Preparation method of antistatic polypropylene material

Abstract

The invention provides an antistatic polypropylene material preparation method, which comprises: S1, adding hydrogen peroxide to deep sea fish oil, carrying out a stirring reaction, removing a water layer, and washing to obtain oxidized deep sea fish oil; s2, putting polyethylene glycol, oxidized deep sea fish oil and a catalyst into a reaction kettle, and heating and stirring; washing and drying to obtain modified fish oil; s3, modified fish oil is added into the nanometer tourmaline powder ethanol dispersion liquid, ultrasonic dispersion is carried out while stirring is carried out, ethanol is removed, degassing is carried out, and a nanometer tourmaline powder / modified fish oil compound is obtained; s4, polypropylene, a nano tourmaline powder / modified fish oil compound and antioxidant are adopted for preparing particles for the outer layer of the film; preparing material particles for the inner layer of the film from polypropylene and an antioxidant; and S5, preparing the antistatic polypropylene material from the material particles for the outer layer of the film and the material particles for the inner layer of the film through a co-extrusion casting process. The polypropylene material prepared by the invention is excellent in antistatic property, and meanwhile, the mechanical property is also improved.

Description

Technical Field

[0001] The invention relates to the technical field of polymer materials, and in particular to a method for preparing an antistatic polypropylene material. Background Art

[0002] Polypropylene has a high cost-effectiveness, is non-toxic, and has excellent mechanical properties, heat resistance, and corrosion resistance. Therefore, using polypropylene film as a packaging material has broad application prospects and many advantages. Polypropylene film is prone to static electricity during use as a packaging material. Static electricity can easily adsorb impurities such as dust and pollutants on the surface of polypropylene film packaging materials, which not only affects the appearance of the packaging material, but may also contaminate the packaged products and reduce product quality. Therefore, it is necessary to perform antistatic treatment on the outer surface of the polypropylene film.

[0003] At present, when the outer surface of polypropylene film is treated for antistatic, corona treatment is generally performed. Corona treatment ionizes and activates the surface of plastic film through the action of electric field, and can also effectively remove static electricity on the plastic surface, reduce the adsorption of dust and pollutants, etc., and improve the overall quality of the product. However, the antistatic performance of polypropylene film treated by this method is not durable. Therefore, by adding antistatic agents to eliminate the static electricity of polypropylene, the antistatic durability is significantly stronger.

[0004] Among them, fatty acid ester antistatic agent is a non-ionic antistatic agent, non-toxic or low-toxic, with stable thermal performance, excellent processing performance, good compatibility with polypropylene, and good overall antistatic effect. At present, existing literature mixes fish oil, glycerol and catalyst, and refluxes to obtain modified fish oil, and adds the modified fish oil as fatty acid ester antistatic agent to polypropylene to prepare antistatic polypropylene material, which can reduce the surface resistivity and volume resistivity of polypropylene, and expand the purpose of fish oil. Among them, fish oil is a byproduct of fishery resources, and the expansion of its purpose is conducive to reducing the waste of fishery resources and improving the utilization efficiency of resources.

[0005] However, the modified fish oil obtained in the prior art has a relatively limited effect on improving the antistatic effect of polypropylene. As the packaging field increases the quality requirements for polypropylene film packaging materials, it is necessary to develop modified fish oils with better antistatic properties, and it is necessary to make the polypropylene material have excellent antistatic properties and excellent mechanical properties. Summary of the invention

[0006] The purpose of the present invention is to provide a method for preparing an antistatic polypropylene material. The antistatic polypropylene material is a double-layer co-extruded film material. By adding a proper amount of antistatic agent into the outer layer of the polypropylene film, the outer layer of the polypropylene film has excellent antistatic effect and excellent mechanical properties. At the same time, the present invention uses deep-sea fish oil as the main raw material of the antistatic agent, which effectively expands the application of deep-sea fish oil.

[0007] To achieve the above objectives, the present invention is implemented through the following technical solutions: A method for preparing an antistatic polypropylene material comprises the following steps: S1: Under visible light conditions, hydrogen peroxide is added to the deep-sea fish oil, and the mixture is stirred and reacted at 50-55°C for 2.5-3 hours, and then the water layer is removed and the fish oil layer is washed with a sodium chloride solution to obtain oxidized deep-sea fish oil; S2: placing polyethylene glycol, oxidized deep-sea fish oil and a catalyst in a reaction kettle, heating to 130-135°C while stirring and stirring at a constant temperature for 3-5 hours; after the reaction is completed, washing with a sodium chloride solution and then vacuum drying to obtain modified fish oil; S3: preparing a nano-tourmaline powder ethanol dispersion; adding modified fish oil to the nano-tourmaline powder ethanol dispersion, dispersing it ultrasonically for 3 to 6 hours while stirring, and then removing ethanol by vacuum distillation while stirring, and after removing ethanol, performing vacuum degassing to obtain a nano-tourmaline powder / modified fish oil composite; S4: mixing polypropylene, nano-tourmaline powder / modified fish oil compound and antioxidant in a high-speed mixer, and then placing them in a twin-screw extruder for melt blending, extrusion and granulation to obtain pellets for the outer layer of the film; mixing polypropylene and antioxidant in a high-speed mixer, and then placing them in a twin-screw extruder for melt blending, extrusion and granulation to obtain pellets for the inner layer of the film; S5: adding the pellets for the outer layer of the film and the pellets for the inner layer of the film into two screw extruders for melting, and extruding the two layers of melt through a die to form a cast film, which is then shaped, cooled, and rolled to obtain the antistatic polypropylene material.

[0008] Preferably, in step S1, the deep-sea fish oil is one of tuna oil, salmon oil, cod oil, sardine oil, and mackerel oil, or a mixture of two or more of them in any proportion.

[0009] Preferably, in step S1, the mass fraction of the hydrogen peroxide is 10-15%, and the amount of hydrogen peroxide added is 35-50% of the mass of the deep-sea fish oil.

[0010] Preferably, in step S2, the mass ratio of the polyethylene glycol to the oxidized deep-sea fish oil is 1:4-5.5; and the average molecular weight of the polyethylene glycol is 400-600.

[0011] Preferably, in step S2, the catalyst is a sodium bisulfate aqueous solution, the mass fraction of the sodium bisulfate aqueous solution is 30-40%, and the amount of the sodium bisulfate aqueous solution is 1.5-2% of the mass of the oxidized deep-sea fish oil; During the reaction, the water in the sodium bisulfate aqueous solution and the water produced by the reaction are condensed in a condenser and then discharged.

[0012] Preferably, in step S1 and step S2, the mass fraction of the sodium chloride solution is 2-3%.

[0013] Preferably, in step S3, the concentration of nano-tourmaline powder in the nano-tourmaline powder ethanol dispersion is 30-60 mg / mL; the preparation method of the nano-tourmaline powder ethanol dispersion comprises the following steps: adding nano-tourmaline powder with a particle size of 50-200 nm to anhydrous ethanol, and ultrasonically dispersing for 2-5 hours while stirring to obtain the nano-tourmaline powder.

[0014] Preferably, in step S3, the mass volume ratio of the modified fish oil to the nano-tourmaline powder ethanol dispersion is 1 g: 3-5 mL.

[0015] Preferably, in step S4, the granules for the outer layer of the film include the following raw materials in weight percentage: 2.2-3.5% of nano-tourmaline powder / modified fish oil compound, 0.2-0.3% of antioxidant, and the balance of polypropylene; The granules for the inner layer of the film include the following raw materials in weight percentage: 0.05-0.1% antioxidant and the balance polypropylene.

[0016] Preferably, in step S4, when preparing the pellets for the outer layer of the film and the pellets for the inner layer of the film, the temperature of the twin-screw extruder is 170-195°C, and the temperatures of zones one to ten are: 170°C, 170°C, 175°C, 180°C, 185°C, 190°C, 190°C, 185°C, 180°C, 180°C, and the head temperature is 195°C.

[0017] The beneficial effects of the present invention are: 1. The present invention adopts oxidized deep-sea fish oil and polyethylene glycol to react to prepare modified fish oil. By reasonably controlling the reaction conditions and the amount of polyethylene glycol added and the molecular weight, the prepared modified fish oil can contain more polyethylene glycol fatty acid esters, so that the modified fish oil exhibits higher antistatic properties and better compatibility with polypropylene.

[0018] 2. In the process of preparing the modified fish oil, the deep-sea fish oil is first oxidized with an appropriate amount of hydrogen peroxide. After the hydrogen peroxide oxidation treatment, the reactivity of the deep-sea fish oil is increased, so that the prepared modified fish oil as a whole exhibits more excellent antistatic properties, and the composite prepared with the nano tourmaline powder exhibits better effects in terms of antistatic properties and mechanical properties. If too much hydrogen peroxide is used for oxidation treatment and the oxidation time is too long, it will lead to excessive oxidation, which will lead to reduced performance of the modified fish oil.

[0019] 3. On the basis of the modified fish oil prepared by the present invention, it is mixed with nano-tourmaline powder ethanol dispersion, and stirred ultrasonic dispersion treatment is carried out, after the subsequent decompression distillation removes ethanol, the nano-tourmaline powder can be highly dispersed in the modified fish oil, when the antistatic agent nano-tourmaline powder / modified fish oil complex prepared is mixed with polypropylene to prepare antistatic polypropylene material, the nano-tourmaline powder is highly dispersed in polypropylene, and the compatibility between nano-tourmaline powder and polypropylene is significantly enhanced. Highly dispersed nano-tourmaline powder can significantly reduce the volume resistivity and surface resistivity of polypropylene material, and the antistatic performance of polypropylene material is significantly improved. Meanwhile, the addition of nano-tourmaline powder can also enhance the strength, toughness and heat resistance of polypropylene material.

[0020] 4. The antistatic polypropylene material of the present invention is a double-layer co-extruded film material. By adding a proper amount of antistatic agent into the outer layer of the polypropylene film, the outer layer of the polypropylene film has excellent antistatic effect, effectively reducing the adsorption of impurities such as dust and pollutants, and has excellent mechanical properties, so that the polypropylene film packaging material is not easily damaged; at the same time, the present invention uses deep-sea fish oil as the main raw material of the antistatic agent, which effectively expands the application of deep-sea fish oil. DETAILED DESCRIPTION

[0021] In order to make the purpose, technical solution and advantages of the embodiments of the present invention clearer, the technical solution in the embodiments of the present invention will be clearly and completely described below in combination with the embodiments of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0022] Embodiment 1: A method for preparing an antistatic polypropylene material comprises the following steps: S1: Under visible light conditions, add 12% hydrogen peroxide to tuna oil, and the amount of hydrogen peroxide added is 40% of the mass of deep-sea fish oil; stir and react at 55°C for 3 hours, and the stirring speed is 120r / min, then remove the water layer, and use a 3% sodium chloride solution to wash the fish oil layer to obtain oxidized deep-sea fish oil; S2: Add polyethylene glycol 400 and oxidized deep-sea fish oil in a mass ratio of 1:5 to the reactor, and then add a sodium bisulfate aqueous solution with a mass fraction of 2% of the oxidized deep-sea fish oil to the reactor, and the mass fraction of the sodium bisulfate aqueous solution is 35%; heat to 135°C while stirring and stir at a constant temperature for 3 hours, and the stirring speed is 200r / min. During the reaction, the water in the sodium bisulfate aqueous solution and the water generated by the reaction are condensed and discharged through a condenser; after the reaction is completed, wash with a sodium chloride solution with a mass fraction of 3%, and then vacuum dry to remove residual moisture to obtain modified fish oil; S3: Add nano-tourmaline powder with a particle size of 50-200 nm to anhydrous ethanol, and disperse it ultrasonically for 3 h while stirring. The stirring speed is 360 r / min and the ultrasonic power is 500 W to prepare an ethanol dispersion of nano-tourmaline powder with a concentration of 50 mg / mL; Add modified fish oil to the nano-tourmaline powder ethanol dispersion, the mass volume ratio of the modified fish oil to the nano-tourmaline powder ethanol dispersion is 1g:5mL; ultrasonically disperse for 5h while stirring, the stirring speed is 360r / min, the ultrasonic power is 300W, and then remove the ethanol by vacuum distillation while stirring, and after removing the ethanol, perform vacuum degassing to obtain a nano-tourmaline powder / modified fish oil composite; S4: Place polypropylene, nano-tourmaline powder / modified fish oil complex and antioxidant 1010 in a high mixer for mixing, and then place them in a twin-screw extruder for melt blending, extrusion and granulation to obtain pellets for the outer layer of the film; place polypropylene and antioxidant 1010 in a high mixer for mixing, and then place them in a twin-screw extruder for melt blending, extrusion and granulation to obtain pellets for the inner layer of the film; when preparing the pellets for the outer layer of the film and the pellets for the inner layer of the film, the temperature of the twin-screw extrusion is 170~195℃, and the temperatures of zones 1 to 10 are respectively 170℃, 170℃, 175℃, 180℃, 185℃, 190℃, 190℃, 185℃, 180℃, 180℃, and the head temperature is 195℃.

[0023] The material particles for the outer layer of the film include the following raw materials in weight percentage: 3% of nano tourmaline powder / modified fish oil compound, 0.2% of antioxidant 1010, and the balance is polypropylene; the material particles for the inner layer of the film include the following raw materials in weight percentage: 0.1% of antioxidant 1010, and the balance is polypropylene.

[0024] S5: adding the pellets for the outer layer of the film and the pellets for the inner layer of the film into two screw extruders for melting, and extruding the two layers of melt through a die to form a cast film, which is then shaped, cooled, and rolled to obtain the antistatic polypropylene material.

[0025] Embodiment 2: A method for preparing an antistatic polypropylene material comprises the following steps: S1: Under visible light conditions, add 15% hydrogen peroxide to tuna oil, and the amount of hydrogen peroxide added is 35% of the mass of deep-sea fish oil; stir and react at 52°C for 2.5 hours, and the stirring speed is 120r / min, then remove the water layer, and use a 3% sodium chloride solution to wash the fish oil layer to obtain oxidized deep-sea fish oil; S2: Add polyethylene glycol 600 and oxidized deep-sea fish oil in a mass ratio of 1:5.5 to the reactor, and then add a sodium bisulfate aqueous solution with a mass fraction of 1.5% of the mass of the oxidized deep-sea fish oil to the reactor, and the mass fraction of the sodium bisulfate aqueous solution is 40%; heat to 130°C while stirring and stir at a constant temperature for 4 hours, and the stirring speed is 200r / min. During the reaction, the water in the sodium bisulfate aqueous solution and the water generated by the reaction are condensed and discharged through a condenser; after the reaction is completed, wash with a sodium chloride solution with a mass fraction of 3%, and then vacuum dry to remove residual moisture to obtain modified fish oil; S3: Add nano-tourmaline powder with a particle size of 50-200 nm to anhydrous ethanol, and disperse it ultrasonically for 3 h while stirring. The stirring speed is 360 r / min and the ultrasonic power is 500 W to prepare an ethanol dispersion of nano-tourmaline powder with a concentration of 50 mg / mL; Add modified fish oil to the nano-tourmaline powder ethanol dispersion, the mass volume ratio of the modified fish oil to the nano-tourmaline powder ethanol dispersion is 1g:5mL; ultrasonic dispersion is performed for 4 hours while stirring, the stirring speed is 360r / min, the ultrasonic power is 300W, and then the ethanol is removed by reduced pressure distillation while stirring, and after the ethanol is removed, vacuum degassing is performed to obtain a nano-tourmaline powder / modified fish oil composite; S4: Place polypropylene, nano-tourmaline powder / modified fish oil complex and antioxidant 1010 in a high mixer for mixing, and then place them in a twin-screw extruder for melt blending, extrusion and granulation to obtain pellets for the outer layer of the film; place polypropylene and antioxidant 1010 in a high mixer for mixing, and then place them in a twin-screw extruder for melt blending, extrusion and granulation to obtain pellets for the inner layer of the film; when preparing the pellets for the outer layer of the film and the pellets for the inner layer of the film, the temperature of the twin-screw extrusion is 170~195℃, and the temperatures of zones 1 to 10 are respectively 170℃, 170℃, 175℃, 180℃, 185℃, 190℃, 190℃, 185℃, 180℃, 180℃, and the head temperature is 195℃.

[0026] The material particles for the outer layer of the film include the following raw materials in weight percentage: 3.5% of nano tourmaline powder / modified fish oil compound, 0.2% of antioxidant 1010, and the balance of polypropylene; the material particles for the inner layer of the film include the following raw materials in weight percentage: 0.05% of antioxidant 1010, and the balance of polypropylene.

[0027] S5: adding the pellets for the outer layer of the film and the pellets for the inner layer of the film into two screw extruders for melting, and extruding the two layers of melt through a die to form a cast film, which is then shaped, cooled, and rolled to obtain the antistatic polypropylene material.

[0028] Embodiment 3: A method for preparing an antistatic polypropylene material comprises the following steps: S1: Under visible light conditions, add 10% hydrogen peroxide to tuna oil, and the amount of hydrogen peroxide added is 50% of the mass of deep-sea fish oil; stir and react at 52°C for 3 hours, and the stirring speed is 120r / min, then remove the water layer, and use a 2% sodium chloride solution to wash the fish oil layer to obtain oxidized deep-sea fish oil; S2: Add polyethylene glycol 600 and oxidized deep-sea fish oil in a mass ratio of 1:4 into the reactor, and then add a sodium bisulfate aqueous solution with a mass fraction of 2% of the oxidized deep-sea fish oil into the reactor, and the mass fraction of the sodium bisulfate aqueous solution is 35%; heat to 135°C while stirring and stir at a constant temperature for 4 hours, and the stirring speed is 200r / min. During the reaction, the water in the sodium bisulfate aqueous solution and the water generated by the reaction are condensed and discharged through a condenser; after the reaction is completed, wash with a sodium chloride solution with a mass fraction of 2%, and then vacuum dry to remove residual moisture to obtain modified fish oil; S3: Add nano-tourmaline powder with a particle size of 50-200 nm to anhydrous ethanol, and disperse it ultrasonically for 3.5 h while stirring at a stirring speed of 360 r / min and an ultrasonic power of 500 W to prepare an ethanol dispersion of nano-tourmaline powder with a concentration of 45 mg / mL; Add modified fish oil to the nano-tourmaline powder ethanol dispersion, the mass volume ratio of the modified fish oil to the nano-tourmaline powder ethanol dispersion is 1g:3mL; ultrasonic dispersion is performed for 5.5h while stirring, the stirring speed is 360r / min, the ultrasonic power is 300W, and then the ethanol is removed by reduced pressure distillation while stirring, and after the ethanol is removed, vacuum degassing is performed to obtain a nano-tourmaline powder / modified fish oil composite; S4: Place polypropylene, nano-tourmaline powder / modified fish oil complex and antioxidant 1010 in a high mixer for mixing, and then place them in a twin-screw extruder for melt blending, extrusion and granulation to obtain pellets for the outer layer of the film; place polypropylene and antioxidant 1010 in a high mixer for mixing, and then place them in a twin-screw extruder for melt blending, extrusion and granulation to obtain pellets for the inner layer of the film; when preparing the pellets for the outer layer of the film and the pellets for the inner layer of the film, the temperature of the twin-screw extrusion is 170~195℃, and the temperatures of zones 1 to 10 are respectively 170℃, 170℃, 175℃, 180℃, 185℃, 190℃, 190℃, 185℃, 180℃, 180℃, and the head temperature is 195℃.

[0029] The material particles for the outer layer of the film include the following raw materials in weight percentage: 3% of nano tourmaline powder / modified fish oil compound, 0.2% of antioxidant 1010, and the balance is polypropylene; the material particles for the inner layer of the film include the following raw materials in weight percentage: 0.1% of antioxidant 1010, and the balance is polypropylene.

[0030] S5: adding the pellets for the outer layer of the film and the pellets for the inner layer of the film into two screw extruders for melting, and extruding the two layers of melt through a die to form a cast film, which is then shaped, cooled, and rolled to obtain the antistatic polypropylene material.

[0031] Embodiment 4: A method for preparing an antistatic polypropylene material comprises the following steps: S1: Under visible light conditions, add 10% hydrogen peroxide to tuna oil, and the amount of hydrogen peroxide added is 35% of the mass of deep-sea fish oil; stir and react at 50°C for 3 hours at a stirring speed of 120r / min, then remove the water layer, and wash the fish oil layer with a 3% sodium chloride solution to obtain oxidized deep-sea fish oil; S2: Add polyethylene glycol 400 and oxidized deep-sea fish oil in a mass ratio of 1:4 to the reactor, and then add a sodium bisulfate aqueous solution with a mass fraction of 2% of the oxidized deep-sea fish oil to the reactor, and the mass fraction of the sodium bisulfate aqueous solution is 30%; heat to 135°C while stirring and stir at a constant temperature for 3 hours, and the stirring speed is 200r / min. During the reaction, the water in the sodium bisulfate aqueous solution and the water generated by the reaction are condensed and discharged through a condenser; after the reaction is completed, wash with a sodium chloride solution with a mass fraction of 3%, and then vacuum dry to remove residual moisture to obtain modified fish oil; S3: Add nano-tourmaline powder with a particle size of 50-200 nm to anhydrous ethanol, and disperse it ultrasonically for 5 h while stirring. The stirring speed is 360 r / min and the ultrasonic power is 500 W to prepare a nano-tourmaline powder ethanol dispersion with a concentration of 60 mg / mL; Add modified fish oil to the nano-tourmaline powder ethanol dispersion, the mass volume ratio of the modified fish oil to the nano-tourmaline powder ethanol dispersion is 1g:5mL; ultrasonic dispersion is performed for 4 hours while stirring, the stirring speed is 360r / min, the ultrasonic power is 300W, and then the ethanol is removed by reduced pressure distillation while stirring, and after the ethanol is removed, vacuum degassing is performed to obtain a nano-tourmaline powder / modified fish oil composite; S4: Place polypropylene, nano-tourmaline powder / modified fish oil complex and antioxidant 1010 in a high mixer for mixing, and then place them in a twin-screw extruder for melt blending, extrusion and granulation to obtain pellets for the outer layer of the film; place polypropylene and antioxidant 1010 in a high mixer for mixing, and then place them in a twin-screw extruder for melt blending, extrusion and granulation to obtain pellets for the inner layer of the film; when preparing the pellets for the outer layer of the film and the pellets for the inner layer of the film, the temperature of the twin-screw extrusion is 170~195℃, and the temperatures of zones 1 to 10 are respectively 170℃, 170℃, 175℃, 180℃, 185℃, 190℃, 190℃, 185℃, 180℃, 180℃, and the head temperature is 195℃.

[0032] The granules for the outer layer of the film include the following raw materials in weight percentage: 2.8% of nano tourmaline powder / modified fish oil compound, 0.3% of antioxidant 1010, and the balance of polypropylene; the granules for the inner layer of the film include the following raw materials in weight percentage: 0.08% of antioxidant 1010, and the balance of polypropylene.

[0033] S5: adding the pellets for the outer layer of the film and the pellets for the inner layer of the film into two screw extruders for melting, and extruding the two layers of melt through a die to form a cast film, which is then shaped, cooled, and rolled to obtain the antistatic polypropylene material.

[0034] Embodiment 5: A method for preparing an antistatic polypropylene material comprises the following steps: S1: Under visible light conditions, add 12% hydrogen peroxide to tuna oil, and the amount of hydrogen peroxide added is 50% of the mass of deep-sea fish oil; stir and react at 52°C for 2.5 hours, and the stirring speed is 120r / min, then remove the water layer, and use a 2% sodium chloride solution to wash the fish oil layer to obtain oxidized deep-sea fish oil; S2: Add polyethylene glycol 600 and oxidized deep-sea fish oil in a mass ratio of 1:4.5 to the reactor, and then add a sodium bisulfate aqueous solution with a mass fraction of 1.8% of the mass of the oxidized deep-sea fish oil to the reactor, and the mass fraction of the sodium bisulfate aqueous solution is 40%; heat to 130°C while stirring and stir at a constant temperature for 5 hours, and the stirring speed is 200r / min. During the reaction, the water in the sodium bisulfate aqueous solution and the water generated by the reaction are condensed and discharged through a condenser; after the reaction is completed, wash with a sodium chloride solution with a mass fraction of 2%, and then vacuum dry to remove residual moisture to obtain modified fish oil; S3: Add nano-tourmaline powder with a particle size of 50-200 nm to anhydrous ethanol, and disperse it ultrasonically for 2 h while stirring. The stirring speed is 360 r / min and the ultrasonic power is 500 W to prepare an ethanol dispersion of nano-tourmaline powder with a concentration of 30 mg / mL; Add modified fish oil to the nano-tourmaline powder ethanol dispersion, the mass volume ratio of the modified fish oil to the nano-tourmaline powder ethanol dispersion is 1g:3.5mL; ultrasonically disperse for 3h while stirring, the stirring speed is 360r / min, the ultrasonic power is 300W, and then remove ethanol by reduced pressure distillation while stirring, and after removing the ethanol, perform vacuum degassing to obtain a nano-tourmaline powder / modified fish oil composite; S4: Place polypropylene, nano-tourmaline powder / modified fish oil complex and antioxidant 1010 in a high mixer for mixing, and then place them in a twin-screw extruder for melt blending, extrusion and granulation to obtain pellets for the outer layer of the film; place polypropylene and antioxidant 1010 in a high mixer for mixing, and then place them in a twin-screw extruder for melt blending, extrusion and granulation to obtain pellets for the inner layer of the film; when preparing the pellets for the outer layer of the film and the pellets for the inner layer of the film, the temperature of the twin-screw extrusion is 170~195℃, and the temperatures of zones 1 to 10 are respectively 170℃, 170℃, 175℃, 180℃, 185℃, 190℃, 190℃, 185℃, 180℃, 180℃, and the head temperature is 195℃.

[0035] The granules for the outer layer of the film include the following raw materials in weight percentage: 3% of nano tourmaline powder / modified fish oil compound, 0.25% of antioxidant 1010, and the balance of polypropylene; the granules for the inner layer of the film include the following raw materials in weight percentage: 0.1% of antioxidant 1010, and the balance of polypropylene.

[0036] S5: adding the pellets for the outer layer of the film and the pellets for the inner layer of the film into two screw extruders for melting, and extruding the two layers of melt through a die to form a cast film, which is then shaped, cooled, and rolled to obtain the antistatic polypropylene material.

[0037] Embodiment 6: A method for preparing an antistatic polypropylene material comprises the following steps: S1: Under visible light conditions, add 15% hydrogen peroxide to tuna oil, and the amount of hydrogen peroxide added is 45% of the mass of deep-sea fish oil; stir and react at 55°C for 2.5 hours, and the stirring speed is 120r / min, then remove the water layer, and use a 2% sodium chloride solution to wash the fish oil layer to obtain oxidized deep-sea fish oil; S2: Add polyethylene glycol 600 and oxidized deep-sea fish oil in a mass ratio of 1:5.5 to the reactor, and then add a sodium bisulfate aqueous solution with a mass fraction of 1.5% of the mass of the oxidized deep-sea fish oil to the reactor, and the mass fraction of the sodium bisulfate aqueous solution is 35%; heat to 133°C while stirring and stir at a constant temperature for 4 hours, and the stirring speed is 200r / min. During the reaction, the water in the sodium bisulfate aqueous solution and the water generated by the reaction are condensed and discharged through a condenser; after the reaction is completed, wash with a sodium chloride solution with a mass fraction of 2%, and then vacuum dry to remove residual moisture to obtain modified fish oil; S3: Add nano-tourmaline powder with a particle size of 50-200 nm to anhydrous ethanol, and disperse it ultrasonically for 3 h while stirring at a stirring speed of 360 r / min and an ultrasonic power of 500 W to prepare an ethanol dispersion of nano-tourmaline powder with a concentration of 45 mg / mL; Add modified fish oil to the nano-tourmaline powder ethanol dispersion, the mass volume ratio of the modified fish oil to the nano-tourmaline powder ethanol dispersion is 1g:3mL; ultrasonically disperse for 6 hours while stirring, the stirring speed is 360r / min, the ultrasonic power is 300W, and then the ethanol is removed by reduced pressure distillation while stirring, and after the ethanol is removed, vacuum degassing is performed to obtain a nano-tourmaline powder / modified fish oil composite; S4: Place polypropylene, nano-tourmaline powder / modified fish oil complex and antioxidant 1010 in a high mixer for mixing, and then place them in a twin-screw extruder for melt blending, extrusion and granulation to obtain pellets for the outer layer of the film; place polypropylene and antioxidant 1010 in a high mixer for mixing, and then place them in a twin-screw extruder for melt blending, extrusion and granulation to obtain pellets for the inner layer of the film; when preparing the pellets for the outer layer of the film and the pellets for the inner layer of the film, the temperature of the twin-screw extrusion is 170~195℃, and the temperatures of zones 1 to 10 are respectively 170℃, 170℃, 175℃, 180℃, 185℃, 190℃, 190℃, 185℃, 180℃, 180℃, and the head temperature is 195℃.

[0038] The granules for the outer layer of the film include the following raw materials in weight percentage: 3.2% of nano-tourmaline powder / modified fish oil compound, 0.22% of antioxidant 1010, and the balance of polypropylene; the granules for the inner layer of the film include the following raw materials in weight percentage: 0.06% of antioxidant 1010, and the balance of polypropylene.

[0039] S5: adding the pellets for the outer layer of the film and the pellets for the inner layer of the film into two screw extruders for melting, and extruding the two layers of melt through a die to form a cast film, which is then shaped, cooled, and rolled to obtain the antistatic polypropylene material.

[0040] Comparative Example 1: The difference from Example 1 is that the deep-sea fish oil is not oxidized by hydrogen peroxide. The method for preparing modified fish oil comprises the following steps: Add polyethylene glycol 400 and deep-sea fish oil in a mass ratio of 1:5 into a reactor, and then add a sodium bisulfate aqueous solution with a mass fraction of 2% of the deep-sea fish oil into the reactor, and the mass fraction of the sodium bisulfate aqueous solution is 35%; heat to 135°C while stirring and stir at a constant temperature for 3 hours, and the stirring speed is 200r / min. During the reaction, the water in the sodium bisulfate aqueous solution and the water generated by the reaction are condensed in a condenser and discharged; after the reaction is completed, wash with a sodium chloride solution with a mass fraction of 3%, and then vacuum dry to remove residual moisture to obtain modified fish oil.

[0041] Comparative Example 2: The difference from Example 1 is that instead of using nano-tourmaline powder ethanol dispersion and modified fish oil to prepare nano-tourmaline powder / modified fish oil composite, modified fish oil and nano-tourmaline powder are directly mixed with polypropylene to prepare the material particles for the outer layer of the film.

[0042] The method for preparing the pellets for the outer layer of the film comprises the following steps: Polypropylene, modified fish oil (prepared by the same method as in Example 1), nano-tourmaline powder (particle size of 50-200 nm), and antioxidant 1010 are placed in a high mixer for mixing, and then placed in a twin-screw extruder for melt blending, extrusion, and granulation to obtain pellets for the outer layer of the film; the twin-screw extrusion temperature is 170-195°C, and the temperatures of zones 1 to 10 are respectively 170°C, 170°C, 175°C, 180°C, 185°C, 190°C, 190°C, 185°C, 180°C, 180°C, and the die temperature is 195°C.

[0043] The material particles for the outer layer of the film include the following raw materials in percentage by weight: 2.5% of modified fish oil, 0.5% of nano tourmaline powder, 0.2% of antioxidant 1010, and the balance of polypropylene.

[0044] Comparative Example 3: The difference from Example 1 is that the oxidation treatment process of deep-sea fish oil in step S1 is different. The preparation method of oxidized deep-sea fish oil includes the following steps: adding 30% hydrogen peroxide by mass to tuna oil under visible light conditions, and the amount of hydrogen peroxide added is 80% of the mass of the deep-sea fish oil; stirring the reaction at 55° C. for 5 hours at a stirring speed of 120 r / min, then removing the water layer, and washing the fish oil layer with a sodium chloride solution with a mass fraction of 3% to obtain oxidized deep-sea fish oil.

[0045] Comparative Example 4: The difference from Example 1 is that the amounts of oxidized deep-sea fish oil and polyethylene glycol added in step S2 are different, and the molecular weight of the polyethylene glycol used is different.

[0046] The preparation method of modified fish oil comprises the following steps: adding polyethylene glycol 800 and oxidized deep-sea fish oil (the preparation method is the same as that in Example 1) in a mass ratio of 1:7.5 into a reactor, and then adding a sodium bisulfate aqueous solution with a mass fraction of 2% of the oxidized deep-sea fish oil into the reactor, wherein the mass fraction of the sodium bisulfate aqueous solution is 35%; heating to 135° C. and stirring at a constant temperature for 3 hours while stirring at a speed of 200 r / min; during the reaction, water in the sodium bisulfate aqueous solution and water generated by the reaction are condensed in a condenser and then discharged; after the reaction is completed, washing with a sodium chloride solution with a mass fraction of 3%, and then vacuum drying is performed to remove residual moisture to obtain modified fish oil.

[0047] Comparative Example 5: The difference from Example 1 is that only nano tourmaline powder is used as an antistatic agent, and the preparation method of the granules for the outer layer of the film includes the following steps: Polypropylene, nano-tourmaline powder (particle size of 50-200nm) and antioxidant 1010 are placed in a high mixer for mixing, and then placed in a twin-screw extruder for melt blending, extrusion and granulation to obtain pellets for the outer layer of the film; the twin-screw extrusion temperature is 170-195°C, and the temperatures of zones 1 to 10 are respectively 170°C, 170°C, 175°C, 180°C, 185°C, 190°C, 190°C, 185°C, 180°C, 180°C, and the die temperature is 195°C.

[0048] The material particles used for the outer layer of the film include the following raw materials in percentage by weight: 1% of nano tourmaline powder, 10-100.2% of antioxidant, and the balance of polypropylene.

[0049] Comparative Example 6: The difference from Example 1 is that only modified fish oil is used as the antistatic agent, and the preparation method of the pellets for the outer layer of the film includes the following steps: Polypropylene, modified fish oil (preparation method is the same as that in Example 1) and antioxidant 1010 are placed in a high mixer for mixing, and then placed in a twin-screw extruder for melt blending, extrusion and granulation to obtain pellets for the outer layer of the film; the twin-screw extrusion temperature is 170-195°C, and the temperatures of zones 1 to 10 are respectively 170°C, 170°C, 175°C, 180°C, 185°C, 190°C, 190°C, 185°C, 180°C, 180°C, and the die temperature is 195°C.

[0050] The pellets used for the outer layer of the film include the following raw materials in percentage by weight: 3% modified fish oil, 0.2% antioxidant 1010, and the balance polypropylene.

[0051] Comparative Example 7: The difference from Example 1 is that no antistatic agent is added. The preparation method of the pellets for the outer layer of the film comprises the following steps: Place polypropylene and antioxidant 1010 in a high mixer for mixing, and then place them in a twin-screw extruder for melt blending, extrusion and granulation to obtain pellets for the outer layer of the film; the twin-screw extrusion temperature is 170-195°C, and the temperatures of zones 1 to 10 are respectively 170°C, 170°C, 175°C, 180°C, 185°C, 190°C, 190°C, 185°C, 180°C, 180°C, and the die temperature is 195°C.

[0052] The pellets for the outer layer of the film include the following raw materials in percentage by weight: 0.2% of antioxidant 1010 and the balance of polypropylene.

[0053] Performance Test: The antistatic polypropylene material used in the film outer layer of Examples 1 to 6 and Comparative Examples 1 to 7 was used to prepare corresponding polypropylene material test samples for resistivity and mechanical properties testing.

[0054] 1. The surface resistivity and volume resistivity were tested according to GB / T 1410-2006, and the sample size was 100 mm × 100 mm × 4 mm. The resistivity test results are shown in Table 1.

[0055] Table 1:

[0056] Comparing the resistivity test results of the polypropylene materials in Examples 1 to 6 in Table 1 with Comparative Example 7, it can be seen that the surface resistivity and volume resistivity of the corresponding polypropylene materials can be significantly reduced by using the method of the present invention to prepare the outer layer of the film, so that the antistatic effect can be effectively improved. By comparing Example 1 with Comparative Example 1 and Comparative Example 3, it can be seen that if the deep-sea fish oil is not oxidized or over-oxidized, the antistatic performance of the obtained modified fish oil will be reduced. At the same time, the change in the performance of the modified fish oil will also affect the dispersion of the nano-tourmaline powder, thereby affecting the performance of the antistatic performance of the nano-tourmaline powder. By comparing Example 1 with Comparative Example 2, it can be seen that if the nano-tourmaline powder ethanol dispersion and the modified fish oil are not used to prepare the nano-tourmaline powder / modified fish oil composite, the antistatic effect of the polypropylene material will also be weakened. By comparing Example 1 with Comparative Example 4, it can be seen that when preparing the modified fish oil, if the amount of polyethylene glycol added is small and the molecular weight is large, the resistivity will also be reduced. From the comparison between Example 1 and Comparative Examples 5 and 6, it can be seen that if only nano-tourmaline powder or modified fish oil is used as the antistatic agent, the antistatic effect of the obtained polypropylene material is significantly reduced.

[0057] 2. The tensile strength test shall be carried out according to the method in GB / T1040.1-2018 "Determination of tensile properties of plastics", and the notched impact strength test shall be carried out according to the method in GB / T1843-2008 "Determination of cantilever beam impact strength of plastics".

[0058] Table 2:

[0059] Comparing the mechanical property test results of the polypropylene materials in Examples 1 to 6 in Table 2 with Comparative Example 7, it can be seen that the anti-film outer layer material particles prepared by the method of the present invention can improve the mechanical properties of the corresponding polypropylene materials. Comparing Example 1 and Comparative Example 1 in Table 2, it can be seen that if the deep-sea fish oil is not oxidized, the tensile strength and notched impact strength will be reduced. It may be that the deep-sea fish oil is oxidized to change the performance of the modified fish oil, so that the dispersion performance of the nano-tourmaline powder and the compatibility with polypropylene are enhanced. Comparing Example 1 and Comparative Example 2, it can be seen that the mechanical properties of the nano-tourmaline powder / modified fish oil composite are significantly weakened without using nano-tourmaline powder ethanol dispersion and modified fish oil. It may be that the nano-tourmaline powder is directly added, resulting in the enhancement of the agglomeration of the nano-tourmaline powder, thereby affecting the mechanical properties. Comparing Example 1 and Comparative Example 3, it can be seen that if the deep-sea fish oil is excessively oxidized, the mechanical properties of polypropylene will also decrease. From the comparison between Example 1 and Comparative Example 4, it can be seen that when preparing modified fish oil, if the amount of polyethylene glycol added is small and the molecular weight is large, there will be some influence on its mechanical properties. From the comparison between Example 1 and Comparative Example 5, it can be seen that even if the amount of nano-tourmaline powder added is increased, but the modified fish oil is not added in an appropriate amount, the mechanical properties of polypropylene will be slightly weakened. From the comparison between Example 1 and Comparative Example 6, it can be seen that if only modified fish oil is used as an antistatic agent, the mechanical properties of polypropylene will decrease significantly.

[0060] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit the same. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that the technical solutions described in the aforementioned embodiments may still be modified, or some of the technical features may be replaced by equivalents. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for preparing an antistatic polypropylene material, characterized in that: The following steps are involved: S1: Under visible light conditions, hydrogen peroxide is added to the deep-sea fish oil, and the mixture is stirred and reacted at 50-55°C for 2.5-3 hours, and then the water layer is removed and the fish oil layer is washed with a sodium chloride solution to obtain oxidized deep-sea fish oil; S2: placing polyethylene glycol, oxidized deep-sea fish oil and a catalyst in a reaction kettle, heating to 130-135°C while stirring and stirring at a constant temperature for 3-5 hours; after the reaction is completed, washing with a sodium chloride solution and then vacuum drying to obtain modified fish oil; S3: preparing a nano-tourmaline powder ethanol dispersion; adding modified fish oil to the nano-tourmaline powder ethanol dispersion, dispersing it ultrasonically for 3 to 6 hours while stirring, and then removing ethanol by vacuum distillation while stirring, and after removing ethanol, performing vacuum degassing to obtain a nano-tourmaline powder / modified fish oil composite; S4: mixing polypropylene, nano-tourmaline powder / modified fish oil compound and antioxidant in a high-speed mixer, and then placing them in a twin-screw extruder for melt blending, extrusion and granulation to obtain pellets for the outer layer of the film; mixing polypropylene and antioxidant in a high-speed mixer, and then placing them in a twin-screw extruder for melt blending, extrusion and granulation to obtain pellets for the inner layer of the film; S5: adding the pellets for the outer layer of the film and the pellets for the inner layer of the film into two screw extruders for melting, and extruding the two layers of melt through a die to form a cast film, which is then shaped, cooled, and rolled to obtain the antistatic polypropylene material.

2. The method for preparing the antistatic polypropylene material according to claim 1, characterized in that: In step S1, the deep-sea fish oil is one of tuna oil, salmon oil, cod oil, sardine oil, and mackerel oil, or a mixture of two or more of them in any proportion.

3. The method for preparing the antistatic polypropylene material according to claim 1, characterized in that: In step S1, the mass fraction of the hydrogen peroxide is 10-15%, and the amount of hydrogen peroxide added is 35-50% of the mass of the deep-sea fish oil.

4. The method for preparing the antistatic polypropylene material according to claim 1, characterized in that: In step S2, the mass ratio of the polyethylene glycol to the oxidized deep-sea fish oil is 1:4-5.5; and the average molecular weight of the polyethylene glycol is 400-600.

5. The method for preparing the antistatic polypropylene material according to claim 1, characterized in that: In step S2, the catalyst is a sodium bisulfate aqueous solution, the mass fraction of the sodium bisulfate aqueous solution is 30-40%, and the amount of the sodium bisulfate aqueous solution is 1.5-2% of the mass of the oxidized deep-sea fish oil; During the reaction, the water in the sodium bisulfate aqueous solution and the water produced by the reaction are condensed in a condenser and then discharged.

6. The method for preparing the antistatic polypropylene material according to claim 1, characterized in that: In step S1 and step S2, the mass fraction of the sodium chloride solution is 2-3%.

7. The method for preparing an antistatic polypropylene material according to any one of claims 1 to 6, characterized in that: In step S3, the concentration of nano-tourmaline powder in the nano-tourmaline powder ethanol dispersion is 30-60 mg / mL; the preparation method of the nano-tourmaline powder ethanol dispersion comprises the following steps: adding nano-tourmaline powder with a particle size of 50-200 nm to anhydrous ethanol, and ultrasonically dispersing for 2-5 hours while stirring to obtain the nano-tourmaline powder.

8. The method for preparing an antistatic polypropylene material according to any one of claims 1 to 6, characterized in that: In step S3, the mass volume ratio of the modified fish oil to the nano-tourmaline powder ethanol dispersion is 1 g: 3-5 mL.

9. The method for preparing an antistatic polypropylene material according to any one of claims 1 to 6, characterized in that: In step S4, the material particles for the outer layer of the film include the following raw materials in weight percentage: 2.2-3.5% of nano-tourmaline powder / modified fish oil compound, 0.2-0.3% of antioxidant, and the balance of polypropylene; The granules for the inner layer of the film include the following raw materials in weight percentage: 0.05-0.1% antioxidant and the balance polypropylene.

10. The method for preparing an antistatic polypropylene material according to any one of claims 1 to 6, characterized in that: In step S4, when preparing the pellets for the outer layer of the film and the pellets for the inner layer of the film, the temperature of the twin-screw extruder is 170-195°C, and the temperatures of zones one to ten are 170°C, 170°C, 175°C, 180°C, 185°C, 190°C, 190°C, 185°C, 180°C, 180°C, and the head temperature is 195°C.

Images