylated graphene oxide was dispersed in 100 mL of cyclohexanone and ultrasonically dispersed. Then, 3 mg of vinyl silicone oil was added dropwise, followed by 0.03 mg of 2,2'-azobisisobutyronitrile. Under nitrogen protection, the mixture was heated to 63 °C and stirred for 7 h. After the reaction was completed, 0.025 mg of hydroquinone was added to terminate the reaction. Then, ethanol was added to precipitate the product. The product was centrifuged, washed, and dried to obtain silicone oil-modified graphene oxide.

[0124] S4. Add 150 mg of ethyl acetate to 10 mg of silicone oil-modified graphene oxide, stir and mix under heating conditions, then add 2 mg of ascorbic acid, continue stirring and reacting. After the reaction is complete, cool, centrifuge and wash, and vacuum dry to obtain the antistatic agent.

[0125] Compared with Example 1, the silicone oil-modified graphene oxide in Comparative Example 3 did not react with the hydroxyl-terminated polyoxyethylene-polyoxypropylene block copolymer.

[0126] Comparative Example 4

[0127] A smooth and antistatic composite masterbatch comprises the following components in parts by weight:

[0128] 70 parts polypropylene, 15 parts antistatic agent, 6 parts polyether modified silicone oil, 2 parts polyethylene wax, 0.4 parts 2,6-di-tert-butyl-p-cresol, and 0.1 parts (2,4-di-tert-butylphenyl) phosphite.

[0129] The preparation method of the slippery antistatic composite masterbatch includes the following steps:

[0130] S10. Weigh each component raw material according to the weight percentage;

[0131] S20. Add the antistatic agent, slip agent, polyethylene wax and antioxidant to the mixer. The mixer speed is 1000 r / min and the mixing time is 4 min. Mix evenly to obtain the premix.

[0132] S30. Add the premixed material and polypropylene together into a twin-screw extruder. The production temperature of the twin-screw extruder is controlled at 230℃ and the screw speed is 415r / min for melt blending.

[0133] S40. The melt-blended material is extruded through the extruder head, and after being water-cooled and stretched, it is pelletized using a pelletizer and dried to obtain a smooth and antistatic composite masterbatch.

[0134] The method for preparing the antistatic agent includes the following steps:

[0135] S1. 12 mg of graphene oxide was added to 20 mL of N-methylpyrrolidone and ultrasonically dispersed to obtain a graphene oxide dispersion. 60 mg of maleic anhydride and 1 mg of pyridine were added to the graphene oxide dispersion. Under nitrogen protection, the temperature was raised to 85 °C and the mixture was stirred to react. After the reaction was completed, the mixture was centrifuged and washed, and then vacuum dried at 60 °C to obtain carboxylated graphene oxide.

[0136] S2. 10 mg of carboxylated graphene oxide was dispersed in 100 mL of cyclohexanone and ultrasonically dispersed. Then, 3 mg of vinyl silicone oil was added dropwise, followed by 0.03 mg of 2,2'-azobisisobutyronitrile. Under nitrogen protection, the mixture was heated to 63 °C and stirred for 7 h. After the reaction was completed, 0.025 mg of hydroquinone was added to terminate the reaction. Then, ethanol was added to precipitate the product. The product was centrifuged, washed, and dried to obtain silicone oil-modified graphene oxide.

[0137] S3. Dissolve 80 mg of hydroxyl-terminated polyoxyethylene-polyoxypropylene block copolymer in 100 mL of cyclohexanone, then add 10 mg of silicone oil-modified graphene oxide and 0.3 mg of p-toluenesulfonic acid. Under nitrogen protection, heat to 95 °C and stir to react. After the reaction is completed, distill under reduced pressure, wash, and vacuum dry to obtain modified graphene.

[0138] S4. Add 150 mg of ethyl acetate to 10 mg of modified graphene, stir and mix under heating conditions, then add 2 mg of ascorbic acid, continue stirring and reacting. After the reaction is complete, cool, centrifuge and wash, and vacuum dry to obtain the antistatic agent.

[0139] Compared with Example 1, Comparative Example 4 did not contain behenamide in its slip agent.

[0140] Test methods and results

[0141] The composite masterbatches obtained in Examples 1-3 and Comparative Examples 1-4 were mixed with polypropylene at a weight ratio of 1:500, and then placed in a high-speed mixer and stirred at 300-500 r / min for 5 min to achieve uniform dispersion. The mixture was then formed into a 25 μm thick film using a twin-screw extruder, a casting machine, and a biaxial stretching machine. The film was cut into 10 cm × 10 cm square samples, with at least 5 parallel samples prepared for each test group. The surface resistivity of the samples from Examples 1-3 and Comparative Examples 1-4 was tested according to national standard GB / T1410-2006; the coefficient of friction of the samples from Examples 1-3 and Comparative Examples 1-4 was tested according to GB / 10006-2004. The test results are shown in Table 1.

[0142] Table 1 Performance Test Results

[0143] Group Surface resistivity (Ω) Static friction coefficient Example 1 7.58 x 10 10 ]] 0.21 Example 2 3.87 x 10 11 ]] 0.29 Example 3 6.32 x 10 11 ]] 0.24 Comparative Example 1 9.64 x 10 15 ]] 0.43 Comparative Example 2 7.83 x 10 14 ]] 0.37 Comparative Example 3 5.92 x 10 15 ]] 0.39 Comparative Example 4 9.98 x 10 12 ]] 0.58

[0144] As can be seen from the results in the table above, compared with comparative examples 1 to 4, the films prepared from the composite masterbatches obtained in Examples 1 to 3 of the present invention have lower surface resistivity, significantly improved antistatic effect, lower static friction coefficient, and better slip performance.

[0145] The above are merely preferred embodiments of the present invention and do not limit the patent scope of the present invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the patent protection scope of the present invention.

Claims

1. A smooth and antistatic composite masterbatch, characterized in that, It includes the following components in parts by weight: 60-80 parts polypropylene, 10-20 parts antistatic agent, 5-15 parts slip agent, 1-3 parts dispersant, and 0.1-1 parts antioxidant; The method for preparing the antistatic agent includes the following steps: S1. Graphene oxide is added to N-methylpyrrolidone and ultrasonically dispersed to obtain a graphene oxide dispersion. Maleic anhydride and pyridine are added to the graphene oxide dispersion. Under nitrogen protection, the temperature is raised to 80-90°C and the mixture is stirred to react. After the reaction is completed, the mixture is centrifuged, washed, and vacuum dried to obtain carboxylated graphene oxide. S2. The carboxylated graphene oxide is dispersed in cyclohexanone and ultrasonically dispersed. Then, vinyl silicone oil is added dropwise, followed by 2,2'-azobisisobutyronitrile. Under nitrogen protection, the mixture is heated and stirred. After the reaction is completed, hydroquinone is added to terminate the reaction. Then, ethanol is added to precipitate the mixture. After centrifugation, washing, and drying, silicone oil-modified graphene oxide is obtained. S3. Dissolve the hydroxyl-terminated polyoxyethylene-polyoxypropylene block copolymer in cyclohexanone, then add the silicone oil-modified graphene oxide and p-toluenesulfonic acid. Under nitrogen protection, heat to 90-100°C and stir the reaction. After the reaction is completed, distill under reduced pressure, wash, and dry under vacuum to obtain modified graphene. S4. Ethyl acetate was added to the modified graphene, and the mixture was stirred under heating conditions. Ascorbic acid was then added, and the reaction was continued with stirring. After the reaction was completed, the mixture was cooled, centrifuged and washed, and then vacuum dried to obtain an antistatic agent. The slip agent includes behenicolamide and polyether-modified silicone oil.

2. The slippery antistatic composite masterbatch according to claim 1, characterized in that, The dispersant includes at least one of polyethylene wax and oxidized polyethylene wax; the antioxidant includes 2,6-di-tert-butyl-p-cresol and (2,4-di-tert-butylphenyl) phosphite, wherein the mass ratio of 2,6-di-tert-butyl-p-cresol and (2,4-di-tert-butylphenyl) phosphite is (4-6):(1-3).

3. The slippery antistatic composite masterbatch according to claim 1, characterized in that, The mass ratio of behenicol amide to polyether modified silicone oil is 1:(1.2-2.5).

4. The slippery antistatic composite masterbatch according to claim 1, characterized in that, In step S1, the ratio of graphene oxide, N-methylpyrrolidone, maleic anhydride, and pyridine is (4-8 mg): (8-12 mL): (25-35 mg): (0.1-1 mg). The vacuum drying temperature is 55–65°C, and the vacuum drying time is 5–7 hours.

5. The slippery antistatic composite masterbatch according to claim 1, characterized in that, In step S2, the mass ratio of carboxylated graphene oxide, vinyl silicone oil, 2,2'-azobisisobutyronitrile, and hydroquinone is (8-12):(2-4):(0.02-0.04):(0.02-0.03). The temperature is raised to 60-65°C, and the stirring reaction time is 6-8 hours.

6. The slippery antistatic composite masterbatch according to claim 1, characterized in that, In step S3, the mass ratio of the hydroxyl-terminated polyoxyethylene-polyoxypropylene block copolymer, the silicone oil-modified graphene oxide, and the p-toluenesulfonic acid is (8-10):(1-2):(0.03-0.04). The vacuum drying temperature is 75–85°C, and the vacuum drying time is 3–5 hours.

7. The slippery antistatic composite masterbatch according to claim 1, characterized in that, In step S4, the mass ratio of the modified graphene, ethyl acetate, and ascorbic acid is (1-2):(10-30):(0.1-0.3). The temperature is then raised to 60–65°C; The vacuum drying temperature is 65–75°C, and the vacuum drying time is 7.5–8.5 h.

8. A method for preparing a slip-resistant and antistatic composite masterbatch as described in any one of claims 1 to 7, characterized in that, Includes the following steps: S10. Weigh each component raw material according to the weight percentage; S20. Add the antistatic agent, slip agent, dispersant and antioxidant to the mixer and mix evenly to obtain the premix; S30. Add the premixed material and polypropylene together into a twin-screw extruder for melt blending; S40. The melt-blended material is extruded through the extruder head, water-cooled and stretched, then pelletized using a pelletizer and dried to obtain a smooth and antistatic composite masterbatch.

9. The preparation method of the slippery antistatic composite masterbatch as described in claim 8, characterized in that, In step S20, the speed of the mixer is 500-1500 r / min, and the mixing time is 3-5 min; in step S30, the production temperature of the twin-screw extruder is controlled at 225-235℃, and the screw speed is 400-430 r / min.

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