A carbon black masterbatch and its preparation method

Abstract

This application discloses a carbon black masterbatch and its preparation method, relating to the field of polymer material coloring technology. The carbon black masterbatch comprises the following raw materials in parts by weight: 30-60 parts quaternary ammonium salt grafted carbon black, 40-70 parts resin carrier, 2-4 parts dopamine hydrochloride, 0.3-1 parts boron nitride, 0.3-1.2 parts cerium oxide, 0.5-1.67 parts epoxy cyclohexyl-cage polysilsesquioxane, 2-4 parts amino zinc-based metal-organic framework, 1-3 parts maleic anhydride grafted polypropylene, 1-5 parts dispersant, 0.5-2 parts antioxidant, and 0.5-1.5 parts hindered amine light stabilizer. The carbon black masterbatch of this application possesses comprehensive deodorizing properties, including highly efficient physical adsorption, catalytic degradation, source inhibition of bacteria, and long-lasting stability.

Description

Technical Field

[0001] This application relates to the field of polymer material coloring technology, and in particular to a carbon black masterbatch and its preparation method. Background Technology

[0002] Carbon black masterbatch is one of the main black colorants in the plastics industry. It is usually made by melt blending, extrusion granulation, and other processes involving carbon black, resin carrier, and various processing aids. It is widely used in food contact packaging, automotive interior parts, and appliance casings. However, carbon black masterbatch generally suffers from odor problems during production and application, especially in high-end applications such as automotive interiors and food packaging where odor is sensitive. This has become a key technological bottleneck restricting the industry's upgrading.

[0003] The odor mainly comes from three aspects: First, carbon black has strong adsorption properties, adsorbing a large amount of volatile organic compounds (such as benzene series, alkanes, aldehydes and ketones) during production, storage and transportation. These substances are slowly released during post-processing or use. Second, the resin carrier undergoes thermal oxidation degradation during high-temperature extrusion, generating small molecule aldehydes, ketones, carboxylic acids and sulfur-containing compounds (such as methanethiol and dimethyl sulfide). Third, additives such as dispersants and lubricants volatilize or decompose during processing, releasing irritating odors.

[0004] Currently, two main technologies are used to control the odor of carbon black masterbatch: one is physical adsorption using porous materials such as activated carbon, zeolite molecular sieves, and diatomaceous earth; the other is chemical neutralization reactions using organic acids, metal salts, or metal oxides. However, physical adsorption methods suffer from adsorption saturation and secondary release issues; chemical neutralization methods have limitations such as corrosion risks and limited reaction selectivity. Summary of the Invention

[0005] To improve deodorization function and mechanical properties, this application provides a carbon black masterbatch and its preparation method.

[0006] In a first aspect, this application provides a carbon black masterbatch, which adopts the following technical solution: A carbon black masterbatch comprises the following raw materials in parts by weight: 30-60 parts quaternary ammonium salt grafted carbon black, 40-70 parts resin carrier, 2-4 parts dopamine hydrochloride, 0.3-1 part boron nitride, 0.3-1.2 parts cerium oxide, 0.5-1.67 parts epoxy cyclohexyl-cage polysilsesquioxane, 2-4 parts amino zinc-based metal-organic framework, 1-3 parts maleic anhydride grafted polypropylene, 1-5 parts dispersant, 0.5-2 parts antioxidant, and 0.5-1.5 parts hindered amine light stabilizer.

[0007] By employing the above technical solutions, this application constructs a synergistic deodorization system integrating physical adsorption, chemical degradation, and source suppression. Specifically, epoxy cyclohexyl-cage-shaped polysilsesquioxane and amino zinc-based metal-organic frameworks form chemical bonds through an epoxy-amino ring-opening reaction, constructing a stable organic-inorganic hybrid interface. This interface not only significantly enhances the dispersion stability and shear resistance of the metal-organic framework in the resin matrix, but the nanocage-like structure of the epoxy cyclohexyl-cage-shaped polysilsesquioxane itself can also synergistically adsorb small molecule odor substances. Through chemical bonding, it can more effectively form size complementarity with the pore adsorption of the amino zinc-based metal-organic framework. Quaternary ammonium salt grafted carbon black is uniformly dispersed in the resin matrix under the multiple anchoring effects of polydopamine (formed by in-situ polymerization of dopamine hydrochloride). The quaternary ammonium salt functional groups endow the material with long-lasting antibacterial properties, inhibiting odors produced by microbial metabolism at the source. Cerium oxide, as a highly efficient catalytic active component, utilizes its Ce... 3+ / Ce 4+ Redox cycle characteristics (Ce 3+ / Ce 4+ The site, acting as a Lewis acid center, forms a stable coordination bond with the lone pair electrons of the free amino groups on the surface of the zinc-based metal-organic framework (MOF). It accumulates near the pores of the MOF, synergistically catalyzing the conversion of adsorbed odor molecules into odorless small molecules, achieving integrated adsorption-degradation. The high thermal conductivity of boron nitride and the free radical quenching ability of cerium oxide form a synergistic "physical heat dissipation-chemical quenching" mechanism, effectively inhibiting the formation of small-molecule odor byproducts during thermal oxidation. The synergistic effect of these components gives the carbon black masterbatch a comprehensive deodorization performance, combining highly efficient physical adsorption, catalytic degradation, source inhibition of bacteria, and long-lasting stability.

[0008] Optionally, the preparation steps of the quaternary ammonium salt grafted carbon black include: mixing carbon black and ethanol solution, ultrasonically dispersing, adding dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride, heating and stirring, centrifuging, washing, and drying to obtain quaternary ammonium salt grafted carbon black.

[0009] By adopting the above technical solution, this application utilizes dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride as an organosilicon quaternary ammonium salt modifier. After hydrolysis of its silanoxy groups in an aqueous ethanol solution, a covalent condensation reaction occurs with the hydroxyl groups on the carbon black surface, firmly grafting the quaternary ammonium salt functional groups onto the carbon black surface to form a stable chemically bonded layer that is water-resistant and heat-resistant, overcoming the defect of easy desorption in physical adsorption modification. Simultaneously, the grafted long-chain alkyl groups and quaternary ammonium salt cations effectively reduce the surface polarity of the carbon black, and through electrostatic repulsion, they interact with... The steric hindrance synergistically inhibits the secondary agglomeration of carbon black particles, significantly improving its dispersion uniformity and interfacial compatibility in non-polar resin carriers such as polypropylene, thereby enhancing the masterbatch's coloring power, blackness uniformity, and mechanical properties (such as notched impact strength and tensile strength). In addition, the covalently fixed quaternary ammonium salt functional groups endow carbon black with long-lasting broad-spectrum antibacterial properties, inhibiting odor substances produced by microbial metabolism from the source, and synergistically enhancing the overall deodorizing effect and long-term stability of the carbon black masterbatch with other functional components in the system.

[0010] Optionally, the preparation steps of the aminated zinc-based metal-organic framework include: mixing the zinc-based metal-organic framework and N,N-dimethylformamide, ultrasonically dispersing, adding 2-aminobenzimidazole, heating and stirring, centrifuging, washing, and drying to obtain the aminated zinc-based metal-organic framework.

[0011] By adopting the above technical solution, this application uses a zinc-based metal-organic framework as a matrix. Under ultrasonic dispersion assistance, 2-aminobenzimidazole molecules are fully penetrated into the framework channels and surface. Through ligand exchange or post-synthetic modification reactions, amino functional groups are uniformly introduced into the organic ligand backbone of the metal-organic framework, achieving stable anchoring of the amino group in the framework structure. Simultaneously, 2-aminobenzimidazole itself possesses broad-spectrum antibacterial activity (the benzimidazole ring can inhibit microbial DNA synthesis), and zinc ions in the metal-organic framework can be slowly released, producing a synergistic antibacterial effect. This modification process, on the one hand, retains the original high specific surface area and ordered pore structure of the zinc-based metal-organic framework, ensuring its efficient physical adsorption capacity for odor molecules (such as ammonia, thiols, etc.); on the other hand, the introduced amino functional groups can not only chemically bond with components such as polydopamine and epoxycyclohexyl-cage polysilsesquioxane, enhancing the interfacial interaction between functional components, but also act as basic active sites to chemically adsorb acidic odor molecules, significantly improving the specific capture efficiency of acidic volatile organic compounds. Meanwhile, amination modification improves the interfacial compatibility between the metal-organic framework and the resin matrix, which is beneficial to its uniform dispersion in the masterbatch.

[0012] Optionally, the weight ratio of the epoxy cyclohexyl-cage polysilsesquioxane and the amino zinc-based metal-organic framework is (0.25-0.8):1.

[0013] By adopting the above technical solution, this application utilizes a specific weight ratio of epoxy cyclohexyl-cage-polysilsesquioxane and amino zinc-based metal-organic framework to construct a stable organic-inorganic hybrid network structure, synergistically improving the deodorization performance and structural stability of the masterbatch. Specifically, the nanocage-like framework of epoxy cyclohexyl-cage-polysilsesquioxane and the porous structure of the amino zinc-based metal-organic framework are nested within each other, enhancing the dispersion stability and shear resistance of the metal-organic framework in the resin matrix. Furthermore, the hydrophobic properties of the cage-like silsesquioxane provide a protective microenvironment for the metal-organic framework channels, effectively suppressing the damage to the porous structure caused by high temperature and high shear during processing. Simultaneously, at this ratio, epoxy cyclohexyl-cage-polysilsesquioxane can fully exert its role as an interfacial compatibilizer, promoting the uniform distribution of functional components such as quaternary ammonium salt-grafted carbon black and polydopamine in the resin carrier, forming a three-dimensional functional network that runs through the entire masterbatch. The aforementioned synergistic effect allows the high specific surface area adsorption function of the aminated zinc-based metal-organic framework to be retained to the greatest extent. The nanocage-like structure of epoxycyclohexyl-cage polysilsesquioxane synergistically participates in the physical capture of small molecule odor substances. The hybrid interface formed by the two through chemical bonding further provides an ideal reaction microenvironment for the catalytic degradation of cerium oxide, thereby achieving efficient coupling of the "physical adsorption-chemical bonding-catalytic degradation" triple deodorization mechanism, significantly improving the overall deodorization performance and structural stability of the masterbatch.

[0014] Optionally, the weight ratio of the quaternary ammonium salt grafted carbon black to dopamine hydrochloride is (13-15):1.

[0015] By adopting the above technical solution, this application uses a specific weight ratio of quaternary ammonium salt grafted carbon black and dopamine hydrochloride to achieve precise control of the coating efficiency and functional synergy of carbon black surface. At this ratio, polydopamine formed by in-situ polymerization of dopamine hydrochloride acts as a molecular-level anchoring agent. Its catechol groups interact with the cationic layer and hydrophobic alkyl chains on the surface of quaternary ammonium salt grafted carbon black through multiple interactions (including π-π stacking, hydrogen bonding, and hydrophobic effects), forming a uniform and dense coating layer. This fully utilizes the strong adhesiveness of polydopamine to firmly anchor carbon black particles in the resin matrix, thereby effectively inhibiting secondary agglomeration of carbon black under high filling amounts, and avoiding self-agglomeration or masking of the coloring power of carbon black caused by excessive polydopamine.

[0016] Optionally, the weight ratio of boron nitride to cerium oxide is 1:(1-3).

[0017] By employing the above technical solution, this application utilizes a specific weight ratio of boron nitride and cerium oxide to achieve synergistic enhancement of thermal management and chemical stability. Specifically, the thermal conductivity of boron nitride and the chemical stabilization of cerium oxide form a synergistic mechanism of "physical heat dissipation - chemical quenching": boron nitride accelerates heat dissipation, reducing the rate of free radical generation at its source; cerium oxide, aided by the thermal conductivity of boron nitride, makes the temperature distribution of the system more uniform, thereby significantly improving its free radical quenching efficiency. The synergistic effect of these two components significantly inhibits the generation of odorous byproducts such as small-molecule aldehydes, ketones, carboxylic acids, and sulfur-containing compounds due to thermal oxidative degradation of resin carriers and additives during high-temperature processing, reducing the formation of odorous substances at their source.

[0018] Optionally, the boron nitride has a particle size of 3-10 μm, and the cerium oxide has a particle size of 20-100 nm.

[0019] By adopting the above technical solution, this application controls the particle size of boron nitride to 3-10 μm and the particle size of cerium oxide to 20-100 nm, achieving spatial scale complementarity and functional synergy of the two functional fillers in the masterbatch system. The thermally conductive network constructed by micron-sized boron nitride provides a uniform thermal field distribution environment for nano-sized cerium oxide, avoiding cerium oxide deactivation due to local overheating; the nano-sized cerium oxide, through interface filling, fills the microscopic gaps between boron nitride particles, further optimizing the heat conduction path. In addition, the micron-sized boron nitride ensures that it is not prone to agglomeration during melt blending, while the nano-sized cerium oxide gives it higher reactivity. Under the synergistic effect of the two, it not only ensures the efficient operation of the "physical heat dissipation-chemical quenching" dual mechanism, but also avoids the processing difficulties caused by excessively small particle size or the uneven dispersion caused by excessively large particle size, significantly improving the thermal stability and deodorization durability of the masterbatch during high-temperature processing and long-term use.

[0020] Optionally, the antioxidant is at least one of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and tris(2,4-di-tert-butylphenyl) phosphite, and the dispersing agent is at least one of stearic acid, zinc stearate, and polyethylene wax.

[0021] Optionally, the resin carrier is polypropylene.

[0022] Optionally, the hindered amine light stabilizer is polysuccinate (4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol).

[0023] By adopting the above technical solution, this application uses poly(4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol) ester as a hindered amine light stabilizer. Its high molecular weight structure endows the masterbatch with excellent resistance to migration and volatility, ensuring that it continues to play a role in free radical capture and peroxide decomposition during long-term use and high-temperature processing. It forms a triple synergistic mechanism of "physical heat dissipation-chemical quenching-free radical capture" with the physical heat dissipation of boron nitride and the chemical quenching of cerium oxide, which inhibits the thermal oxidative degradation of resin carriers and additives from the source, and significantly reduces the generation of odor byproducts such as small molecule aldehydes, ketones, carboxylic acids and sulfur-containing compounds. At the same time, there is a synergistic antioxidant effect between this light stabilizer and the catechol structure of polydopamine, which further enhances the stability of the masterbatch under melt processing and outdoor use conditions, and its good interfacial compatibility avoids the deterioration of mechanical properties.

[0024] Secondly, this application provides a method for preparing carbon black masterbatch, which adopts the following technical solution: A method for preparing carbon black masterbatch includes the following steps: S1. Mix epoxycyclohexyl-cage polysilsesquioxane, amino zinc-based metal-organic framework and first solvent, disperse by ultrasonication, heat and stir under inert gas protection to obtain hybrid filler dispersion; S2. Mix quaternary ammonium salt grafted carbon black, dopamine hydrochloride and the second solvent, stir evenly, centrifuge, wash and dry to obtain polydopamine-anchored quaternary ammonium salt grafted carbon black. S3. Add the hybrid filler dispersion and polydopamine-anchored quaternary ammonium salt grafted carbon black to the resin carrier and stir evenly. Then add boron nitride, cerium oxide and maleic anhydride grafted polypropylene and stir evenly. Add dispersant, antioxidant and hindered amine light stabilizer and stir evenly. Melt extrusion, cool and pelletize to obtain carbon black masterbatch.

[0025] Optionally, the first solvent is N,N-dimethylformamide, and the second solvent is tris(hydroxymethyl)aminomethane hydrochloride buffer.

[0026] Optionally, in step S1, the ultrasonic power is 300-500W and the heating temperature is 80-120℃.

[0027] Optionally, in step S2, the stirring speed is 300-500 rpm, the centrifugation speed is 8000-10000 rpm, and the drying temperature is 80-100℃.

[0028] Optionally, in step S3, the melt extrusion temperature is 180-230℃.

[0029] In summary, this application includes at least one of the following beneficial technical effects: 1. This application constructs a synergistic deodorization system integrating physical adsorption, chemical degradation, and source suppression. Specifically, epoxy cyclohexyl-cage-shaped polysilsesquioxane and amino zinc-based metal-organic frameworks form a chemical bond through an epoxy-amino ring-opening reaction, constructing a stable organic-inorganic hybrid interface. This interface not only significantly enhances the dispersion stability and shear resistance of the metal-organic framework in the resin matrix, but the nanocage-like structure of the epoxy cyclohexyl-cage-shaped polysilsesquioxane itself can also synergistically adsorb small molecule odor substances. Through chemical bonding, it can more effectively form size complementarity with the pore adsorption of the amino zinc-based metal-organic framework. Quaternary ammonium salt grafted carbon black is uniformly dispersed in the resin matrix under the multiple anchoring effects of polydopamine (formed by in-situ polymerization of dopamine hydrochloride). The quaternary ammonium salt functional groups endow the material with long-lasting antibacterial properties, inhibiting odors produced by microbial metabolism at the source. Cerium oxide, as a highly efficient catalytic active component, utilizes its Ce... 3+ / Ce 4+ Redox cycle characteristics (Ce 3+ / Ce 4+ The site, acting as a Lewis acid center, forms a stable coordination bond with the lone pair electrons of the free amino groups on the surface of the zinc-based metal-organic framework (MOF). It accumulates near the pores of the MOF and synergistically catalyzes the conversion of adsorbed odor molecules into odorless small molecules, achieving integrated adsorption-degradation. The high thermal conductivity of boron nitride and the free radical quenching ability of cerium oxide form a synergistic "physical heat dissipation-chemical quenching" mechanism, effectively inhibiting the formation of small-molecule odor byproducts during thermal oxidation. The synergistic effect of these components gives the carbon black masterbatch a comprehensive deodorization performance that combines highly efficient physical adsorption, catalytic degradation, source inhibition of bacteria, and long-lasting stability. 2. This application employs a specific weight ratio of epoxy cyclohexyl-cage-polysilsesquioxane and amino zinc-based metal-organic framework to construct a stable organic-inorganic hybrid network structure, synergistically improving the deodorization performance and structural stability of the masterbatch. Specifically, the nanocage-like framework of epoxy cyclohexyl-cage-polysilsesquioxane and the porous structure of the amino zinc-based metal-organic framework are nested within each other, enhancing the dispersion stability and shear resistance of the metal-organic framework in the resin matrix. Furthermore, the hydrophobic properties of the cage-like silsesquioxane provide a protective microenvironment for the metal-organic framework channels, effectively suppressing the damage to the porous structure caused by high temperature and high shear during processing. Simultaneously, at this ratio, epoxy cyclohexyl-cage-polysilsesquioxane can fully exert its role as an interfacial compatibilizer, promoting the uniform distribution of functional components such as quaternary ammonium salt-grafted carbon black and polydopamine in the resin carrier, forming a three-dimensional functional network that runs throughout the entire masterbatch. The aforementioned synergistic effect allows the high specific surface area adsorption function of the aminated zinc-based metal-organic framework to be retained to the maximum extent. The nanocage-like structure of epoxycyclohexyl-cage-polysilsesquioxane synergistically participates in the physical capture of small molecule odor substances. The hybrid interface formed by the two through chemical bonding further provides an ideal reaction microenvironment for the catalytic degradation of cerium oxide, thereby achieving efficient coupling of the "physical adsorption-chemical bonding-catalytic degradation" triple deodorization mechanism, significantly improving the overall deodorization performance and structural stability of the masterbatch. 3. This application employs a specific weight ratio of quaternary ammonium salt grafted carbon black and dopamine hydrochloride, enabling precise control of the carbon black surface coating efficiency and functional synergy. At this ratio, polydopamine, formed by in-situ polymerization of dopamine hydrochloride, acts as a molecular-level anchoring agent. Its catechol groups interact with the cationic layer and hydrophobic alkyl chains on the surface of the quaternary ammonium salt grafted carbon black through multiple interactions (including π-π stacking, hydrogen bonding, and hydrophobic effects), forming a uniform and dense coating layer. This fully utilizes the strong adhesive properties of polydopamine to firmly anchor carbon black particles to the resin matrix, effectively inhibiting secondary agglomeration of carbon black under high filler content, while also avoiding self-agglomeration or masking of the carbon black's coloring power due to excessive polydopamine. 4. This application employs a specific weight ratio of boron nitride and cerium oxide, achieving synergistic enhancement of thermal management and chemical stability. Specifically, the thermal conductivity of boron nitride and the chemical stabilization of cerium oxide form a synergistic "physical heat dissipation-chemical quenching" mechanism: boron nitride accelerates heat dissipation, reducing the rate of free radical generation at its source; cerium oxide, aided by the thermal conductivity of boron nitride, makes the system temperature distribution more uniform, thereby significantly improving its free radical quenching efficiency. This synergistic effect significantly suppresses the formation of odorous byproducts such as small-molecule aldehydes, ketones, carboxylic acids, and sulfur-containing compounds generated during the thermal oxidative degradation of resin carriers and additives during high-temperature processing, reducing the generation of odorous substances at their source. Detailed Implementation

[0030] The technical solutions in the embodiments of this application will be clearly and completely described below with reference to the embodiments of this application. Obviously, the described embodiments are only some embodiments of this application, and not all embodiments. Based on the embodiments of this application, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of this application.

[0031] This application discloses a carbon black masterbatch comprising the following raw materials in parts by weight: 30-60 parts of quaternary ammonium salt grafted carbon black, 40-70 parts of resin carrier, 2-4 parts of dopamine hydrochloride, 0.3-1 parts of boron nitride, 0.3-1.2 parts of cerium oxide, 0.5-1.67 parts of epoxy cyclohexyl-cage polysilsesquioxane, 2-4 parts of amino zinc-based metal-organic framework, 1-3 parts of maleic anhydride grafted polypropylene, 1-5 parts of dispersant, 0.5-2 parts of antioxidant, and 0.5-1.5 parts of hindered amine light stabilizer.

[0032] This application discloses a method for preparing carbon black masterbatch, including the following steps: S1. Mix epoxy cyclohexyl-cage polysilsesquioxane, amino zinc-based metal-organic framework and first solvent, ultrasonically disperse at 300-500W for 20-40min, and heat and stir at 80-120℃ for 30-60min under inert gas protection to obtain hybrid filler dispersion. S2. Mix quaternary ammonium salt grafted carbon black, dopamine hydrochloride and the second solvent, stir at 300-500 rpm for 1-2 hours, centrifuge at 8000-10000 rpm for 10-20 minutes, wash, and dry at 80-100℃ for 12-24 hours to obtain polydopamine-anchored quaternary ammonium salt grafted carbon black. S3. Add the hybrid filler dispersion and polydopamine-anchored quaternary ammonium salt grafted carbon black to the resin carrier, stir at 100-300 rpm for 10-20 min, then add boron nitride, cerium oxide and maleic anhydride grafted polypropylene, stir at 600-800 rpm for 10-20 min, then add dispersant, antioxidant and hindered amine light stabilizer in sequence, stir at 100-300 rpm for 10-20 min, melt extrude at 180-230℃, cool, and pelletize to obtain carbon black masterbatch.

[0033] All raw materials used in the embodiments of this application are commercially available, wherein: Carbon black, particle size 32nm, Nester Carbon Black Co., Ltd. Zinc-based metal-organic framework, MOF-74(Zn), Xi'an Qiyue Biotechnology Co., Ltd. Dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride solution, 40wt% purity, Shanghai Aladdin Biochemical Technology Co., Ltd. 2-Aminobenzimidazole, Shanghai Aladdin Biochemical Technology Co., Ltd.; Epoxycyclohexyl-cage-shaped polysilsesquioxane, Forsmann Technology (Beijing) Co., Ltd.; Dopamine hydrochloride, Shanghai Aladdin Biochemical Technology Co., Ltd. Boron nitride, particle size 3-10μm, Shanghai Aladdin Biochemical Technology Co., Ltd. Cerium oxide, particle size 20-100nm, Shanghai Aladdin Biochemical Technology Co., Ltd.; Maleic anhydride-grafted polypropylene, grafting rate 1.0%, Nanjing Feiteng New Material Technology Co., Ltd. Polypropylene, melt index 9 g / 10 min, Nagase (China) Co., Ltd. Pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid], antioxidant MIANOX1010, Nanjing Milan Chemical Co., Ltd.; Tris(2,4-di-tert-butylphenyl) phosphite, antioxidant MIANOX168, Nanjing Milan Chemical Co., Ltd.; Zinc stearate, Shanghai Aladdin Biochemical Technology Co., Ltd.; Polyethylene wax, Nanjing Feiteng New Material Technology Co., Ltd.; Poly(4-hydroxy-2,2,6,6-tetramethyl-1-piperidinol) ester, light stabilizer UV622, Nanjing Milan Chemical Co., Ltd.; N,N-Dimethylformamide, Shanghai Maclean Biochemical Technology Co., Ltd.; Tris-HCl buffer, pH=8.5, 10mM, Shanghai Maclean Biotechnology Co., Ltd.

[0034] Preparation Example 1 Preparation of quaternary ammonium salt grafted carbon black: 60 g of carbon black and 800 mL of ethanol solution (prepared by mixing 640 mL of anhydrous ethanol and 160 mL of water) were mixed and ultrasonically dispersed at 500 W for 30 min. 30 g of dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride solution was added, and the pH was adjusted to 5 using acetic acid. The mixture was heated and stirred at 60 °C and 800 rpm for 6 h under nitrogen protection. After the reaction was complete, the mixture was centrifuged at 8000 rpm for 20 min, the supernatant was removed, and the mixture was washed three times with deionized water and vacuum dried at 80 °C for 12 h to obtain quaternary ammonium salt grafted carbon black.

[0035] Preparation Example 2 Preparation of aminated zinc-based metal-organic frameworks: 4 g of zinc-based metal-organic frameworks and 100 mL of N,N-dimethylformamide were mixed and ultrasonically dispersed at 400 W for 30 min. 0.4 g of 2-aminobenzimidazole was added, and the mixture was stirred at 50 °C and 800 rpm for 12 h under nitrogen protection. After the reaction was completed, the mixture was centrifuged at 10,000 rpm for 10 min, washed once with N,N-dimethylformamide, then washed twice with methanol, and freeze-dried at -50 °C for 5 h, and then freeze-dried at -20 °C for 24 h to obtain aminated zinc-based metal-organic frameworks.

[0036] Example 1 0.5 g of epoxycyclohexyl-cage-type polysilsesquioxane, 2 g of the amino zinc-based metal-organic framework obtained in Preparation Example 2, and 30 mL of N,N-dimethylformamide were mixed and ultrasonically dispersed at 300 W for 40 min. The mixture was then heated and stirred at 80 °C for 60 min under nitrogen protection to obtain a hybrid filler dispersion. 30 g of quaternary ammonium salt grafted carbon black obtained in Preparation Example 1, 2 g of dopamine hydrochloride, and 200 mL of Tris-HCl buffer were mixed and stirred at 300 rpm for 2 h. The mixture was centrifuged at 8000 rpm for 20 min, washed three times with deionized water, and dried at 80 °C for 24 h to obtain polydopamine-anchored quaternary ammonium salt grafted carbon black. The hybrid filler dispersion and polydopamine-anchored quaternary ammonium salt grafted carbon black were then mixed. Add to 70g of polypropylene, stir at 100rpm for 20min, then add 0.3g of boron nitride, 0.3g of cerium oxide and 1g of maleic anhydride-grafted polypropylene, stir at 600rpm for 20min, then add 1g of zinc stearate, 0.5g of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and 0.5g of poly(4-hydroxy-2,2,6,6-tetramethyl-1-piperidinol) ester, stir at 100rpm for 20min, melt extrude at 180℃, cool, and pelletize to obtain carbon black masterbatch.

[0037] Example 2 0.75 g of epoxycyclohexyl-cage-type polysilsesquioxane, 3 g of the amino zinc-based metal-organic framework obtained in Preparation Example 2, and 40 mL of N,N-dimethylformamide were mixed and ultrasonically dispersed at 400 W for 30 min. The mixture was then heated and stirred at 100 °C for 45 min under nitrogen protection to obtain a hybrid filler dispersion. 45 g of quaternary ammonium salt grafted carbon black obtained in Preparation Example 1, 3 g of dopamine hydrochloride, and 300 mL of Tris-HCl buffer were mixed and stirred at 400 rpm for 1.5 h. The mixture was centrifuged at 9000 rpm for 15 min, washed three times with deionized water, and dried at 90 °C for 18 h to obtain polydopamine-anchored quaternary ammonium salt grafted carbon black. The hybrid filler dispersion and polydopamine-anchored quaternary ammonium salt grafted carbon black were added to 55g of polypropylene and stirred at 200rpm for 15min. Then, 0.6g of boron nitride, 0.6g of cerium oxide and 2g of maleic anhydride grafted polypropylene were added and stirred at 700rpm for 15min. Then, 1.5g of polyethylene wax, 1.5g of zinc stearate, 0.5g of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 0.5g of tris(2,4-di-tert-butylphenyl) phosphite and 1g of poly(4-hydroxy-2,2,6,6-tetramethyl-1-piperidinol) ester were added and stirred at 200rpm for 15min. The mixture was melt-extruded at 200℃, cooled, and pelletized to obtain carbon black masterbatch.

[0038] Example 3 1 g of epoxycyclohexyl-cage-type polysilsesquioxane, 4 g of the amino zinc-based metal-organic framework obtained in Preparation Example 2, and 50 mL of N,N-dimethylformamide were mixed and ultrasonically dispersed at 500 W for 20 min. The mixture was then heated and stirred at 120 °C for 30 min under nitrogen protection to obtain a hybrid filler dispersion. 60 g of quaternary ammonium salt grafted carbon black obtained in Preparation Example 1, 4 g of dopamine hydrochloride, and 400 mL of Tris-HCl buffer were mixed and stirred at 500 rpm for 1 h. The mixture was centrifuged at 10,000 rpm for 10 min, washed three times with deionized water, and dried at 100 °C for 12 h to obtain polydopamine. Anchored quaternary ammonium salt grafted carbon black: The hybrid filler dispersion and polydopamine-anchored quaternary ammonium salt grafted carbon black were added to 40g of polypropylene and stirred at 300rpm for 10min. Then, 1g of boron nitride, 1g of cerium oxide and 3g of maleic anhydride grafted polypropylene were added and stirred at 800rpm for 10min. Then, 2g of polyethylene wax, 3g of zinc stearate, 1g of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 1g of tris(2,4-di-tert-butylphenyl) phosphite and 1.5g of poly(4-hydroxy-2,2,6,6-tetramethyl-1-piperidinol) ester were added and stirred at 300rpm for 10min. The mixture was melt-extruded at 230℃, cooled, and pelletized to obtain carbon black masterbatch.

[0039] Comparative Example 1 The difference between this comparative example and Example 2 is that the amino-zinc-based metal-organic framework in Example 2 is replaced by a zinc-based metal-organic framework.

[0040] Comparative Example 2 The difference between this comparative example and Example 2 is that in this comparative example, the quaternary ammonium salt grafted carbon black in Example 2 is replaced with carbon black.

[0041] Comparative Example 3 The difference between this comparative example and Example 2 is that the epoxy cyclohexyl-cage polysilsesquioxane in Example 2 is replaced by an amino zinc-based metal-organic framework.

[0042] Comparative Example 4 The difference between this comparative example and Example 2 is that the amino zinc-based metal-organic framework in Example 2 is replaced by an epoxy cyclohexyl-cage polysilsesquioxane.

[0043] Comparative Example 5 The difference between this comparative example and Example 2 is that in this comparative example, boron nitride and other substances in Example 2 are replaced with cerium oxide.

[0044] Comparative Example 6 The difference between this comparative example and Example 2 is that in this comparative example, the cerium oxide in Example 2 is replaced by boron nitride.

[0045] Comparative Example 7 The difference between this comparative example and Example 2 is that the mass of cerium oxide in Example 2 is replaced with an amino zinc-based metal-organic framework and an epoxy cyclohexyl-cage polysilsesquioxane. Specifically, the mass of the amino zinc-based metal-organic framework is 3.48 g, and the mass of the epoxy cyclohexyl-cage polysilsesquioxane is 0.87 g.

[0046] Comparative Example 8 The difference between this comparative example and Example 2 is that the amino zinc-based metal-organic framework and epoxy cyclohexyl-cage polysilsesquioxane in Example 2 are replaced by cerium oxide, specifically, the mass of cerium oxide is 4.35g.

[0047] The carbon black masterbatches prepared in Examples 1-3 and Comparative Examples 1-8 were subjected to odor tests, notched impact strength tests, and tensile strength tests. The results are shown in Table 1.

[0048] Odor testing: The odor level of the carbon black masterbatch was evaluated according to Volkswagen AG's PV3900 odor assessment standard. The total volatile organic compounds (TVOC) of the carbon black masterbatch were evaluated according to the PV3341 standard.

[0049] Notched impact strength: The notched impact strength was tested according to GB / T 1043 "Determination of impact properties of simply supported plastic beams - Part 1: Non-instrumental impact test".

[0050] Mechanical property testing: The tensile strength of the masterbatch was tested according to ISO527-2-2019.

[0051] Table 1. Performance of carbon black masterbatch in Examples 1-3 and Comparative Examples 1-8

[0052] As shown in Examples 1-3 and Table 1, the carbon black masterbatches of Examples 1-3 of this application have an odor level of Grade 1, a TVOC of less than 8 μg C / g, and a notched impact strength of 21.9 kJ / m. 2 The tensile strength is above 198.3 MPa. This indicates that the present application constructs a synergistic deodorization system integrating physical adsorption, chemical degradation, and source suppression, enabling the carbon black masterbatch to possess both highly efficient deodorization performance and good mechanical properties.

[0053] As shown in Example 2, Comparative Example 1, and Table 1, the carbon black masterbatch of Example 2 of this application has an odor level of Grade 1, a TVOC of 5 μg C / g, and a notched impact strength of 23.2 kJ / m. 2 The tensile strength was 203.8 MPa, significantly better than that of Comparative Example 1. This indicates that the present application modifies the zinc-based metal-organic framework by amylation, allowing its amino functional groups to undergo an epoxy-amino ring-opening reaction with epoxycyclohexyl-cage polysilsesquioxane, forming a stable chemical bonding interface and constructing a structurally complete and uniformly distributed organic-inorganic hybrid network, thereby significantly improving the chemical adsorption efficiency. Compared to Example 2, the unmodified zinc-based metal-organic framework in Comparative Example 1 lacks the aforementioned chemical bonding sites, and can only form a weak physical mixture with epoxycyclohexyl-cage polysilsesquioxane, resulting in uneven dispersion and poor interfacial bonding in the resin matrix. The pore structure is easily damaged during processing, the adsorption efficiency is significantly reduced, and it cannot form an efficient catalytic degradation microenvironment with cerium oxide, thus significantly increasing the odor level.

[0054] As shown in Example 2, Comparative Example 2, and Table 1, the carbon black masterbatch of Example 2 of this application has an odor level of Grade 1, a TVOC of 5 μg C / g, and a notched impact strength of 23.2 kJ / m. 2The tensile strength was 203.8 MPa, significantly better than Comparative Example 2. This indicates that by grafting quaternary ammonium salts onto carbon black, this application effectively inhibits secondary agglomeration of carbon black particles during masterbatch processing through the synergistic effect of electrostatic repulsion and steric hindrance, ensuring uniform distribution within the polypropylene carrier. Furthermore, the long-chain alkyl groups of the quaternary ammonium salt interact strongly with the catechol groups of polydopamine and the anhydride groups of maleic anhydride-grafted polypropylene, forming a stable interfacial bond. This reduces stress concentration caused by interfacial defects, significantly improving the notched impact strength and tensile strength of the masterbatch. Compared to Example 2, the unmodified carbon black in Comparative Example 2 lacks an active modification layer, making it prone to agglomeration during melt blending, resulting in uneven dispersion. This not only reduces the coloring effect but also weakens the mechanical properties due to localized stress concentration. Simultaneously, the highly hydrophobic surface of the unmodified carbon black has poor compatibility with the polar resin carrier, making it difficult to form a stable anchoring structure with polydopamine, weakening the synergistic effect of odor adsorption and catalytic degradation, thus significantly increasing the odor level.

[0055] As shown in Example 2, Comparative Examples 3-4, and Table 1, the carbon black masterbatch of Example 2 of this application has an odor level of Grade 1, a TVOC of 5 μg C / g, and a notched impact strength of 23.2 kJ / m. 2 The tensile strength was 203.8 MPa, significantly better than Comparative Examples 3-4. This indicates that this application constructs a stable organic-inorganic hybrid network structure through the synergistic compounding of epoxy cyclohexyl-cage-shaped polysilsesquioxane and aminated zinc-based metal-organic framework, significantly improving the deodorization and mechanical properties of the masterbatch. Compared to Example 2, although the simple aminated zinc-based metal-organic framework in Comparative Example 3 can physically adsorb and chemically capture odor molecules, it is prone to pore collapse or agglomeration during melt processing, resulting in a significant decrease in adsorption efficiency. Furthermore, the interfacial bonding force between the aminated zinc-based metal-organic framework and the resin carrier and other functional components (such as polydopamine-anchored carbon black, boron nitride, etc.) is insufficient, leading to uneven dispersion, increased interfacial defects, and consequently reduced mechanical properties. Compared to Example 2, although the simple epoxy cyclohexyl-cage-shaped polysilsesquioxane in Comparative Example 4 has a nanocage structure that can adsorb small molecule odor substances, it cannot achieve efficient enrichment and specific capture of odor molecules.

[0056] As shown in Example 2, Comparative Examples 5-6, and Table 1, the carbon black masterbatch of Example 2 of this application has an odor level of Grade 1, a TVOC of 5 μg C / g, and a notched impact strength of 23.2 kJ / m. 2The tensile strength was 203.8 MPa, significantly better than that of Comparative Examples 5-6. This indicates that the synergistic compounding of boron nitride and cerium oxide in this application constructs a dual synergistic mechanism of "physical heat dissipation-chemical quenching," which significantly inhibits small-molecule odor byproducts generated by thermal oxidative degradation of resin carriers and additives during high-temperature processing, while simultaneously improving the mechanical properties of the masterbatch. Compared to Example 2, although the pure cerium oxide in Comparative Example 5 can quench free radicals and catalyze the degradation of odor molecules, its dispersibility in the resin matrix is ​​limited, and its contribution to inhibiting thermal oxidative degradation is limited. Moreover, it is prone to agglomeration during melt blending, leading to increased interface defects and decreased mechanical properties. Compared to Example 2, the pure boron nitride in Comparative Example 6 can accelerate heat dissipation and reduce the rate of free radical generation, but it cannot fill the microscopic gaps between micron-sized particles, resulting in insufficient continuity and uniformity of the thermally conductive network.

[0057] As shown in Example 2, Comparative Examples 7-8, and Table 1, the carbon black masterbatch of Example 2 of this application has an odor level of Grade 1, a TVOC of 5 μg C / g, and a notched impact strength of 23.2 kJ / m. 2 The tensile strength was 203.8 MPa, significantly better than Comparative Examples 7-8. This indicates that the synergistic combination of epoxy cyclohexyl-cage-like polysilsesquioxane, amino zinc-based metal-organic framework, and cerium oxide in this application can achieve efficient deodorization and good mechanical properties. Compared to Example 2, although the simple epoxy cyclohexyl-cage-like polysilsesquioxane and amino zinc-based metal-organic framework in Comparative Example 7 can form a hybrid network through chemical bonding and provide physical adsorption, it lacks the catalytic degradation function of cerium oxide. The adsorbed odor molecules cannot be decomposed into odorless small molecules in time, resulting in the secondary release of odor substances after adsorption saturation. At the same time, the small molecule byproducts generated during thermal oxidation cannot be effectively removed, resulting in a reduced deodorization effect. Compared to Example 2, although the cerium oxide alone in Comparative Example 8 can catalyze the degradation of some odor molecules, its nanoparticles are prone to agglomeration at high addition levels, failing to form a uniform dispersion, resulting in a significant decrease in catalytic efficiency. At the same time, the lack of porous adsorption of the aminated zinc-based metal-organic framework and the nanocage-like synergistic capture of epoxy cyclohexyl-cage polysilsesquioxane means that odor molecules cannot be effectively enriched near the catalytic site, resulting in a significant reduction in deodorization effect and mechanical properties.

[0058] Examples 4-5 Based on Example 2, except for the weight ratio of epoxycyclohexyl-cage polysilsesquioxane and zinc-aminated metal-organic framework, the other components and preparation methods are the same as in Example 2, and the total weight of epoxycyclohexyl-cage polysilsesquioxane and zinc-aminated metal-organic framework remains unchanged.

[0059] Example 4 The difference between this embodiment and Embodiment 2 is that the weight ratio of epoxycyclohexyl-cage polysilsesquioxane and zinc-aminated metal-organic framework in this embodiment is 0.5:1. Specifically, the weight of epoxycyclohexyl-cage polysilsesquioxane is 1.25g and the weight of zinc-aminated metal-organic framework is 2.5g.

[0060] Example 5 The difference between this embodiment and Embodiment 2 is that the weight ratio of epoxycyclohexyl-cage polysilsesquioxane and zinc-aminated metal-organic framework in this embodiment is 0.8:1. Specifically, the weight of epoxycyclohexyl-cage polysilsesquioxane is 1.67g and the weight of zinc-aminated metal-organic framework is 2.08g.

[0061] Examples 6-7 Based on Example 4, except for the weight ratio of quaternary ammonium salt grafted carbon black and dopamine hydrochloride, the other components and preparation methods are the same as in Example 4, and the total weight of quaternary ammonium salt grafted carbon black and dopamine hydrochloride remains unchanged.

[0062] Example 6 The difference between this embodiment and embodiment 4 is that the weight ratio of quaternary ammonium salt grafted carbon black to dopamine hydrochloride in this embodiment is 14:1. Specifically, the weight of quaternary ammonium salt grafted carbon black is 44.8g and the weight of dopamine hydrochloride is 3.2g.

[0063] Example 7 The difference between this embodiment and embodiment 4 is that the weight ratio of quaternary ammonium salt grafted carbon black to dopamine hydrochloride in this embodiment is 13:1. Specifically, the weight of quaternary ammonium salt grafted carbon black is 44.57g and the weight of dopamine hydrochloride is 3.43g.

[0064] Examples 8-9 Based on Example 6, except for the weight ratio of boron nitride and cerium oxide, the other components and preparation methods are the same as in Example 6, and the total weight of boron nitride and cerium oxide remains unchanged.

[0065] Example 8 The difference between this embodiment and embodiment 6 is that the weight ratio of boron nitride to cerium oxide in this embodiment is 1:2. Specifically, the weight of boron nitride is 0.4g and the weight of cerium oxide is 0.8g.

[0066] Example 9 The difference between this embodiment and Embodiment 6 is that the weight ratio of boron nitride to cerium oxide in this embodiment is 1:3. Specifically, the weight of boron nitride is 0.3g and the weight of cerium oxide is 0.9g.

[0067] Performance Test 2 The carbon black masterbatches prepared in Examples 2 and 4-9 were subjected to odor tests, notched impact strength tests, and tensile strength tests. The test results are shown in Table 2 below.

[0068] Table 2 Performance of carbon black masterbatch in Examples 2 and 4-9

[0069] As shown in Examples 2, 4-5, and Table 2, the carbon black masterbatch of Example 4 of this application has an odor level of Grade 1, a TVOC of 4 μg C / g, and a notched impact strength of 23.8 kJ / m. 2 The tensile strength was 205.5 MPa, significantly better than that of Examples 2 and 5. This indicates that the present application uses a specific weight ratio of epoxy cyclohexyl-cage polysilsesquioxane and zinc-ammonia-based metal-organic framework to construct a more stable and efficient organic-inorganic hybrid network structure, thereby significantly improving deodorization performance and mechanical properties. Compared to Example 4, the proportion of zinc-ammonia-based metal-organic framework in Example 2 is too high, which can lead to pore collapse or agglomeration during melt processing, resulting in decreased physical adsorption efficiency and significantly reduced mechanical properties. Compared to Example 4, the proportion of epoxy cyclohexyl-cage polysilsesquioxane in Example 5 is too high, which can lead to self-aggregation in the system, increased interface defects, and decreased deodorization performance and mechanical properties.

[0070] As shown in Examples 4, 6-7, and Table 2, the notched impact strength of the carbon black masterbatch in Example 6 of this application is 24.4 kJ / m. 2 The tensile strength was 211.3 MPa, significantly better than that of Examples 4 and 7. This indicates that the present application uses a specific weight ratio of quaternary ammonium salt grafted carbon black and dopamine hydrochloride, which significantly improves deodorization performance and mechanical properties. Compared to Example 6, the excessively high proportion of quaternary ammonium salt grafted carbon black in Example 4 leads to an incomplete polydopamine coating layer, insufficient anchoring of the carbon black surface, and a tendency for secondary agglomeration during melt processing, resulting in decreased dispersion uniformity, stress concentration points, and weakened notched impact strength and tensile strength. Compared to Example 6, the excessively high proportion of dopamine hydrochloride in Example 7 leads to an excessively thick polydopamine coating layer or even self-aggregation. On the one hand, this excessively masks the quaternary ammonium salt active sites on the carbon black surface, weakening antibacterial and interfacial compatibility functions; on the other hand, the excessively thick coating layer introduces brittleness at the interface, reducing impact toughness.

[0071] As shown in Examples 6, 8-9 and Table 2, the notched impact strength of the carbon black masterbatch in Example 8 of this application is 25.6 kJ / m. 2The tensile strength was 216.0 MPa, significantly better than that of Examples 6 and 9. This indicates that the use of a specific weight ratio of boron nitride and cerium oxide in this application can significantly optimize the balance between thermal management efficiency and free radical scavenging ability, thereby greatly improving the mechanical properties of the masterbatch while maintaining excellent deodorization performance. Compared to Example 8, the excessively high proportion of boron nitride in Example 6 leads to insufficient continuity of the thermally conductive network, and the nano-sized cerium oxide cannot fully fill the microscopic gaps between the micron-sized boron nitride particles, resulting in a decrease in free radical quenching efficiency and a reduction in mechanical properties. Compared to Example 8, the excessively high proportion of cerium oxide in Example 9 causes the nanoparticles to easily agglomerate in the resin matrix, reducing dispersion uniformity and leading to a reduction in mechanical properties.

[0072] The above are all preferred embodiments of this application, and are not intended to limit the scope of protection of this application. Therefore, all equivalent changes made in accordance with the structure, shape and principle of this application should be covered within the scope of protection of this application.

Claims

1. A carbon black masterbatch, characterized in that, The raw materials include the following parts by weight: 30-60 parts quaternary ammonium salt grafted carbon black, 40-70 parts resin carrier, 2-4 parts dopamine hydrochloride, 0.3-1 part boron nitride, 0.3-1.2 parts cerium oxide, 0.5-1.67 parts epoxy cyclohexyl-cage polysilsesquioxane, 2-4 parts amino zinc-based metal-organic framework, 1-3 parts maleic anhydride grafted polypropylene, 1-5 parts dispersant, 0.5-2 parts antioxidant, and 0.5-1.5 parts hindered amine light stabilizer.

2. The carbon black masterbatch according to claim 1, characterized in that, The preparation steps of the quaternary ammonium salt grafted carbon black include: mixing carbon black and ethanol solution, ultrasonically dispersing, adding dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride, heating and stirring, centrifuging, washing, and drying to obtain quaternary ammonium salt grafted carbon black.

3. The carbon black masterbatch according to claim 1, characterized in that, The preparation steps of the aminated zinc-based metal-organic framework include: mixing the zinc-based metal-organic framework and N,N-dimethylformamide, ultrasonically dispersing, adding 2-aminobenzimidazole, heating and stirring, centrifuging, washing, and drying to obtain the aminated zinc-based metal-organic framework.

4. The carbon black masterbatch according to claim 1, characterized in that, The weight ratio of the epoxy cyclohexyl-cage polysilsesquioxane to the amino zinc-based metal-organic framework is (0.25-0.8):

1.

5. The carbon black masterbatch according to claim 1, characterized in that, The weight ratio of the quaternary ammonium salt grafted carbon black to dopamine hydrochloride is (13-15):

1.

6. The carbon black masterbatch according to claim 1, characterized in that, The weight ratio of boron nitride to cerium oxide is 1:(1-3).

7. The carbon black masterbatch according to claim 1, characterized in that, The boron nitride has a particle size of 3-10 μm, and the cerium oxide has a particle size of 20-100 nm.

8. The carbon black masterbatch according to claim 1, characterized in that, The antioxidant is at least one of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and tris(2,4-di-tert-butylphenyl)phosphite, and the dispersant is at least one of stearic acid, zinc stearate, and polyethylene wax.

9. The carbon black masterbatch according to claim 1, characterized in that, The resin carrier is polypropylene, and the hindered amine light stabilizer is poly(4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol) ester.

10. A method for preparing carbon black masterbatch according to any one of claims 1-9, characterized in that, Includes the following steps: S1. Mix epoxycyclohexyl-cage polysilsesquioxane, amino zinc-based metal-organic framework and first solvent, disperse by ultrasonication, heat and stir under inert gas protection to obtain hybrid filler dispersion; S2. Mix quaternary ammonium salt grafted carbon black, dopamine hydrochloride and the second solvent, stir evenly, centrifuge, wash and dry to obtain polydopamine-anchored quaternary ammonium salt grafted carbon black. S3. Add the hybrid filler dispersion and polydopamine-anchored quaternary ammonium salt grafted carbon black to the resin carrier and stir evenly. Then add boron nitride, cerium oxide and maleic anhydride grafted polypropylene and stir evenly. Add dispersant, antioxidant and hindered amine light stabilizer and stir evenly. Melt extrusion, cool and pelletize to obtain carbon black masterbatch.

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