Wet-process rubber master batch based on three-phase synergistic reinforcement and preparation method and application of wet-process rubber master batch
By constructing a three-dimensional reinforcing system of carbon black-CNTs-rubber molecular chains and combining it with wet masterbatch process to achieve nanoscale dispersion of CNTs, the performance bottleneck of traditional tire tread compound is solved, the wear resistance and cut resistance of tires are improved, and the energy consumption and mixing cost are reduced.
Patent Information
- Application Number
- CN202510952504.1
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-07-10
- Publication Date
- 2025-12-02
AI Technical Summary
The carbon black reinforcing system in traditional tire tread compounds has performance bottlenecks, leading to increased dynamic heat generation, reduced fatigue life, and insufficient cut resistance. Carbon nanotubes are prone to agglomeration in the rubber matrix and are costly, which limits their application in the tire industry.
A three-dimensional reinforcing system of carbon black-CNTs-rubber molecular chains was constructed. Nanoscale dispersion of CNTs was achieved through a wet masterbatch process. The amount of CNTs added was optimized, and a uniform composite material was formed by combining specific carbon black and dispersant.
Significantly improves tire wear resistance, cut resistance, and dynamic mechanical properties, reduces energy consumption and compounding costs, and provides high-performance tire solutions.
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Abstract
Description
Technical Field
[0001] This application belongs to the field of rubber composite materials technology, and relates to a wet-process masterbatch based on three-phase synergistic reinforcement, its preparation method and application. Background Technology
[0002] As the core component that directly contacts the road surface, the tire tread compound's wear resistance, cut resistance, and dynamic mechanical properties directly affect the tire's service life and driving safety. Traditional tire tread compounds commonly use carbon black (such as N134, N115, and N220) as the main reinforcing agent, with typical formulations containing 30-60 parts of carbon black to the rubber matrix. However, carbon black reinforcement systems have significant performance bottlenecks: when the carbon black content exceeds 50 parts, the compound hardness increases sharply, leading to intensified dynamic heat generation; experiments show that excessive carbon black can reduce fatigue life by more than 20%. In engineering machinery tire applications, driving on gravel roads easily causes tread groove tearing, with traditional compounds exhibiting a cut growth rate as high as 100%, making it difficult to meet the demands of harsh working conditions. Furthermore, the rigid network formed by carbon black aggregates reduces the compound's dynamic flexibility, with the Payne effect ΔG' value typically exceeding 600 kPa, limiting the tire's adaptability under complex working conditions.
[0003] Carbon nanotubes (CNTs) are considered ideal materials for reinforcing rubber due to their ultra-high aspect ratio (>1000) and excellent mechanical properties (elastic modulus up to 1 TPa). However, their industrial application faces multiple technical obstacles: CNTs have high surface energy and are prone to agglomeration in rubber matrices. Traditional dry mixing requires high-shear equipment (increasing energy consumption by 40%) or complex pre-functionalization treatment (such as wet spray mixing) to achieve initial dispersion; the dosage effect is significantly contradictory. When the amount of CNTs added exceeds 3%, interfacial stress concentration leads to a 15% decrease in tear strength; high-purity CNTs are expensive, and the synergistic reinforcing mechanism with carbon black is not yet clear, which limits their large-scale application in the tire industry.
[0004] To address the aforementioned technical challenges, this invention proposes a wet-process masterbatch technology based on three-phase synergistic reinforcement. By constructing a three-dimensional reinforcing system of carbon black-CNTs-rubber molecular chains and combining it with the wet-process masterbatch process to achieve nanoscale dispersion of CNTs, the performance bottleneck of single fillers is overcome by optimizing the amount of CNTs added. Summary of the Invention
[0005] Regarding the current purification issues, one of the objectives of this application is to provide a wet-process masterbatch based on three-phase synergistic reinforcement, its preparation method, and its application. By constructing a three-dimensional reinforcing system of carbon black-CNTs-rubber molecular chains and combining it with the wet-process masterbatch process to achieve nanoscale dispersion of CNTs, and by optimizing the amount of CNTs added, the performance bottleneck of single fillers can be overcome, which can significantly improve the wear resistance, cut resistance, and dynamic mechanical properties of tires.
[0006] This application provides a wet-process masterbatch based on three-phase synergistic reinforcement, its preparation method and application. The raw materials for preparing the wet-process masterbatch based on three-phase synergistic reinforcement, by weight, include 100 parts of natural latex, 45-55 parts of carbon black, 0.5-4 parts of modified multi-walled carbon nanotubes, and 0.5-1 parts of dispersant.
[0007] In some embodiments of this application, the solid content of the natural latex is 60%.
[0008] In some embodiments of this application, the method for preparing the carbon black includes the following steps:
[0009] A1. Mix the first carbon black and the second carbon black, and premix them in a high-speed mixer to obtain compound carbon black;
[0010] A2. Mix the compounded carbon black and concentrated nitric acid, and reflux at a constant temperature of 78-82℃. After that, filter to separate the carbon black, wash with deionized water until the filtrate is neutral, and place the washed carbon black in a vacuum drying oven and dry at 78-82℃ for 10-14 hours to obtain the final product.
[0011] In some embodiments of this application, the mass ratio of the first carbon black to the second carbon black is 1:(0.8-1.2).
[0012] In some embodiments of this application, the first carbon black has an oil absorption value of 108-118 mL / 100 g and an external surface area of 119-129 m². 2 / g, 325 mesh sieve residue ≤500ppm.
[0013] In some embodiments of this application, the second carbon black has an oil absorption value of 120-130 mL / 100 g and an external surface area of 107-117 m². 2 / g, bulk density is 315-395kg / m³ 3 .
[0014] In some embodiments of this application, the first carbon black and the second carbon black are both purchased from Cabot Corporation of the United States, and are N115 and N234, respectively.
[0015] In some embodiments of this application, the specific conditions for premixing in step A1 are: rotation speed of 500-800 r / min and time of 10-15 min.
[0016] In some embodiments of this application, in step A2, the solid-liquid ratio of the compounded carbon black and concentrated nitric acid is 1 g: (8-12) mL.
[0017] In some embodiments of this application, the concentration of nitric acid in the concentrated nitric acid is 60%-65%.
[0018] In some embodiments of this application, the specific conditions for the reflux reaction are: temperature of 78-82℃, reaction time of 3-5h, ultrasonic treatment for 10min every 30min, ultrasonic power of 380-420W, and frequency of 38-42kHz.
[0019] In some embodiments of this application, the method for preparing the modified multi-walled carbon nanotubes includes the following steps: adding multi-walled carbon nanotubes to a mixed acid, ultrasonicating and then refluxing the reaction, slowly pouring the reacted liquid into ice water for dilution, filtering and washing with deionized water until neutral, and drying at 78-82℃ for 10-14 hours to obtain the product.
[0020] In some embodiments of this application, the multi-walled carbon nanotubes have a diameter of 20-30 nm and a purity of >95%.
[0021] In some embodiments of this application, the mixed acid is a mixture of concentrated sulfuric acid and concentrated nitric acid.
[0022] In some embodiments of this application, the volume ratio of concentrated sulfuric acid to concentrated nitric acid is 3:1.
[0023] In some embodiments of this application, the concentration of sulfuric acid in the concentrated sulfuric acid is 98%.
[0024] In some embodiments of this application, the solid-liquid ratio of the multi-walled carbon nanotubes and the mixed acid is 1 g:(45-55) mL.
[0025] In some embodiments of this application, the specific conditions for the ultrasonic treatment are: ultrasonic power of 280-320W, frequency of 38-42kHz, and duration of 1.5-2.5h.
[0026] In some embodiments of this application, the specific conditions for the reflux reaction 2 are: a temperature of 58-62°C and a reaction time of 5-7 hours.
[0027] In some embodiments of this application, the volume ratio of the reacted liquid to ice water is 1:10.
[0028] In some embodiments of this application, the amount of modified multi-walled carbon nanotubes added is 1%-3% of the mass of natural latex.
[0029] In some embodiments of this application, the mass ratio of the carbon black to the modified multi-walled carbon nanotubes is (20-30):1.
[0030] In some embodiments of this application, the dispersant includes any one of polyvinylpyrrolidone and N-methylpyrrolidone.
[0031] In some embodiments of this application, the method for preparing the wet masterbatch based on three-phase synergistic reinforcement includes the following steps:
[0032] S1. Pre-dispersion treatment: Modified multi-walled carbon nanotubes, carbon black and dispersant are mixed and sheared to form a homogeneous suspension;
[0033] S2. In-situ composite: Using wet composite technology, the homogeneous suspension obtained in step S1 is sprayed and flocculated with natural rubber latex to form composite masterbatch particles, which are then dehydrated, dried and shaped to obtain the final product.
[0034] In some embodiments of this application, the specific conditions for shearing in step S1 are: shearing speed of 10000r / min-12000r / min and shearing time of 28-32min.
[0035] In some embodiments of this application, the specific conditions for the spraying process in step S2 are: the spraying pressure is 0.3-0.5 MPa.
[0036] In some embodiments of this application, the specific steps of flocculation are as follows: first, add a 5% sulfuric acid solution to the system pH to 5.5-6.0, stir at 300-400 r / min for 14-16 min, add more sulfuric acid solution to the pH to 4.0-4.5, reduce the stirring speed to 150-200 r / min, stir for 20-30 min, and continuously purge with nitrogen gas for protection during the stirring process, with a nitrogen flow rate of 0.5-1.0 L / min.
[0037] In some embodiments of this application, the dehydration is pressure filtration dehydration, with a pressure of 0.6-0.8 MPa and a holding time of 30-40 min.
[0038] In some embodiments of this application, the drying is vacuum drying, with a drying temperature of 80-90℃, a vacuum degree of 0.08-0.1MPa, and a drying time of 4-6h.
[0039] In some embodiments of this application, the molding is extrusion granulation, the screw speed is 80-100 r / min, the barrel temperature is controlled in stages, the feeding section temperature is 58-62℃, the compression section temperature is 78-82℃, the metering section temperature is 88-92℃, and the die head temperature is 98-102℃.
[0040] In some embodiments of this application, the wet masterbatch based on three-phase synergistic reinforcement is used to prepare tire tread compound.
[0041] In some embodiments of this application, the tire tread compound is prepared by means of raw materials, which, by weight, include 150-155 parts of wet-process masterbatch based on three-phase synergistic reinforcement, 1-3 parts of stearic acid, 4-6 parts of zinc oxide, 0.5-1.5 parts of antioxidant 4020, 1-3 parts of sulfur, and 1-1.5 parts of accelerator CZ.
[0042] In some embodiments of this application, the method for preparing the tire tread compound includes the following steps:
[0043] 1) Mixing: Wet masterbatch, zinc oxide, stearic acid, antioxidant 4020 are added to an internal mixer for a first stage of mixing, and then accelerator CZ is added for a second stage of mixing to obtain masterbatch.
[0044] 2) Final mixing: Add the masterbatch rubber to the open mill, add sulfur and CZ, set the roll temperature to 65-70℃, the roll gap to 1.5-2.0mm, wrap the rolls, pass through the thin mill 6-8 times, sheet out, and cool at room temperature to obtain the final rubber.
[0045] 3) Vulcanization: The final rubber compound is vulcanized and molded to obtain the final product.
[0046] In some embodiments of this application, the specific conditions for the first stage of mixing are as follows: initial temperature of 90-95℃, rotor speed of 60-70 r / min, top bolt pressure of 0.5-0.7 MPa, maintained for 3-4 minutes until the temperature rises to 130-135℃, and then the glue is discharged.
[0047] In some embodiments of this application, the specific conditions for the two-stage mixing are as follows: initial temperature of 70-75℃, rotor speed of 40-50 r / min, top bolt pressure of 0.5-0.7 MPa, maintained for 2-3 minutes until the temperature rises to 100-105℃, and then the glue is discharged.
[0048] In some embodiments of this application, the specific conditions for vulcanization molding are: vulcanization temperature of 150-160℃, vulcanization pressure of 10-15MPa, and vulcanization time of 28-32min.
[0049] Compared with the prior art, this application achieves at least the following technical effects:
[0050] This invention proposes a wet-process masterbatch technology based on three-phase synergistic reinforcement. By constructing a three-dimensional reinforcing system of carbon black-CNTs-rubber molecular chains, and combining it with the wet-process masterbatch process, nanoscale dispersion of CNTs is achieved, avoiding high-energy-consuming mixing. Based on optimizing the amount of CNTs added, cost and performance are balanced, breaking through the performance bottleneck of single fillers. This can significantly improve the wear resistance, cut resistance, and dynamic mechanical properties of tires, providing a cost-effective and process-feasible solution for the high-performance of engineering machinery tires.
[0051] This invention selects specific natural latex, carbon black, and multi-walled carbon nanotubes as raw materials for preparing wet-process masterbatch, and then uses them to prepare tire tread compound, which can improve the toughness, wear resistance and cut resistance of tire tread compound.
[0052] This invention uses two specific carbon black compounds to further improve the reinforcing effect; by subjecting the compounded carbon black to nitric acid oxidation modification, the various properties of the tire tread compound and the dispersion stability of the carbon black in the latex are further improved.
[0053] This invention optimizes the dispersion and compounding of multi-walled carbon nanotubes through a wet masterbatch process, reducing energy consumption during mixing while improving product uniformity, thereby enhancing the various properties of the final tire tread compound. Detailed Implementation
[0054] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below. However, it should be understood that the description herein is merely illustrative and not intended to limit the scope of the invention.
[0055] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The terminology used herein in the specification is for the purpose of describing particular embodiments only and is not intended to limit the scope of the invention. All reagents and instruments used herein are commercially available, and the characterization methods involved are described in relevant prior art and will not be repeated herein.
[0056] All raw materials used in this invention are commercially available, specifically:
[0057] Natural latex with a solid content of 60% is high-ammonia concentrated latex from Hainan Natural Rubber Industry Group Jinxiang Co., Ltd.
[0058] The first type of carbon black has an oil absorption value of 108-118 mL / 100g and an external surface area of 119-129 m². 2 / g, residue on 325 mesh sieve ≤500ppm; oil absorption value of the second carbon black is 120-130mL / 100g, and external surface area is 107-117m². 2 / g, bulk density is 315-395kg / m³ 3 Both are from Jiangxi Black Cat Carbon Black Co., Ltd., and are N115 and N234 respectively.
[0059] Multi-walled carbon nanotubes, with a diameter of 20-30 nm and a purity of >95%, are from Jiangxi Black Cat High-Performance Materials Co., Ltd., HMT120.
[0060] Polyvinylpyrrolidone, from Shanghai Aladdin Chemical Reagent Co., Ltd., has an average relative molecular mass of 24,000.
[0061] Example 1
[0062] This embodiment provides a wet-process masterbatch based on three-phase synergistic reinforcement. The raw materials for preparing the wet-process masterbatch based on three-phase synergistic reinforcement include, by weight, 100 parts of natural latex, 50 parts of carbon black, 2 parts of modified multi-walled carbon nanotubes, and 0.8 parts of dispersant.
[0063] The method for preparing the carbon black comprises the following steps:
[0064] A1. Mix the first carbon black and the second carbon black, and premix them in a high-speed mixer to obtain compound carbon black;
[0065] A2. Mix the compounded carbon black and concentrated nitric acid, and reflux at 80°C. After that, filter to separate the carbon black, wash with deionized water until the filtrate is neutral, and place the washed carbon black in a vacuum drying oven and dry at 80°C for 12 hours to obtain the final product.
[0066] The mass ratio of the first carbon black to the second carbon black is 1:1.
[0067] In step A1, the specific premixing conditions are: rotation speed of 650 r / min and time of 12 min.
[0068] In step A2, the solid-liquid ratio of the compounded carbon black and concentrated nitric acid is 1g:10mL.
[0069] The concentration of nitric acid in the concentrated nitric acid is 65%.
[0070] The specific conditions for the reflux reaction are: temperature 80℃, reaction time 4h, ultrasonic treatment for 10min every 30min, ultrasonic power 400W, and frequency 40kHz.
[0071] The method for preparing the modified multi-walled carbon nanotubes includes the following steps: adding multi-walled carbon nanotubes to a mixed acid, ultrasonically treating them, and then refluxing them for reaction 2. The reacted liquid is then slowly poured into ice water for dilution, filtered, washed with deionized water until neutral, and dried at 80°C for 12 hours to obtain the final product.
[0072] The mixed acid is a mixture of concentrated sulfuric acid and concentrated nitric acid.
[0073] The volume ratio of concentrated sulfuric acid to concentrated nitric acid is 3:1.
[0074] The concentration of sulfuric acid in the concentrated sulfuric acid is 98%.
[0075] The solid-liquid ratio of the multi-walled carbon nanotubes and the mixed acid is 1g:50mL.
[0076] The specific conditions for the ultrasonic treatment are: ultrasonic power of 300W, frequency of 40kHz, and time of 2h.
[0077] The specific conditions for the reflux reaction 2 are: temperature 60℃ and reaction time 6h.
[0078] The volume ratio of the reacted liquid to ice water is 1:10.
[0079] The dispersant is polyvinylpyrrolidone.
[0080] The preparation method of the wet masterbatch based on three-phase synergistic reinforcement includes the following steps:
[0081] S1. Pre-dispersion treatment: Modified multi-walled carbon nanotubes, carbon black and dispersant are mixed and sheared to form a homogeneous suspension;
[0082] S2. In-situ composite: Using wet composite technology, the homogeneous suspension obtained in step S1 is sprayed and flocculated with natural rubber latex to form composite masterbatch particles, which are then dehydrated, dried and shaped to obtain the final product.
[0083] In step S1, the specific conditions for shearing are: shearing speed of 11000 r / min and shearing time of 30 min.
[0084] In step S2, the specific conditions for the spraying process are: the spraying pressure is 0.4 MPa.
[0085] The specific steps of the flocculation are as follows: First, add a 5% sulfuric acid solution to the system until the pH is 6.0, stir at 350 r / min for 15 min, add more sulfuric acid solution until the pH is 4.0, reduce the stirring speed to 180 r / min, stir for 25 min, and continuously introduce nitrogen gas for protection during the stirring process, with a nitrogen flow rate of 0.8 L / min.
[0086] The dehydration is performed by pressure filtration, with a pressure of 0.7 MPa and a holding time of 35 min.
[0087] The drying process is vacuum drying, with a drying temperature of 85℃, a vacuum degree of 0.09MPa, and a drying time of 5 hours.
[0088] The molding process is extrusion granulation, with a screw speed of 90 r / min and segmented temperature control of the barrel: 60°C for the feeding section, 80°C for the compression section, 90°C for the metering section, and 100°C for the die.
[0089] Example 2
[0090] The difference between this embodiment and Embodiment 1 is that the raw materials for preparing the wet-process masterbatch based on three-phase synergistic reinforcement, by weight, include 100 parts of natural latex, 50 parts of carbon black, 3 parts of modified multi-walled carbon nanotubes, and 0.5 parts of dispersant.
[0091] Comparative Example 1
[0092] The difference between this comparative example and Example 1 is that the raw materials for preparing the wet-process masterbatch based on three-phase synergistic reinforcement include 100 parts of natural latex and 50 parts of carbon black by weight.
[0093] Comparative Example 2
[0094] The difference between this comparative example and Example 1 is that the raw materials for preparing the wet-process masterbatch based on three-phase synergistic reinforcement, by weight, include 100 parts of natural latex, 50 parts of carbon black, 1 part of modified multi-walled carbon nanotubes, and 0.5 parts of dispersant.
[0095] Comparative Example 3
[0096] The difference between this comparative example and Example 1 is that the raw materials for preparing the wet-process masterbatch based on three-phase synergistic reinforcement, by weight, include 100 parts of natural latex, 50 parts of carbon black, 4 parts of modified multi-walled carbon nanotubes, and 0.5 parts of dispersant.
[0097] Comparative Example 4
[0098] The difference between this comparative example and Example 1 is that the preparation method of the carbon black is as follows:
[0099] The first carbon black N115 was mixed with concentrated nitric acid and refluxed at 80°C. The carbon black was then separated by filtration and washed with deionized water until the filtrate was neutral. The washed carbon black was then placed in a vacuum drying oven and dried at 80°C for 12 hours to obtain the final product.
[0100] Comparative Example 5
[0101] The difference between this comparative example and Example 1 is that the preparation method of the carbon black is as follows: the first carbon black and the second carbon black are mixed and premixed in a high-speed mixer to obtain the final product.
[0102] The mass ratio of the first carbon black to the second carbon black is 1:1.
[0103] Comparative Example 6
[0104] The difference between this comparative example and Example 1 is that the raw materials for preparing the wet-process masterbatch based on three-phase synergistic reinforcement, by weight, include 100 parts of natural latex, 50 parts of carbon black, 2 parts of multi-walled carbon nanotubes, and 0.8 parts of dispersant.
[0105] Example 3
[0106] This embodiment provides a tire tread compound. The raw materials for preparing the tire tread compound, by weight, include 152.5 parts of wet masterbatch based on three-phase synergistic reinforcement prepared in Example 1, 2 parts of stearic acid, 5 parts of zinc oxide, 1 part of antioxidant 4020, 2 parts of sulfur, and 1.2 parts of accelerator CZ.
[0107] The preparation method of the tire tread compound includes the following steps:
[0108] 1) Mixing: Wet masterbatch, zinc oxide, stearic acid, and antioxidant 4020 are added to an internal mixer and mixed for a period of time to obtain masterbatch;
[0109] 2) Final mixing: Add the masterbatch to the open mill, add sulfur and CZ, set the roll temperature to 70℃, the roll gap to 2.0mm, wrap the rolls, pass through the thin mill 7 times, sheet out, and cool at room temperature to obtain the final rubber.
[0110] 3) Vulcanization: The final rubber compound is vulcanized and molded to obtain the final product.
[0111] The specific conditions for the first stage of mixing are as follows: initial temperature of 90℃, rotor speed of 65r / min, top bolt pressure of 0.6MPa, maintained for 3.5min until the temperature rises to 135℃, and then the glue is discharged.
[0112] The specific conditions for the two-stage mixing are as follows: initial temperature of 70℃, rotor speed of 45r / min, top bolt pressure of 0.6MPa, maintained for 2.5min until the temperature rises to 105℃, and then the glue is discharged.
[0113] The specific conditions for vulcanization molding are: vulcanization temperature of 150℃, vulcanization pressure of 13MPa, and vulcanization time of 30min.
[0114] Example 4
[0115] The difference between this embodiment and Embodiment 3 is that the raw materials for preparing the tire tread compound, by weight, include 153.5 parts of the wet-process masterbatch based on three-phase synergistic reinforcement prepared in Embodiment 2, 2 parts of stearic acid, 5 parts of zinc oxide, 1 part of antioxidant 4020, 2 parts of sulfur, and 1.2 parts of accelerator CZ.
[0116] Comparative Example 7
[0117] This comparative example provides a tire tread compound, the raw materials of which, by weight, include 100 parts of natural latex, 50 parts of carbon black, 2 parts of modified multi-walled carbon nanotubes, 2 parts of stearic acid, 5 parts of zinc oxide, 1 part of antioxidant 4020, 2 parts of sulfur, and 1.2 parts of accelerator CZ.
[0118] The preparation method of the tire tread compound includes the following steps:
[0119] 1) Mixing: Natural latex, carbon black, modified multi-walled carbon nanotubes, zinc oxide, stearic acid, and antioxidant 4020 are added to an internal mixer and mixed for a period of time to obtain masterbatch.
[0120] 2) Final mixing: Add the masterbatch to the open mill, add sulfur and CZ, set the roll temperature to 70℃, the roll gap to 2.0mm, wrap the rolls, pass through the thin mill 7 times, sheet out, and cool at room temperature to obtain the final rubber.
[0121] 3) Vulcanization: The final rubber compound is vulcanized and molded to obtain the final product.
[0122] The specific conditions for the first stage of mixing are as follows: initial temperature of 90℃, rotor speed of 65r / min, top bolt pressure of 0.6MPa, maintained for 3.5min until the temperature rises to 135℃, and then the glue is discharged.
[0123] The specific conditions for the two-stage mixing are as follows: initial temperature of 70℃, rotor speed of 45r / min, top bolt pressure of 0.6MPa, maintained for 2.5min until the temperature rises to 105℃, and then the glue is discharged.
[0124] The specific conditions for vulcanization molding are: vulcanization temperature of 150℃, vulcanization pressure of 13MPa, and vulcanization time of 30min.
[0125] Comparative Example 8
[0126] The difference between this comparative example and Example 3 is that the raw materials for preparing the tire tread compound, by weight, include 150 parts of the wet-process masterbatch based on three-phase synergistic reinforcement prepared in Comparative Example 1, 2 parts of stearic acid, 5 parts of zinc oxide, 1 part of antioxidant 4020, 2 parts of sulfur, and 1.2 parts of accelerator CZ.
[0127] Comparative Example 9
[0128] The difference between this comparative example and Example 3 is that the raw materials for preparing the tire tread compound, by weight, include 151.5 parts of the wet masterbatch based on three-phase synergistic reinforcement prepared in Comparative Example 2, 2 parts of stearic acid, 5 parts of zinc oxide, 1 part of antioxidant 4020, 2 parts of sulfur, and 1.2 parts of accelerator CZ.
[0129] Comparative Example 10
[0130] The difference between this comparative example and Example 3 is that the raw materials for preparing the tire tread compound, by weight, include 154.5 parts of the wet masterbatch based on three-phase synergistic reinforcement prepared in Comparative Example 3, 2 parts of stearic acid, 5 parts of zinc oxide, 1 part of antioxidant 4020, 2 parts of sulfur, and 1.2 parts of accelerator CZ.
[0131] Comparative Example 11
[0132] The difference between this comparative example and Example 3 is that the raw materials for preparing the tire tread compound, by weight, include 152.5 parts of the wet masterbatch based on three-phase synergistic reinforcement prepared in Comparative Example 4, 2 parts of stearic acid, 5 parts of zinc oxide, 1 part of antioxidant 4020, 2 parts of sulfur, and 1.2 parts of accelerator CZ.
[0133] Comparative Example 12
[0134] The difference between this comparative example and Example 3 is that the raw materials for preparing the tire tread compound, by weight, include 152.5 parts of the wet masterbatch based on three-phase synergistic reinforcement prepared in Comparative Example 5, 2 parts of stearic acid, 5 parts of zinc oxide, 1 part of antioxidant 4020, 2 parts of sulfur, and 1.2 parts of accelerator CZ.
[0135] Comparative Example 13
[0136] The difference between this comparative example and Example 3 is that the raw materials for preparing the tire tread compound, by weight, include 152.5 parts of the wet masterbatch based on three-phase synergistic reinforcement prepared in Comparative Example 6, 2 parts of stearic acid, 5 parts of zinc oxide, 1 part of antioxidant 4020, 2 parts of sulfur, and 1.2 parts of accelerator CZ.
[0137] Performance testing
[0138] The properties of the tire tread compounds prepared in Examples 3-4 and Comparative Examples 7-13 were tested. The testing standards are as follows: Shore hardness A is tested according to GB / T 531.1-2008; tensile strength, stress at 100% constant elongation, stress at 300% constant elongation, and elongation at break are tested according to GB / T 528-2009; tear strength is tested according to GB / T 529-2008; springback is tested according to GB / T 1681-2009; compression heat rise is tested according to GB / T 1687-2016; density is tested according to GB / T 533-2008; Akron abrasion volume is tested according to GB / T 1689-2014; DIN abrasion is tested according to GB / T 9867-2008; RPA test method is strain 0.28%-50%, temperature 60℃, frequency 1Hz; thermal conductivity and thermal diffusivity test method is tested according to GB / T11205-2009; cutting abrasion test method is rotation speed 750rpm, cutting frequency 60 times / minute, and test time 15 minutes. The test results are shown in Table 1.
[0139] Table 1
[0140]
[0141]
[0142] As shown in Table 1, the wet masterbatch based on three-phase synergistic reinforcement used in Experimental Examples 3 and 4 can uniformly disperse carbon nanotubes and carbon black, resulting in excellent tensile strength, tear strength, resilience, elongation at a given point, thermal conductivity, and cut resistance. Comparative Example 7 was prepared using a traditional dry method; Comparative Example 8 did not add modified carbon nanotubes; Comparative Example 9 had too little modified carbon nanotubes; Comparative Example 10 had too much modified carbon nanotubes; Comparative Example 11 did not add a second carbon black; Comparative Example 12 did not modify the carbon black; and Comparative Example 13 did not modify the multi-walled carbon nanotubes. All of these factors negatively impacted the various properties of the prepared tire tread compound. Therefore, by adopting the wet masterbatch technology based on three-phase synergistic reinforcement described in this application, a three-dimensional reinforcing system of carbon black-CNTs-rubber molecular chains is constructed. Combined with the wet masterbatch process, nanoscale dispersion of CNTs is achieved. Based on optimizing the amount of CNTs added, the performance bottleneck of single filler is broken through, which can significantly improve the wear resistance, cut resistance and dynamic mechanical properties of tires. This provides a cost-effective and process-feasible solution for the high performance of engineering machinery tires.
[0143] The applicant declares that this application illustrates a wet-process masterbatch based on three-phase synergistic reinforcement, its preparation method, and its application through the above embodiments. However, this application is not limited to the above embodiments, meaning that this application does not necessarily rely on the above embodiments for implementation. Those skilled in the art should understand that any improvements to this application, equivalent substitutions of raw materials for the product, addition of auxiliary components, and selection of specific methods, all fall within the protection and disclosure scope of this application.
[0144] The preferred embodiments of this application have been described in detail above. However, this application is not limited to the specific details of the above embodiments. Within the scope of the technical concept of this application, various simple modifications can be made to the technical solution of this application, and these simple modifications all fall within the protection scope of this application.
[0145] It should also be noted that the various specific technical features described in the above embodiments can be combined in any suitable manner without contradiction. In order to avoid unnecessary repetition, this application will not describe the various possible combinations separately.
Claims
1. A wet-process masterbatch based on three-phase synergistic reinforcement, characterized in that, The wet-process masterbatch based on three-phase synergistic reinforcement comprises, by weight, 100 parts of natural latex, 45-55 parts of carbon black, 0.5-4 parts of modified multi-walled carbon nanotubes, and 0.5-1 parts of dispersant; the solid content of the natural latex is 60%; the preparation method of the carbon black includes the following steps: A1. Mix the first carbon black and the second carbon black, and premix them in a high-speed mixer to obtain compound carbon black; A2. Mix the compounded carbon black and concentrated nitric acid, and reflux at a constant temperature of 78-82℃. After that, filter to separate the carbon black, wash with deionized water until the filtrate is neutral, and place the washed carbon black in a vacuum drying oven and dry at 78-82℃ for 10-14 hours to obtain the final product.
2. The wet-process masterbatch based on three-phase synergistic reinforcement according to claim 1, characterized in that, The multi-walled carbon nanotubes have a diameter of 20-30 nm and a purity of >95%.
3. The wet-process masterbatch based on three-phase synergistic reinforcement according to claim 2, characterized in that, The method for preparing the modified multi-walled carbon nanotubes includes the following steps: adding multi-walled carbon nanotubes to a mixed acid, ultrasonically treating them, and then refluxing them for reaction 2. The reacted liquid is slowly poured into ice water for dilution, filtered, washed with deionized water until neutral, and dried at 78-82℃ for 10-14 hours to obtain the product.
4. The wet-process masterbatch based on three-phase synergistic reinforcement according to claim 1, characterized in that, The dispersant includes any one of polyvinylpyrrolidone and N-methylpyrrolidone.
5. The wet-process masterbatch based on three-phase synergistic reinforcement according to claim 1, characterized in that, The amount of modified multi-walled carbon nanotubes added is 1%-3% of the mass of natural latex; the mass ratio of carbon black to modified multi-walled carbon nanotubes is (20-30):
1.
6. A method for preparing wet-process masterbatch based on three-phase synergistic reinforcement according to any one of claims 1 to 5, characterized in that, Includes the following steps: S1. Pre-dispersion treatment: Modified multi-walled carbon nanotubes, carbon black and dispersant are mixed and sheared to form a homogeneous suspension; S2. In-situ composite: Using wet composite technology, the homogeneous suspension obtained in step S1 is sprayed with natural latex, flocculated, and composite masterbatch particles are formed. Then, the particles are dehydrated, dried, and shaped to obtain the final product.
7. The method for preparing wet-process masterbatch based on three-phase synergistic reinforcement according to claim 6, characterized in that, In step S1, the specific conditions for shearing are: shearing speed of 10000r / min-12000r / min and shearing time of 28-32min.
8. An application of the wet-process masterbatch based on three-phase synergistic reinforcement according to any one of claims 1 to 5, characterized in that, It is used in the preparation of tire tread compounds.
9. The application of the wet-process masterbatch based on three-phase synergistic reinforcement according to claim 8, characterized in that, The tire tread compound, by weight, comprises 150-155 parts of wet-process masterbatch based on three-phase synergistic reinforcement, 1-3 parts of stearic acid, 4-6 parts of zinc oxide, 0.5-1.5 parts of antioxidant 4020, 1-3 parts of sulfur, and 1-1.5 parts of accelerator CZ.
10. The application of the wet-process masterbatch based on three-phase synergistic reinforcement according to claim 9, characterized in that, The method for preparing the tire tread compound includes the following steps: 1) Mixing: Wet masterbatch, zinc oxide, stearic acid, antioxidant 4020 are added to an internal mixer for a first stage of mixing, and then accelerator CZ is added for a second stage of mixing to obtain masterbatch. 2) Final mixing: Add the masterbatch rubber to the open mill, add sulfur and CZ, set the roll temperature to 65-70℃, the roll gap to 1.5-2.0mm, wrap the rolls, pass through the thin mill 6-8 times, sheet out, and cool at room temperature to obtain the final rubber. 3) Vulcanization: The final rubber compound is vulcanized and molded to obtain the final product.