Preparation method of intrinsic conductive static plastic master batch

Abstract

The application discloses a preparation method of intrinsic conductive static plastic master batch, which comprises the following steps: (1) preparing materials: the components and weight parts are proportioned as follows: conductive polymer material: 10-15 parts; nano organic titanium polymer: 5-10 parts; organic solvent: 20-30 parts; carrier resin: 15-22 parts; coupling agent: 3-5 parts; nano dispersing agent: 8-10 parts; and nano carbon material: 20-25 parts; (2) preparing paste material: the components in the step (1) are crushed and mixed to prepare paste material; (3) refining the material: the paste material in the step (2) is ground and refined; (4) preparing the material into master batch: the refined paste material in the step (3) is uniformly mixed with general plastic and plasticizing agent, and then is melted, extruded and granulated to prepare the intrinsic conductive static plastic master batch.

Description

Technical Field

[0001] The present invention relates to the technical field of nanocomposite materials, and in particular to a method for preparing intrinsically electrostatically conductive plastic masterbatch. Background Art

[0002] With the continuous advancement of electronics, automotive, and aerospace technologies, the technical requirements for anti-static products in the plastics industry are becoming increasingly stringent. Traditional plastic products are insulators, and static electricity inevitably occurs due to friction during use. This can have negative effects on some precision electronic products, and in severe cases, can even damage electronic components.

[0003] For this reason, scientists have recognized the seriousness of the electrostatic effect generated by plastic products. Researchers have therefore begun to incorporate antistatic materials into plastic product processing to eliminate the static effect. For example, a certain amount of organic or inorganic electrostatic conductive agents is added to the plastic. Commonly used ones include phosphoric acids (such as amide phosphates), inorganic semiconductor salts (such as cuprous, silver and their halides), graphite, carbon black, and sodium cellulose sulfate. However, these antistatic agents are easily oxidized, and the conductivity gradually decreases, resulting in poor application results. In recent years, the continuous emergence of new nanomaterials and rare earth materials has provided new materials and opportunities for the study of the antistatic properties of rubber and plastic products.

[0004] For example, Chinese patent CN111547356A discloses an antistatic liner bag for packaging barrels and its preparation and use method. The inner layer is prepared by adding a polymer permanent antistatic agent to a plastic masterbatch, so that the weight ratio of the polymer permanent antistatic agent reaches 5-25%; the outer layer is prepared by adding one or more ionic, non-ionic, amphiphilic or polymer antistatic agents to the plastic masterbatch, so that the weight ratio of the antistatic agent reaches 1-25%. This eliminates the safety hazard of static electricity generated by the inner liner bag of the packaging barrel during actual use.

[0005] For example, Chinese patent CN115260732A discloses an antistatic masterbatch and a preparation method thereof, which comprises 10 to 50 parts of polyethylene oxide resin (PEO), 10 to 40 parts of a thermoplastic elastomer (a copolymer of ethylene and propylene, butene, pentene, hexene, heptene and octene, or SBS, SEBS, SEPS, TPU, etc.), 2 to 10 parts of a compatibilizer (glycidyl methacrylate or maleic anhydride as a grafting monomer, POE, SEBS, SBS grafts, EVA, EMA, EMMA, TPU, etc.), 2 to 15 parts of a plasticizer (ethylene glycol and its polymers, glycerol and its polymers, fatty amine polyoxyethylene ether, etc.), 0 to 20 parts of white carbon black, and a conductive ion agent (alkali metal perchlorate, alkali metal iodide, alkali metal fluoroborate, alkali metal thiocyanate, alkali metal trifluoromethanesulfonic acid, alkali metal hexafluorophosphate, or an ionic liquid salt). 4-20 parts of PEG-10 can be mixed with other additives to produce low-cost permanent antistatic masterbatch that can be industrialized and applied to thermoplastics such as PP, PE, PS, ABS, PA6, SBS, TPU, etc. to achieve a surface resistance of 10 7 ~10 9 Ω / m 2 .

[0006] For example, Chinese patent CN109705401A discloses a composite antistatic plastic concentrate and its preparation method, comprising 5-20 parts aminosilane-modified graphene, 0-10 parts carbon nanotubes, 0-10 parts conductive carbon black, and 100 parts lubricant (prepared from maleic anhydride-grafted polypropylene and a plasticizer in a weight ratio of 100:100-500). The combined weight percentage of the modified graphene, carbon nanotubes, and conductive carbon black in the composite antistatic plastic concentrate is greater than 20%. This plastic concentrate is compatible with existing plastic production processes and can improve the plastic's strength, UV resistance, service life, performance stability, electrical conductivity, and thermal conductivity. It can be added as an additive during normal injection molding processes, eliminating the need for a separate masterbatch granulation process and reducing production costs.

[0007] For example, Chinese patent CN104844820A, "A Carbon Nanotube Conductive Masterbatch, Its Preparation Method, and Application," discloses a method for preparing a carbon nanotube conductive masterbatch. The preparation steps include: S1. Dissolving an antistatic agent in an organic solvent to obtain solution A; S2. Ultrasonic dispersion of carbon nanotubes in an organic solvent, adding solution A under ultrasonic and mechanical stirring, and concentrating to remove the organic solvent to obtain a paste; S3. Heating and melting the paste, then dripping the molten paste by free fall and cooling to obtain the carbon nanotube conductive masterbatch. This carbon nanotube conductive masterbatch has excellent volume resistivity (5 to 6 orders of magnitude lower than that of conductive masterbatches prepared using existing technologies) and can form a highly efficient electrostatic conductive network with a spinodal phase separation structure during application.

[0008] Intrinsic conductivity refers to the ability of a material to conduct electricity through the inherent properties of its atomic or molecular structure, without relying on external doping, modification, or compounding with other components. This conductivity originates from the electron or ion migration mechanism within the material and is directly related to the material's chemical composition, crystal structure, energy band characteristics, or molecular configuration. Its core characteristics are "spontaneity" and "endogenousness," in stark contrast to "extrinsic conductivity" achieved through doping, the addition of conductive fillers (such as carbon black and metal particles), or surface coating.

[0009] The mainstream antistatic products on the market are mainly achieved by adding conductive fillers, low-molecular antistatic agents, and applying conductive coatings, but these methods all have some defects. Antistatic materials filled with conductive carbon black are limited to black in color, and the products have a tendency to decarbonize, which poses a potential risk of contamination to the packaging of electronic components with high cleanliness requirements; the antistatic performance of products added with low-molecular antistatic agents has high requirements on the humidity of the environment and has a certain timeliness; the antistatic materials coated with antistatic coatings have a more complicated implementation method, high cost, and a long production cycle. The antistatic coating is easily damaged, which affects the appearance of the product and also causes the antistatic performance to disappear. From the above patent literature introduction, it can be seen that a common point is that inorganic or organic conductive agents are doped in polymers or plastics, and neither has the intrinsic electrostatic conductivity of the plastic. Summary of the Invention

[0010] In view of the above technical problems, the present invention provides a method for preparing an intrinsically conductive electrostatic plastic masterbatch, comprising the following steps:

[0011] (1) Prepare the ingredients: Mix the ingredients according to the following components and weight ratios:

[0012] Conductive polymer material: 10-15 parts; nano-organic titanium polymer: 5-10 parts; organic solvent: 20-30 parts; carrier resin: 15-22 parts; coupling agent: 3-5 parts; nano-dispersant: 8-10 parts; nano-carbon material: 20-25 parts;

[0013] (2) preparing a paste material: crushing and mixing the components in step (1) to prepare a paste material;

[0014] (3) Material refining: Grinding the paste material in step (2) into fine powder;

[0015] (4) Making the material into masterbatch: The paste material refined in step (3) is evenly mixed with general plastic and plasticizer, melted, extruded and granulated to make the electrostatic plastic masterbatch.

[0016] The nano-organic titanium polymer is prepared according to the method of Chinese invention patent publication number: CN101638483B; wherein the preparation method of the nano-organic titanium polymer comprises the following steps:

[0017] The first step is to weigh 100-150 parts of epoxy resin, 200-300 parts of methyl ethyl ketone, 100-200 parts of N-methyl pyrrolidone, 5-8 parts of titanate catalyst, 50-80 parts of polysulfide rubber, 300-400 parts of 400-mesh titanium powder, 20-30 parts of silane coupling agent, and 20-30 parts of nano-alumina modifier, and load them into a ball mill reactor in order. Then, stainless steel balls with three particle sizes of 15 mm, 10 mm, and 5 mm are added into the ball mill reactor in a weight ratio of 50:30:20, and the ball mill reactor is sealed.

[0018] The second step is to start the ball mill reactor and enter normal operation. The grinding reaction time is greater than 10 hours. After running for 3 hours, the machine is stopped for inspection. After that, the temperature and pressure of the ball mill reactor are checked every 1 hour. When the temperature of the ball mill reactor reaches 150-180℃ and the pressure is 30MPa, the ball mill reaction time is allowed to continue for 1 hour before the machine is stopped.

[0019] The third step is to wait for the ball mill reactor to cool naturally to room temperature, open the ball mill reactor, filter out the stainless steel balls, and obtain a black sludge-like polymerization product with a particle size of 80 to 100 nm.

[0020] More preferably, the nanocarbon material in step (1) comprises:

[0021] Graphene: 8-10 parts, carbon nanotubes (CNT) 5-10 parts, and nanofibers (VGCF) 4-10 parts.

[0022] More preferably, the conductive polymer material is:

[0023] polypyrrole (PPY) and / or polyaniline (PAN).

[0024] More preferably, in step (4), the mass ratio of the paste material to the general plastic and the plasticizer is 1-2:2-3:0.5-1.5.

[0025] More preferably, the organic solvent in step (1) is dimethyl sulfoxide.

[0026] More preferably, the coupling agent in step (1) is a silane coupling agent.

[0027] More preferably, in step (3), the paste material is ground by ball milling, ultrasonic-assisted oscillation is used in the grinding process, and the grinding time is 6 hours.

[0028] More preferably, the carrier resin comprises: a low-viscosity epoxy resin and an epoxy reactive diluent.

[0029] More preferably, the produced intrinsically conductive plastic masterbatch is mixed with plastic particles for film blowing.

[0030] More preferably, the mass mixing ratio of the intrinsically conductive electrostatically conductive plastic masterbatch to the plastic particles is 1:4-5.

[0031] More preferably, the plastic particles can be general-purpose plastics; or special engineering plastics.

[0032] In summary, compared with the prior art, the present invention has the following beneficial effects:

[0033] In plastic masterbatch systems, nanocarbon materials act as conductive agents, uniformly coating the surface of plastic products. Conductive polymers, acting as modifiers, are integrated into the plastic matrix through mixing. Nano-organic titanium polymers and conductive polymers form a multi-level conductive pathway through a "point-sheet-line" contact pattern. When nano-scale conductive fillers (containing conductive polymers and nano-organic titanium polymers) are introduced into traditional micron-filled plastic masterbatches, they fill the gaps between micron-fillers, effectively promoting the formation of a conductive network and lowering the percolation threshold by increasing the probability of contact between fillers and shortening the conductive pathway.

[0034] While the high surface activity of nanoscale conductive fillers facilitates interfiller adsorption and contact, optimizing the construction of a conductive network, their high surface energy can easily lead to localized aggregation, necessitating a synergistic treatment process involving chemical modification with nanodispersants and mechanical milling. Chemical dispersants reduce the nanofiller's surface energy through surface modification, inhibiting agglomeration; mechanical milling utilizes external forces to physically disperse the filler, ensuring its uniform distribution within the gaps between micron-fillers and within the plastic matrix during melt mixing. After dispersion, the nanofillers exist as monodispersed or controlled aggregates, forming a continuous electrostatically conductive network with the conductive polymer and micron-filler, characterized by "point contact, lamellar overlap, and linear continuity." This significantly enhances the electrostatic conductivity of the plastic masterbatch, imbuing it with stable intrinsic electrostatic properties. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] Figure 1 This is an electron microscope picture of the intrinsically conductive electrostatic plastic masterbatch slurry before dispersion;

[0036] Figure 2 This is an electron microscope picture of the intrinsically conductive electrostatic plastic masterbatch slurry after dispersion;

[0037] Figure 3 This is an electron microscope image of a plastic film doped with PE electrostatically conductive masterbatch;

[0038] Figure 4Schematic diagram of the point-sheet-line contact electrostatic network constructed for GM, CNT and VGCF;

[0039] Figure 5 This is a step diagram of the preparation method of intrinsically conductive electrostatic plastic masterbatch; DETAILED DESCRIPTION

[0040] The following is combined with Figure 1-5 The present invention is further described in detail.

[0041] Selected materials

[0042] Polypyrrole (PPY), industrial grade, density: 0.97 g / cm³, purity: 98-99%, Hubei Nona Technology Co., Ltd.

[0043] Polyaniline (PAN), industrial grade, density: 1.2±0.1 g / cm³, purity: 98-99%, Wuhan Huaxiang Kejie Biotechnology Co., Ltd.

[0044] Nano-organic titanium polymer, prepared according to the method of Chinese invention patent publication number: CN101638483B;

[0045] Dimethyl sulfoxide (DMSO), industrial grade, molecular formula: C2H6OS, flash point: ≥95°C, Sichuan Baichun Technology Co., Ltd.

[0046] Graphene (GM) powder, purity: ≥99.0%, Qingdao Detong Nanotechnology Co., Ltd.;

[0047] Carbon nanotube (CNT) powder, model: TNIM1, diameter 5-15 nm, Chengdu Institute of Organic Chemistry, Chinese Academy of Sciences;

[0048] Nanocarbon fiber (VGCF) powder, purity: 99.9%, length: 10-20µm, fiber diameter: 150-200nm, conductivity: ρ=6×10 6 Ω•m, Beijing Dekedaojin Technology Co., Ltd.;

[0049] Nanodispersant (IC-913), a product of Keying, Germany, non-volatile matter ≥ 99.0%, commercially available product;

[0050] Silane coupling agent, model: KH-570, commercially available product;

[0051] High-density polyethylene (PE), ACP9255B, commercially available in the chemical market;

[0052] High-density polypropylene (PP), HHMTR144, commercially available in the chemical market;

[0053] Low-viscosity epoxy resin, which can be AFG-90 epoxy resin, requires a viscosity (25°C) of 1700 cps, an epoxy equivalent weight of 0.96 kg / Eq, and a non-volatile content of ≥98.5%. Other brands of similar products may also be used.

[0054] The epoxy reactive diluent may be a product of brand AGE748, or a similar product of other brands. However, the epoxy value is required to be 0.35±0.2Eq / 100g and the viscosity is 5-10mPa·s.

[0055] Selected equipment

[0056] NH-5L stainless steel vacuum kneader, power 1.1-1.5kW, Shandong Laizhou Gree Machinery Co., Ltd.

[0057] HLD-35 plastic masterbatch granulating and proofing machine, motor power 22kW, heating power 18kW, Nanjing Henglande Machinery Technology Co., Ltd.

[0058] SY-6218-A single-screw film blowing sampler, motor power 2.2kW, heating power 450~1200kW, Dongguan Shiyan Precision Instrument Co., Ltd.

[0059] HPS-2526 four-probe resistance tester, produced by HELPASS / Helpa Technology Co., Ltd.

[0060] Example 1

[0061] The following components are prepared by weight: 10 parts polypyrrole (PPY), 10 parts nano-organic titanium polymer, 20 parts dimethyl sulfoxide (DMSO), 10 parts low-viscosity epoxy resin, 10 parts epoxy reactive diluent (AGE), 10 parts graphene (GM), 10 parts carbon nanotubes (CNT), 5 parts carbon nanofibers (VGCF), 10 parts IC-913 nanodispersant, and 5 parts KH-570 silane coupling agent. The above components are blended according to the slurry formulation and kneaded in a kneader to form a paste. This paste is then milled in an ultrasonically assisted ball mill for 6 hours. After complete dispersion, the material is filtered through a vibrating screen to separate the grinding balls. The material is then mixed uniformly with polyethylene (PE) plastic pellets and a plasticizer in a mass ratio of 2:2:1. The mixture is then transferred to a plastic pelletizer for melt extrusion into a masterbatch. The total mass of the paste in the electrostatic conductive masterbatch should be ≥ 20% by mass. The plasticizer used is a phthalate ester.

[0062] Example 2

[0063] The following components, calculated by weight, are: 12 parts polyaniline (PAN), 5 parts nano-organic titanium polymer, 25 parts dimethyl sulfoxide (DMSO), 12 parts low-viscosity epoxy resin, 10 parts epoxy reactive diluent (AGE), 8 parts graphene (GM), 8 parts carbon nanotubes (CNT), 5 parts nano-carbon fibers (VGCF), 10 parts IC-913 nanodispersant, and 5 parts KH-570 silane coupling agent. The above components are blended according to the slurry formulation and kneaded in a kneader to form a paste. The paste is then milled in an ultrasonically assisted ball mill for 6 hours. After complete dispersion, the material is filtered through a vibrating screen to separate the grinding balls. The material is then mixed uniformly with polypropylene (PP) pellets and a plasticizer in a mass ratio of 1.5:3:0.5. The mixture is then transferred to a plastic pelletizer for melt extrusion into masterbatches. The total mass of the paste in the electrostatically conductive masterbatch should be ≥20%. The plasticizer used is a phthalate ester.

[0064] Example 3

[0065] The following components are prepared by mixing the following ingredients in parts by mass: 5 parts polypyrrole (PPY), 5 parts polyaniline (PAN), 5 parts nano-organic titanium polymer, 25 parts dimethyl sulfoxide (DMSO), 12 parts low-viscosity epoxy resin, 10 parts epoxy reactive diluent (AGE), 8 parts graphene (GM), 10 parts carbon nanotubes (CNT), 7 parts nano-carbon fibers (VGCF), 10 parts IC-913 nano-dispersant, and 3 parts KH-570 silane coupling agent. The above components are blended according to the slurry formulation, kneaded and mixed in a kneader to form a paste, which is then milled in a ball mill with ultrasonic-assisted oscillation for 6 hours. The fully dispersed material is then filtered through a vibrating screen to separate the grinding balls. The material is then mixed uniformly with polycarbonate (PC) plastic pellets and plasticizer in a mass ratio of 1.25:2.75:1, and transferred to a plastic pelletizer for melt extrusion of the masterbatch. The total mass of the paste in the electrostatic conductive masterbatch is ≥20% by mass. The plasticizer used is tricresyl phosphate.

[0066] Example 4

[0067] The following components are prepared by mixing the following ingredients in parts by mass: 10 parts polypyrrole (PPY), 10 parts nano-organic titanium polymer, 20 parts dimethyl sulfoxide (DMSO), 10 parts low-viscosity epoxy resin, 10 parts epoxy reactive diluent (AGE), 10 parts graphene (GM), 5 parts carbon nanotubes (CNT), 10 parts nano-carbon fiber (VGCF), 10 parts IC-913 nano-dispersant, and 5 parts KH-570 silane coupling agent. The above components are blended according to the slurry formulation, kneaded and mixed in a kneader to form a paste, which is then placed in a ball mill with ultrasonic-assisted oscillation and ball milled for 6 hours. The fully dispersed material is then filtered through a vibrating screen to separate the grinding balls. The material is then mixed uniformly with APET / CPE (mixed plastic) and plasticizer in a mass ratio of 1:3:1 and transferred to a plastic pelletizer for melt extrusion of masterbatch. The total mass of the paste in the electrostatic conductive masterbatch is ≥20% by mass. The plasticizer used is dioctyl adipate.

[0068] Example 5

[0069] The following components are prepared by mixing the following ingredients in parts by mass: polypyrrole (PPY) 7 parts, polyaniline (PAN) 5 parts, nano-organic titanium polymer 8 parts, dimethyl sulfoxide (DMSO) 22 parts, low-viscosity epoxy resin 10 parts, epoxy reactive diluent (AGE) 10 parts, graphene (GM) 10 parts, carbon nanotubes (CNT) 10 parts, nano-carbon fiber (VGCF) 5 parts, IC-913 nano-dispersant 8 parts, and KH-570 silane coupling agent 5 parts. The above components are blended according to the slurry formulation, kneaded and mixed in a kneader to form a paste, which is then milled in a ball mill with ultrasonic-assisted oscillation for 6 hours. The fully dispersed material is then filtered through a vibrating screen to separate the grinding balls. The material is then mixed uniformly with APET / CPE (mixed plastic) and plasticizer in a mass ratio of 1:3:1 and transferred to a plastic pelletizer for melt extrusion into masterbatch. The total mass of the paste in the electrostatic conductive masterbatch is ≥20% by mass. The plasticizer used is dioctyl adipate.

[0070] Example 6

[0071] The following components, by weight, are: 15 parts polyaniline (PAN), 5 parts nano-organic titanium polymer, 25 parts dimethyl sulfoxide (DMSO), 12 parts low-viscosity epoxy resin, 8 parts epoxy reactive diluent (AGE), 8 parts graphene (GM), 8 parts carbon nanotubes (CNT), 4 parts nano-carbon fibers (VGCF), 10 parts IC-913 nanodispersant, and 5 parts KH-570 silane coupling agent. The above components are blended according to the slurry formulation and kneaded in a kneader to form a paste. The paste is then milled in an ultrasonically assisted ball mill for 6 hours. After complete dispersion, the material is filtered through a vibrating screen to separate the grinding balls. The material is then mixed uniformly with PA / AL (mixed plastic) and plasticizer in a mass ratio of 1.2:3:0.8. The mixture is then transferred to a plastic pelletizer for melt extrusion into masterbatches. The total mass of the paste in the electrostatically conductive masterbatch should be ≥20%. The plasticizer used is a phthalate ester.

[0072] Example 7

[0073] The following components are prepared by mixing the following ingredients in parts by mass: 15 parts polypyrrole (PPY), 5 parts nano-organic titanium polymer, 25 parts dimethyl sulfoxide (DMSO), 10 parts low-viscosity epoxy resin, 10 parts epoxy reactive diluent (AGE), 10 parts graphene (GM), 5 parts carbon nanotubes (CNT), 10 parts nano-carbon fiber (VGCF), 10 parts IC-913 nano-dispersant, and 5 parts KH-570 silane coupling agent according to the slurry formulation. The ingredients are then kneaded and mixed in a kneader to form a paste, which is then milled in a ball mill with ultrasonic-assisted oscillation for 6 hours. The fully dispersed material is then separated from the grinding balls by a filter vibrating screen. The material is then mixed uniformly with PET / AL / PA / CPE (mixed plastic) and a plasticizer in a mass ratio of 1:2.5:1.5, and transferred to a plastic pelletizer for melt extrusion into masterbatches. The total mass of the paste in the electrostatically conductive masterbatch is ≥20% by mass. The plasticizer used is phthalate.

[0074] Figure 1 and Figure 2 These are comparison photos of the intrinsically conductive electrostatic plastic masterbatch slurry before and after dispersion. It can be seen from the figure that the material state before dispersion is: CNT is spherical, GM is flake-like, VGCF is flocculent, and the structure is disordered; after ball milling in an ultrasonic-assisted oscillation ball mill, the material state after dispersion is: it is impossible to distinguish between spheres, flakes, and flocculents, and they are evenly mixed together with a uniform structure.

[0075] Figure 3 This is an electron micrograph of an electrostatically conductive plastic film produced by blow molding using a conductive plastic masterbatch mixed with PE. The image shows the uniform and dense microstructure within the plastic film, with a clearly visible electrostatically conductive network constructed by the "sheet-point-line" contact pattern.

[0076] Depend on Figure 4 It can be seen that the conductive polymer material is integrated with the plastic matrix through mixing as a modifier, and the nano-organic titanium polymer and the conductive polymer material construct a multi-level conductive path in the form of "point-piece-line" contact, which significantly improves the electrostatic conductivity of the plastic masterbatch and enables it to have stable intrinsic electrostatic conductivity characteristics.

[0077] The conductive masterbatch produced in Examples 1 to 7 was mixed with plastic particles such as PE, PP or PC in the order of Examples 1 to 7 at a mass ratio of 1:1, 1:2, 1:3, 1:4, 1:5, 1:6 and 1:7, respectively. Seven groups of samples were made into films using a plastic film blowing machine, and then performance tests were performed according to national standards.

[0078] The test results are shown in Table 1. From the comparison of the test data of Examples 1 to 7, the conductivity of the plastic films produced is within 1×10 -4 ~1×10 -8 Ω·cm, meeting the technical requirements of the national standard GB / T 39588-2020. Considering product performance and economic applicability, the preferred embodiment 4 or embodiment 5 of the present invention has a high cost-effectiveness. Physical and mechanical properties tests were conducted on electrostatically conductive plastic films made with different conductive masterbatches, different plastic particles, and different mixing ratios. Due to the inherent performance differences between single materials and combined materials, the test results also vary.

[0079] Table 1 Performance test results of seven groups of samples of intrinsically conductive electrostatic plastic masterbatch blown film

[0080]

[0081] This specific embodiment is merely an explanation of the invention and is not a limitation of the invention. After reading this specification, those skilled in the art may make non-creative modifications to this embodiment as needed. However, as long as they are within the scope of protection of the invention, they are protected by patent law.

Claims

1. A method for preparing an intrinsically conductive electrostatic plastic masterbatch, characterized in that: The following steps are involved: (1) Prepare the ingredients: Mix the ingredients according to the following components and weight ratios: Conductive polymer material: 10-15 parts; nano-organic titanium polymer: 5-10 parts; organic solvent: 20-30 parts; carrier resin: 15-22 parts; coupling agent: 3-5 parts; nano-dispersant: 8-10 parts; nano-carbon material: 20-25 parts; (2) preparing a paste material: crushing and mixing the components in step (1) to prepare a paste material; (3) Material refining: grinding and refining the paste material in step (2); (4) preparing the material into masterbatch: uniformly mixing the paste material refined in step (3) with general plastic and plasticizer, melting, extruding and granulating to prepare the electrostatic plastic masterbatch; The preparation method of the nano-organic titanium polymer includes the following steps: The first step is to weigh 100-150 parts of epoxy resin, 200-300 parts of methyl ethyl ketone, 100-200 parts of N-methyl pyrrolidone, 5-8 parts of titanate catalyst, 50-80 parts of polysulfide rubber, 300-400 parts of 400-mesh titanium powder, 20-30 parts of silane coupling agent, and 20-30 parts of nano-alumina modifier, and load them into a ball mill reactor in order. Then, stainless steel balls with three particle sizes of 15 mm in diameter, 10 mm in diameter, and 5 mm in diameter are added into the ball mill reactor in a weight ratio of 50:30:20, and the ball mill reactor is sealed. The second step is to start the ball mill reactor and enter normal operation. The grinding reaction time is greater than 10 hours. After running for 3 hours, the machine is stopped for inspection. After that, the temperature and pressure of the ball mill reactor are checked every 1 hour. When the temperature of the ball mill reactor reaches 150-180℃ and the pressure is 30MPa, the ball mill reaction time is allowed to continue for 1 hour before the machine is stopped. The third step is to wait for the ball mill reactor to cool naturally to room temperature, open the ball mill reactor, filter out the stainless steel balls, and obtain a black sludge-like polymerization product with a particle size of 80 to 100 nm.

2. The method for preparing the intrinsically conductive electrostatic plastic masterbatch according to claim 1, characterized in that: The nano-carbon material in step (1) comprises: Graphene: 8-10 parts, carbon nanotubes 5-10 parts, carbon nanofibers 4-10 parts.

3. The method for preparing the intrinsically conductive electrostatic plastic masterbatch according to claim 1, characterized in that: The conductive polymer material is: polypyrrole and / or polyaniline.

4. The method for preparing the intrinsically conductive electrostatic plastic masterbatch according to claim 1, characterized in that: In the step (4), the mass ratio of the paste material to the general plastic and the plasticizer is 1-2:2-3:0.5-1.

5.

5. The method for preparing the intrinsically conductive electrostatic plastic masterbatch according to claim 1, characterized in that: The organic solvent in step (1) is dimethyl sulfoxide.

6. The method for preparing the intrinsically conductive electrostatic plastic masterbatch according to claim 1, characterized in that: The coupling agent in step (1) is a silane coupling agent.

7. The method for preparing the intrinsically conductive electrostatic plastic masterbatch according to claim 1, characterized in that: In step (3), the paste material is ground by ball milling, and ultrasonic-assisted oscillation is used in the grinding process, and the grinding time is 6 hours.

8. The method for preparing an intrinsically conductive electrostatically conductive plastic masterbatch according to claim 1, wherein the carrier resin comprises: Low viscosity epoxy resin and epoxy reactive diluent.

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