Nano-composite masterbatch, nano-composite rubber material and preparation method of nano-composite masterbatch and nano-composite rubber material

Abstract

The invention relates to a rubber material, and further relates to a nano-composite masterbatch, a nano-composite rubber material and a preparation method of the nano-composite masterbatch and the nano-composite rubber material. The nano composite masterbatch provided by the invention is prepared by taking epoxidized natural rubber latex as base rubber and adding natural rubber latex and white carbon black. The nano-composite masterbatch can be subjected to a ring-opening reaction with silanol groups on the surface of the white carbon black in the mixing and vulcanizing process, covalent bonds are formed between two phases, and due to the combined action of temperature and shearing force in the mixing process, the epoxy groups and the white carbon black can be combined more quickly, so that the filler is uniformly dispersed. According to the preparation method of the nano composite masterbatch disclosed by the invention, the latex does not need to be modified, the process is simple, the production efficiency is high, the energy consumption of equipment is low, the used settling agent and solvent can be separated and recycled by a simple method, and the colloid is made of a bio-based material and meets the green requirement.

Description

Technical Field

[0001] The invention relates to a rubber material, and more particularly to a nano-composite masterbatch, a nano-composite rubber material and a preparation method thereof. Background Art

[0002] The development trend of tires is green and environmental protection, and protecting life and health. At present, the tire tread rubber is mainly based on solution-polymerized styrene butadiene, which depends on petroleum resources, and the preparation process produces a large amount of carbon emissions. Therefore, epoxidized natural rubber is selected to prepare bio-based rubber nanocomposites, and ultra-high performance green tires are developed. In the use of rubber, carbon black and white carbon black are the most common reinforcing agents. Compared with carbon black, white carbon black is a reinforcing filler that does not rely on petroleum resources. Adding white carbon black to the tread rubber can make the tire have low rolling resistance and high anti-slip performance, which is in line with the application trend of "green tires" for energy conservation and emission reduction. However, the traditional white carbon black mixing technology mainly relies on the heating effect of the internal mixer and the strong shear force to knead it into the rubber. It is a process with high energy consumption, low efficiency, and serious dust pollution. In addition, the dispersibility of white carbon black in the rubber system and the bulk of the nano-composite masterbatch during heat treatment have always been difficult to solve.

[0003] Epoxidized natural rubber is a natural rubber obtained by epoxidation modification, and is usually prepared by adding formic acid or acetic acid and hydrogen peroxide to natural rubber latex under acidic conditions. Since epoxidized natural rubber introduces epoxy groups into natural rubber molecules, the polarity of rubber molecules and the interaction between rubber molecules increase, so that it has some special properties, such as excellent air tightness resistance, oil resistance, good anti-slip and low rolling resistance, and good adhesion. Therefore, epoxidized natural rubber has a wide range of uses, especially in green tire applications. Since epoxidized natural rubber has low rolling resistance and high anti-slip, it has a wide range of application prospects in the manufacture of high-performance green tires. However, epoxidized natural rubber products are easily affected by environmental factors during processing or use, and rubber aging occurs. Therefore, epoxidized natural rubber products generally have problems such as short storage time, short service life, and aging and stickiness, which greatly limits the application of epoxidized natural rubber.

[0004] Using natural rubber as the base rubber and compounding a small amount of epoxidized natural rubber as the masterbatch can solve some of the problems existing in rubber products using epoxidized natural rubber as the masterbatch. However, when natural rubber and epoxidized natural rubber are compounded to prepare rubber materials, the compatibility of the two is poor (rubber materials have two glass transition temperatures, and the two glass transition temperatures are quite different). At the same time, when heat-treating silica, the epoxy group will react violently with the hydroxyl group, resulting in a bulking problem (the rubber block will become debris), which in turn leads to poor performance of the prepared rubber material. Summary of the invention

[0005] In view of the deficiencies of the prior art, the present invention provides a nanocomposite masterbatch, a nanocomposite rubber material and a method for preparing the same. The nanocomposite masterbatch provided by the present invention is prepared by using epoxidized natural rubber latex as a base rubber, adding natural rubber latex and white carbon black. The nanocomposite masterbatch is used as a masterbatch for mixing and preparing a nanocomposite rubber material, which can improve the compatibility of natural rubber and epoxidized natural rubber, solve the bulk problem of the nanocomposite masterbatch, and significantly improve the dispersion of white carbon black and other fillers in the nanocomposite rubber material, while meeting the trend of green tire applications.

[0006] One of the purposes of the present invention is to provide a nanocomposite masterbatch.

[0007] The nanocomposite masterbatch is prepared by mixing and flocculating the raw materials of the following components; each component and its weight part: based on dry rubber, latex 100 weight parts; white carbon black slurry 40-120 weight parts, preferably 60-90 weight parts;

[0008] The latex comprises epoxidized natural rubber latex and natural rubber latex; based on dry rubber, the weight ratio of epoxidized natural rubber latex to natural rubber latex is 10-100:90-0, preferably 30-90:70-10;

[0009] The mass content of white carbon black in the white carbon black slurry is 5-15%.

[0010] The invention uses epoxidized natural rubber latex as a base rubber, adds natural rubber latex and white carbon black slurry at the same time, and adopts a wet method to prepare a nano composite masterbatch. The natural rubber and the epoxidized rubber are mixed in the form of latex, and the white carbon black is also added in the form of slurry, so that the compatibility of the natural rubber and the epoxidized rubber in the prepared nano composite masterbatch is good.

[0011] The second object of the present invention is to provide a method for preparing the nanocomposite masterbatch described in one of the invention objects.

[0012] The method for preparing the nano-composite masterbatch comprises: at a temperature of 25-30° C., the natural rubber latex, the epoxidized natural rubber latex and the white carbon black slurry are mixed to form a mixed system, the mixed system is flocculated with a sedimentation agent, and solids are collected to obtain the nano-composite masterbatch.

[0013] The preparation method directly uses latex and white carbon black slurry as raw materials, and the raw materials are both in liquid state and mixed in liquid state. Compared with the dry method, the compatibility of natural rubber and epoxidized natural rubber in the nanocomposite masterbatch prepared by the method of the present invention is significantly improved, and the DMA test results show that the two glass transition temperatures are closer; the dispersion of white carbon black and filler is better, and TEM (transmission electron microscope) shows that the filler is more evenly dispersed, the white carbon black agglomerates less, and the voids are also less.

[0014] The epoxidized natural rubber latex used can be prepared by any existing method for preparing epoxidized natural rubber latex. Specifically, the following preparation method can be used: natural rubber latex is diluted with water, a stabilizer is added and mixed, and then formic acid and hydrogen peroxide are added to react in a 40-50°C water bath under closed conditions, and after the reaction stops, ammonia water is added to a pH of 8-9 to obtain the epoxidized natural rubber latex. This preparation method of epoxidized natural rubber latex adopts emulsion polymerization to directly epoxidize the latex, and the solvent is water instead of an organic solvent, which is more environmentally friendly.

[0015] The stabilizer can be selected from any one or more non-ionic stabilizers, such as OP or alcohol ether active agents; can be selected from two or more non-ionic active agents with similar cloud points; can be selected from one or more of OP-6, OP-8, OP-10, and OP-15. According to some embodiments disclosed in the present invention, the stabilizer is selected from OP-10; compared with OP-6, OP-8, OP-15, etc., OP-10 has a better stabilizing effect. Preferably, the epoxidation degree of the epoxidized natural rubber latex is 5-60, more preferably 10-35.

[0016] The white carbon black slurry can be prepared by any existing method for preparing white carbon black slurry. Specifically, the following preparation method can be adopted: white carbon black is mixed with water and poured into a colloid mill, stirred until the white carbon black is evenly dispersed, and then a coupling agent is added, and the stirring is continued until the coupling agent is evenly dispersed to obtain the white carbon black slurry. The colloid mill is a method of subjecting the material to a strong shear force between the fixed teeth and the moving teeth that are relatively linked at high speed, so that the material is effectively crushed, emulsified, and homogenized. After treatment, the particle size of the white carbon black slurry will be refined. This method of preparing white carbon black slurry does not require ultrasonic mixing, and a colloid mill can be used. Due to the polarity of epoxidized natural rubber latex and its reactivity with silicone hydroxyl groups, the white carbon black slurry can have very excellent dispersion properties in the latex without ultrasonic mixing.

[0017] In the above-mentioned preparation method of white carbon black slurry, the stirring temperature can be 5-10°C; the coupling agent can be selected from silane coupling agents, preferably, the coupling agent is bis-[γ-(triethoxysilyl)propyl]tetrasulfide and fatty alcohol polyoxyethylene ether-9; the weight of the coupling agent is 8-15wt% of the weight of white carbon black.

[0018] The sedimentation agent may be anhydrous ethanol. Using anhydrous ethanol as a sedimentation agent has high flocculation efficiency and will not introduce other elements into the rubber material to affect the performance. The volume ratio of the sedimentation agent to the mixed system is 0.5-3:1.

[0019] The preparation method of the nanocomposite masterbatch may further include cutting the nanocomposite masterbatch into pieces and soaking them in a sodium carbonate solution, standing the pieces, washing with water until neutral, and then drying the pieces at 55-70° C. until constant weight. The mass concentration of the sodium carbonate solution may be 1-3%.

[0020] A third object of the present invention is to provide a nano-composite rubber material.

[0021] The nanocomposite rubber material is prepared by mixing raw materials including the nanocomposite masterbatch as described in one of the purposes of the invention. The epoxy groups in the nanocomposite masterbatch described in one of the purposes of the invention will undergo a ring-opening reaction with the silanol groups on the surface of white carbon black during mixing and vulcanization, forming a covalent bond between the two phases, and due to the combined effects of temperature and shear force during mixing, the mutual bonding between the epoxy groups and the white carbon black will occur faster, so that the filler is evenly dispersed.

[0022] Specifically, the nanocomposite rubber material is prepared by mixing raw materials including the following components; the components and their weight parts are as follows:

[0023] Nanocomposite masterbatch 190-200 parts by weight;

[0024] The antioxidant is 0.5-5 parts by weight, preferably 1-3 parts by weight;

[0025] The activator is 1-10 parts by weight, preferably 3-7 parts by weight;

[0026] The accelerator is 1-8 parts by weight, preferably 2-6 parts by weight;

[0027] The amount of the vulcanizing agent is 0.5-5 parts by weight, preferably 1-3 parts by weight.

[0028] According to some embodiments disclosed in the present invention, the nanocomposite rubber material is prepared by mixing raw materials including the following components; the components and their weight parts are as follows:

[0029] Nanocomposite masterbatch 190.5 parts by weight;

[0030] The antioxidant is 0.5-5 parts by weight, preferably 1-3 parts by weight;

[0031] The activator is 1-10 parts by weight, preferably 3-7 parts by weight;

[0032] The accelerator is 1-8 parts by weight, preferably 2-6 parts by weight;

[0033] The amount of the vulcanizing agent is 0.5-5 parts by weight, preferably 1-3 parts by weight.

[0034] The antioxidant can be selected from any one or more antioxidants currently available in the rubber field. According to some embodiments disclosed in the present invention, the antioxidant is selected from antioxidant 4010NA.

[0035] The activator can be selected from any one or more activators currently available in the rubber field. According to some embodiments disclosed in the present invention, the activator is selected from zinc oxide and stearic acid, and the weight ratio of the two is 5:2.

[0036] The accelerator can be selected from any one or more accelerators currently available in the rubber field. According to some embodiments disclosed in the present invention, the accelerator is selected from accelerator D and accelerator, and the weight ratio of the accelerators is 1.5:2.

[0037] The vulcanizing agent can be selected from any one or more vulcanizing agents currently available in the rubber field. According to some embodiments disclosed in the present invention, the vulcanizing agent is selected from sulfur.

[0038] The fourth object of the present invention is to provide a method for preparing the nano-composite rubber material described in the third object of the present invention.

[0039] The preparation method of the nano-composite rubber material comprises: the nano-composite masterbatch is heat-treated by a twin-screw extruder to obtain a heat-treated masterbatch; wherein the screw temperature is 80-120° C. and the residence time is 1-6 minutes. The heat-treated masterbatch is mixed according to a normal rubber mixing process. Specifically, the heat-treated masterbatch and the other raw materials are mixed. For example, the mixing includes: first mixing with an internal mixer and then mixing with an open mixer.

[0040] According to some embodiments disclosed in the present invention, the preparation method of the nano-composite rubber material includes: heat-treating the nano-composite masterbatch using a twin-screw extruder to obtain a heat-treated masterbatch; mixing the heat-treated masterbatch, zinc oxide, stearic acid and antioxidant using an internal mixer, and then adding an accelerator and sulfur on an open mixer for mixing.

[0041] Compared with the conventional internal mixer and open mixer for mixing, the present invention first uses a twin-screw extruder to heat-treat the nano-composite masterbatch. On the one hand, it can effectively solve the problem of bulk material that will occur in the traditional heat treatment method, prevent the scattering of white carbon black and ensure the stability of material intake; on the other hand, the twin-screw extruder can make the mutual combination between the epoxy group and the white carbon black occur faster, so that the epoxy group can react better with the silanol group, so that the filler is evenly dispersed.

[0042] Compared with the prior art, the present invention has the following beneficial effects:

[0043] 1. The preparation method of the nanocomposite masterbatch disclosed in the present invention can significantly improve the dispersion of white carbon black and other fillers in the nanocomposite rubber material, and can improve the compatibility of natural rubber and epoxidized natural rubber. There is no need to modify the latex, the process is simple, the production efficiency is high, the equipment energy consumption is low, the sedimentation agent and the solvent used can be separated and recovered by a simple method, and the colloid is made of bio-based materials, which meets the green requirements.

[0044] 2. The nanocomposite masterbatch disclosed in the present invention has good compatibility between natural rubber and epoxidized natural rubber, and white carbon black and filler are evenly dispersed, which can meet the downstream product market and provide feasible technical support for the production of the tire industry.

[0045] 3. The preparation method of the nano-composite rubber material disclosed in the present invention solves the bulk problem of the internal mixer and ensures the strong shear force of the open mixer; it solves the bulk problem of the nano-composite masterbatch, significantly improves the problem of dust flying during dry internal mixing of white carbon black, and improves the dispersion degree of white carbon black in rubber.

[0046] 4. The nano-composite rubber material disclosed in the present invention has good compatibility between natural rubber and epoxidized natural rubber, and white carbon black and filler are evenly dispersed; it has excellent vulcanization performance, wear resistance and comprehensive performance.

[0047] In the present invention, the dry glue content refers to the mass content of the dry glue. BRIEF DESCRIPTION OF THE DRAWINGS

[0048] Figure 1 This is a transmission electron microscope image of the nanocomposite rubber material prepared in Example 5 of the present invention;

[0049] Figure 2 This is a transmission electron microscope image of the nanocomposite rubber material prepared in Comparative Example 2 of the present invention;

[0050] Figure 3 This is a transmission electron microscope image of the nanocomposite rubber material prepared in Comparative Example 3 of the present invention;

[0051] Figure 4 This is a transmission electron microscope image of the nanocomposite rubber material prepared in Comparative Example 4 of the present invention;

[0052] Figure 5 This is a state diagram of a masterbatch in Example 5 of the present invention;

[0053] Figure 6 This is a state diagram of the masterbatch in Comparative Example 3 of the present invention. DETAILED DESCRIPTION

[0054] The present invention is described in detail below in conjunction with specific drawings and embodiments. It is necessary to point out that the following embodiments are only used to further illustrate the present invention and cannot be understood as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made to the present invention by those skilled in the art based on the content of the present invention still fall within the scope of protection of the present invention.

[0055] The reagents used in the examples and comparative examples are all commercially available products.

[0056] Example 1

[0057] Step 1, take 480g of natural rubber latex with a dry rubber content of 60% and put it into a 5L reactor, add 480g of water to dilute it to a dry rubber content of 30%, add 32.4g of stabilizer OP-10, stir it in an open state for 30 minutes, then add 120g of formic acid and 473.4g of hydrogen peroxide, react in a closed state in a 40°C water bath for 6 hours, stop the reaction, add ammonia water dropwise until the pH is 8, and obtain an epoxidized natural rubber latex with a dry rubber content of 17.35% and an epoxidation degree of 30;

[0058] Step 2: weigh 600 g of white carbon black solid, add 5400 g of water, stir and mix, pour into a colloid mill, stir at 70 Hz and 5 ° C for 10 minutes, add 60 g of bis-[γ-(triethoxysilyl)propyl] tetrasulfide and 20 g of fatty alcohol polyoxyethylene ether-9, continue stirring for 10 minutes and then stop the reaction to obtain white carbon black slurry;

[0059] Step 3, weighing 162.96g of natural rubber latex with a dry rubber content of 60%, 168.06g of the epoxidized natural rubber latex prepared in step 1, and 977.8g of the white carbon black slurry prepared in step 2, stirring at a speed of 200 rpm for 30 minutes, pouring into 2.5L of anhydrous ethanol to flocculate to obtain a rubber block, cutting the rubber block into pieces and soaking it in a 1% (mass concentration, the same below) sodium carbonate solution for 24 hours, washing it with water until it is neutral, and drying it in a 60°C oven to constant weight to obtain a wet-process prepared nanocomposite masterbatch;

[0060] Step 4: Weigh 190.5 parts by weight of the nanocomposite masterbatch prepared in step 3, 5 parts by weight of zinc oxide, 2 parts by weight of stearic acid, 1 part by weight of antioxidant 4010NA, 1.5 parts by weight of accelerator D, 2 parts by weight of accelerator CZ, and 2 parts by weight of sulfur. Put the nanocomposite masterbatch into a twin-screw extruder, set the screw temperature to 80°C, and hold for 5 minutes to obtain a masterbatch; add the masterbatch to an internal mixer, set the internal mixer temperature to 60°C, and the speed to 60r / min. After mixing for 1 minute, add zinc oxide, stearic acid, and antioxidant and mix for 2 minutes, discharge, and obtain a rubber mix. Discharge the rubber mix on an open mill with cooling water and reduce the temperature to room temperature, then add accelerators and sulfur in sequence on the open mill, cut left and right 3 times, make triangle packages three times, and roll three times to obtain a nanocomposite rubber material.

[0061] Example 2

[0062] Step 1, take 480g of natural rubber latex with a dry rubber content of 60% and put it into a 5L reactor, add 480g of water to dilute it to a dry rubber content of 30%, add 32.4g of stabilizer OP-10, stir it in an open state for 30 minutes, then add 120g of formic acid and 473.4g of hydrogen peroxide, react in a closed state in a 40°C water bath for 6 hours, stop the reaction, add ammonia water dropwise until the pH is 8, and obtain an epoxidized natural rubber latex with a dry rubber content of 17.35% and an epoxidation degree of 30;

[0063] Step 2: weigh 600 g of white carbon black solid, add 5400 g of water, stir and mix, pour into a colloid mill, stir at 70 Hz and 5 ° C for 10 minutes, add 60 g of bis-[γ-(triethoxysilyl)propyl] tetrasulfide and 20 g of fatty alcohol polyoxyethylene ether-9, continue stirring for 10 minutes and then stop the reaction to obtain white carbon black slurry;

[0064] Step 3, weighing 142.59g of natural rubber latex with a dry rubber content of 60%, 252.09g of the epoxidized natural rubber latex prepared in step 1, and 977.8g of the white carbon black slurry prepared in step 2, stirring at 200 rpm for 30 minutes, pouring into 2.5L of anhydrous ethanol and flocculating to obtain a rubber block, cutting the rubber block into pieces, soaking it in 1% sodium carbonate solution for 24 hours, washing it with water until it is neutral, and drying it in a 60°C oven to constant weight to obtain a wet-process prepared nanocomposite masterbatch;

[0065] Step 4: Weigh 190.5 parts by weight of the nanocomposite masterbatch prepared in step 3, 5 parts by weight of zinc oxide, 2 parts by weight of stearic acid, 1 part by weight of antioxidant 4010NA, 1.5 parts by weight of accelerator D, 2 parts by weight of accelerator CZ, and 2 parts by weight of sulfur. Put the nanocomposite masterbatch into a twin-screw extruder, set the screw temperature to 80°C, and hold for 5 minutes to obtain a masterbatch; add the masterbatch to an internal mixer, set the internal mixer temperature to 60°C, and the speed to 60r / min. After mixing for 1 minute, add zinc oxide, stearic acid, and antioxidant and mix for 2 minutes, discharge, and obtain a rubber mix. Discharge the rubber mix on an open mill with cooling water and reduce the temperature to room temperature, then add accelerators and sulfur in sequence on the open mill, cut left and right 3 times, make triangle packages three times, and roll three times to obtain a nanocomposite rubber material.

[0066] Example 3

[0067] Step 1, take 480g of natural rubber latex with a dry rubber content of 60% and put it into a 5L reactor, add 480g of water to dilute it to a dry rubber content of 30%, add 32.4g of stabilizer OP-10, stir it in an open state for 30 minutes, then add 120g of formic acid and 473.4g of hydrogen peroxide, react in a closed state in a 40°C water bath for 6 hours, stop the reaction, add ammonia water dropwise until the pH is 8, and obtain an epoxidized natural rubber latex with a dry rubber content of 17.35% and an epoxidation degree of 30;

[0068] Step 2: weigh 600 g of white carbon black solid, add 5400 g of water, stir and mix, pour into a colloid mill, stir at 70 Hz and 5 ° C for 10 minutes, add 60 g of bis-[γ-(triethoxysilyl)propyl] tetrasulfide and 20 g of fatty alcohol polyoxyethylene ether-9, continue stirring for 10 minutes and then stop the reaction to obtain white carbon black slurry;

[0069] Step 3, weighing 122.22g of natural rubber latex with a dry rubber content of 60%, 336.12g of the epoxidized natural rubber latex prepared in step 1, and 977.8g of the white carbon black slurry prepared in step 2, stirring at 200 rpm for 30 minutes, pouring into 2.5L of anhydrous ethanol to flocculate to obtain a rubber block, cutting the rubber block into pieces, soaking it in 1% sodium carbonate solution for 24 hours, washing it with water until it is neutral, and drying it in a 60°C oven to constant weight to obtain a nano-composite masterbatch prepared by a wet method;

[0070] Step 4: Weigh 190.5 parts by weight of the nanocomposite masterbatch prepared in step 3, 5 parts by weight of zinc oxide, 2 parts by weight of stearic acid, 1 part by weight of antioxidant 4010NA, 1.5 parts by weight of accelerator D, 2 parts by weight of accelerator CZ, and 2 parts by weight of sulfur. Put the nanocomposite masterbatch into a twin-screw extruder, set the screw temperature to 80°C, and hold for 5 minutes to obtain a masterbatch; add the masterbatch to an internal mixer, set the internal mixer temperature to 60°C, and the speed to 60r / min. After mixing for 1 minute, add zinc oxide, stearic acid, and antioxidant and mix for 2 minutes, discharge, and obtain a rubber mix. Discharge the rubber mix on an open mill with cooling water and reduce the temperature to room temperature, then add accelerators and sulfur in sequence on the open mill, cut left and right 3 times, make triangle packages three times, and roll three times to obtain a nanocomposite rubber material.

[0071] Example 4

[0072] Step 1, take 480g of natural rubber latex with a dry rubber content of 60% and put it into a 5L reactor, add 480g of water to dilute it to a dry rubber content of 30%, add 32.4g of stabilizer OP-10, stir it in an open state for 30 minutes, then add 120g of formic acid and 473.4g of hydrogen peroxide, react in a closed state in a 40°C water bath for 6 hours, stop the reaction, add ammonia water dropwise until the pH is 8, and obtain an epoxidized natural rubber latex with a dry rubber content of 17.35% and an epoxidation degree of 30;

[0073] Step 2: weigh 600 g of white carbon black solid, add 5400 g of water, stir and mix, pour into a colloid mill, stir at 70 Hz and 5 ° C for 10 minutes, add 60 g of bis-[γ-(triethoxysilyl)propyl] tetrasulfide and 20 g of fatty alcohol polyoxyethylene ether-9, continue stirring for 10 minutes and then stop the reaction to obtain white carbon black slurry;

[0074] Step 3, weighing 81.48g of natural rubber latex with a dry rubber content of 60%, 504.17g of the epoxidized natural rubber latex prepared in step 1, and 977.8g of the white carbon black slurry prepared in step 2, stirring at a speed of 200 rpm for 30 minutes, pouring into 2.5L of anhydrous ethanol to flocculate to obtain a rubber block, cutting the rubber block into pieces, soaking it in a 1% sodium carbonate solution for 24 hours, washing it with water until it is neutral, and drying it in a 60°C oven to constant weight to obtain a nanocomposite masterbatch prepared by a wet method;

[0075] Step 4: Weigh 190.5 parts by weight of the nanocomposite masterbatch prepared in step 3, 5 parts by weight of zinc oxide, 2 parts by weight of stearic acid, 1 part by weight of antioxidant 4010NA, 1.5 parts by weight of accelerator D, 2 parts by weight of accelerator CZ, and 2 parts by weight of sulfur. Put the nanocomposite masterbatch into a twin-screw extruder, set the screw temperature to 80°C, and hold for 5 minutes to obtain a masterbatch; add the masterbatch to an internal mixer, set the internal mixer temperature to 60°C, and the speed to 60r / min. After mixing for 1 minute, add zinc oxide, stearic acid, and antioxidant and mix for 2 minutes, discharge, and obtain a rubber mix. Discharge the rubber mix on an open mill with cooling water and reduce the temperature to room temperature, then add accelerators and sulfur in sequence on the open mill, cut left and right 3 times, make triangle packages three times, and roll three times to obtain a nanocomposite rubber material.

[0076] Example 5

[0077] Step 1, take 480g of natural rubber latex with a dry rubber content of 60% and put it into a 5L reactor, add 480g of water to dilute it to a dry rubber content of 30%, add 32.4g of stabilizer OP-10, stir it in an open state for 30 minutes, then add 120g of formic acid and 473.4g of hydrogen peroxide, react in a closed state in a 40°C water bath for 6 hours, stop the reaction, add ammonia water dropwise until the pH is 8, and obtain an epoxidized natural rubber latex with a dry rubber content of 17.35% and an epoxidation degree of 30;

[0078] Step 2: weigh 600 g of white carbon black solid, add 5400 g of water, stir and mix, pour into a colloid mill, stir at 70 Hz and 5 ° C for 10 minutes, add 60 g of bis-[γ-(triethoxysilyl)propyl] tetrasulfide and 20 g of fatty alcohol polyoxyethylene ether-9, continue stirring for 10 minutes and then stop the reaction to obtain white carbon black slurry;

[0079] Step 3, weighing 61.11g of natural rubber latex with a dry rubber content of 60%, 588.21g of the epoxidized natural rubber latex prepared in step 1, and 977.8g of the white carbon black slurry prepared in step 2, stirring at 200 rpm for 30 minutes, pouring into 2.5L of anhydrous ethanol to flocculate to obtain a rubber block, cutting the rubber block into pieces and soaking it in 1% sodium carbonate solution for 24 hours, then washing it with water to neutrality, and drying it in a 60°C oven to constant weight to obtain a wet-process prepared nanocomposite masterbatch;

[0080] Step 4: Weigh 190.5 parts by weight of the nanocomposite masterbatch prepared in step 3, 5 parts by weight of zinc oxide, 2 parts by weight of stearic acid, 1 part by weight of antioxidant 4010NA, 1.5 parts by weight of accelerator D, 2 parts by weight of accelerator CZ, and 2 parts by weight of sulfur. Put the nanocomposite masterbatch into a twin-screw extruder, set the screw temperature to 80°C, and the residence time to 5 minutes to obtain a masterbatch; add the masterbatch to an internal mixer, set the internal mixer temperature to 60°C, and the speed to 60r / min. After mixing for 1 minute, add zinc oxide, stearic acid, and antioxidant and mix for 2 minutes, discharge the material, and obtain a mixed rubber. The mixed rubber is sheeted on an open mill with cooling water and the temperature is lowered to room temperature, and then the accelerator and sulfur are added in sequence on the open mill, the left and right cutters are cut 3 times, the triangle packages are made three times, and the rolls are rolled three times to obtain a nanocomposite rubber material. The transmission electron microscope image of the prepared nanocomposite rubber material is shown in Figure 1.

[0081] Example 6

[0082] Step 1, take 480g of natural rubber latex with a dry rubber content of 60% and put it into a 5L reactor, add 480g of water to dilute it to a dry rubber content of 30%, add 32.4g of stabilizer OP-10, stir it in an open state for 30 minutes, then add 120g of formic acid and 473.4g of hydrogen peroxide, react in a closed state in a 40°C water bath for 6 hours, stop the reaction, add ammonia water dropwise until the pH is 8, and obtain an epoxidized natural rubber latex with a dry rubber content of 17.35% and an epoxidation degree of 30;

[0083] Step 2: weigh 600 g of white carbon black solid, add 5400 g of water, stir and mix, pour into a colloid mill, stir at 70 Hz and 5 ° C for 10 minutes, add 60 g of bis-[γ-(triethoxysilyl)propyl] tetrasulfide and 20 g of fatty alcohol polyoxyethylene ether-9, continue stirring for 10 minutes and then stop the reaction to obtain white carbon black slurry;

[0084] Step 3, weighing 40.74g of natural rubber latex with a dry rubber content of 60%, 672.23g of the epoxidized natural rubber latex prepared in step 1, and 977.8g of the white carbon black slurry prepared in step 2, stirring at 200 rpm for 30 minutes, pouring into 2.5L of anhydrous ethanol to flocculate to obtain a rubber block, cutting the rubber block into pieces, soaking it in 1% sodium carbonate solution for 24 hours, washing it with water until it is neutral, and drying it in a 60°C oven to constant weight to obtain a wet-process prepared nanocomposite masterbatch;

[0085] Step 4: Weigh 190.5 parts by weight of the nanocomposite masterbatch prepared in step 3, 5 parts by weight of zinc oxide, 2 parts by weight of stearic acid, 1 part by weight of antioxidant 4010NA, 1.5 parts by weight of accelerator D, 2 parts by weight of accelerator CZ, and 2 parts by weight of sulfur. Put the nanocomposite masterbatch into a twin-screw extruder, set the screw temperature to 80°C, and hold for 5 minutes to obtain a masterbatch; add the masterbatch to an internal mixer, set the internal mixer temperature to 60°C, and the speed to 60r / min. After mixing for 1 minute, add zinc oxide, stearic acid, and antioxidant and mix for 2 minutes, discharge, and obtain a rubber mix. Discharge the rubber mix on an open mill with cooling water and reduce the temperature to room temperature, then add accelerators and sulfur in sequence on the open mill, cut left and right 3 times, make triangle packages three times, and roll three times to obtain a nanocomposite rubber material.

[0086] Example 7

[0087] Step 1, take 480g of natural rubber latex with a dry rubber content of 60% and put it into a 5L reactor, add 480g of water to dilute it to a dry rubber content of 30%, add 32.4g of stabilizer OP-10, stir it in an open state for 30 minutes, then add 120g of formic acid and 473.4g of hydrogen peroxide, react in a closed state in a 40°C water bath for 6 hours, stop the reaction, add ammonia water dropwise until the pH is 8, and obtain an epoxidized natural rubber latex with a dry rubber content of 17.35% and an epoxidation degree of 30;

[0088] Step 2: weigh 600 g of white carbon black solid, add 5400 g of water, stir and mix, pour into a colloid mill, stir at 70 Hz and 5 ° C for 10 minutes, add 60 g of bis-[γ-(triethoxysilyl)propyl] tetrasulfide and 20 g of fatty alcohol polyoxyethylene ether-9, continue stirring for 10 minutes and then stop the reaction to obtain white carbon black slurry;

[0089] Step 3, weigh 840.29g of the epoxidized natural rubber latex prepared in step 1 and 977.8g of the white carbon black slurry prepared in step 2, stir them at 200 rpm for 30 minutes, pour them into 2.5L of anhydrous ethanol and flocculate to obtain a rubber block, cut the rubber block into pieces, soak it in 1% sodium carbonate solution for 24 hours, wash it with water until it is neutral, put it in a 60°C oven and dry it to constant weight to obtain a nano-composite masterbatch prepared by a wet method;

[0090] Step 4: Weigh 190.5 parts by weight of the nanocomposite masterbatch prepared in step 3, 5 parts by weight of zinc oxide, 2 parts by weight of stearic acid, 1 part by weight of antioxidant 4010NA, 1.5 parts by weight of accelerator D, 2 parts by weight of accelerator CZ, and 2 parts by weight of sulfur. Put the nanocomposite masterbatch into a twin-screw extruder, set the screw temperature to 80°C, and hold for 5 minutes to obtain a masterbatch; add the masterbatch to an internal mixer, set the internal mixer temperature to 60°C, and the speed to 60r / min. After mixing for 1 minute, add zinc oxide, stearic acid, and antioxidant and mix for 2 minutes, discharge, and obtain a rubber mix. Discharge the rubber mix on an open mill with cooling water and reduce the temperature to room temperature, then add accelerators and sulfur in sequence on the open mill, cut left and right 3 times, make triangle packages three times, and roll three times to obtain a nanocomposite rubber material.

[0091] Example 8

[0092] Step 1, take 480g of natural rubber latex with a dry rubber content of 60% and put it into a 5L reactor, add 480g of water to dilute it to a dry rubber content of 30%, add 32.4g of stabilizer OP-10, stir it in an open state for 30 minutes, then add 120g of formic acid and 473.4g of hydrogen peroxide, react in a closed state in a 40°C water bath for 6 hours, stop the reaction, add ammonia water dropwise until the pH is 8, and obtain an epoxidized natural rubber latex with a dry rubber content of 17.35% and an epoxidation degree of 30;

[0093] Step 2: weigh 600 g of white carbon black solid, add 5400 g of water, stir and mix, pour into a colloid mill, stir at 70 Hz and 5 ° C for 10 minutes, add 60 g of bis-[γ-(triethoxysilyl)propyl] tetrasulfide and 20 g of fatty alcohol polyoxyethylene ether-9, continue stirring for 10 minutes and then stop the reaction to obtain white carbon black slurry;

[0094] Step 3, weighing 61.11g of natural rubber latex with a dry rubber content of 60%, 588.21g of the epoxidized natural rubber latex prepared in step 1, and 977.8g of the white carbon black slurry prepared in step 2, stirring at 200 rpm for 30 minutes, pouring into 2.5L of anhydrous ethanol to flocculate to obtain a rubber block, cutting the rubber block into pieces and soaking it in 1% sodium carbonate solution for 24 hours, then washing it with water to neutrality, and drying it in a 60°C oven to constant weight to obtain a wet-process prepared nanocomposite masterbatch;

[0095] Step 4: Weigh 190.5 parts by weight of the nanocomposite masterbatch prepared in step 3, 5 parts by weight of zinc oxide, 2 parts by weight of stearic acid, 1 part by weight of antioxidant 4010NA, 1.5 parts by weight of accelerator D, 2 parts by weight of accelerator CZ, and 2 parts by weight of sulfur. Put the nanocomposite masterbatch into a twin-screw extruder, set the screw temperature to 90°C, and hold for 5 minutes to obtain a masterbatch; add the masterbatch to an internal mixer, set the internal mixer temperature to 60°C, and the speed to 60r / min. After mixing for 1 minute, add zinc oxide, stearic acid, and antioxidant and mix for 2 minutes, discharge, and obtain a rubber mix. Discharge the rubber mix on an open mill with cooling water and reduce the temperature to room temperature, then add accelerators and sulfur in sequence on the open mill, cut left and right 3 times, make triangle packages three times, and roll three times to obtain a nanocomposite rubber material.

[0096] Example 9

[0097] Step 1, take 480g of natural rubber latex with a dry rubber content of 60% and put it into a 5L reactor, add 480g of water to dilute it to a dry rubber content of 30%, add 32.4g of stabilizer OP-10, stir it in an open state for 30 minutes, then add 120g of formic acid and 473.4g of hydrogen peroxide, react in a closed state in a 40°C water bath for 6 hours, stop the reaction, add ammonia water dropwise until the pH is 8, and obtain an epoxidized natural rubber latex with a dry rubber content of 17.35% and an epoxidation degree of 30;

[0098] Step 2: weigh 600 g of white carbon black solid, add 5400 g of water, stir and mix, pour into a colloid mill, stir at 70 Hz and 5 ° C for 10 minutes, add 60 g of bis-[γ-(triethoxysilyl)propyl] tetrasulfide and 20 g of fatty alcohol polyoxyethylene ether-9, continue stirring for 10 minutes and then stop the reaction to obtain white carbon black slurry;

[0099] Step 3, weighing 61.11g of natural rubber latex with a dry rubber content of 60%, 588.21g of the epoxidized natural rubber latex prepared in step 1, and 977.8g of the white carbon black slurry prepared in step 2, stirring at 200 rpm for 30 minutes, pouring into 2.5L of anhydrous ethanol to flocculate to obtain a rubber block, cutting the rubber block into pieces and soaking it in 1% sodium carbonate solution for 24 hours, then washing it with water to neutrality, and drying it in a 60°C oven to constant weight to obtain a wet-process prepared nanocomposite masterbatch;

[0100] Step 4: Weigh 190.5 parts by weight of the nanocomposite masterbatch prepared in step 3, 5 parts by weight of zinc oxide, 2 parts by weight of stearic acid, 1 part by weight of antioxidant 4010NA, 1.5 parts by weight of accelerator D, 2 parts by weight of accelerator CZ, and 2 parts by weight of sulfur. Put the nanocomposite masterbatch into a twin-screw extruder, set the screw temperature to 90°C, and hold for 5 minutes to obtain a masterbatch; add the masterbatch to an internal mixer, set the internal mixer temperature to 60°C, and the speed to 60r / min. After mixing for 1 minute, add zinc oxide, stearic acid, and antioxidant and mix for 2 minutes, discharge, and obtain a rubber mix. Discharge the rubber mix on an open mill with cooling water and reduce the temperature to room temperature, then add accelerators and sulfur in sequence on the open mill, cut left and right 3 times, make triangle packages three times, and roll three times to obtain a nanocomposite rubber material.

[0101] Example 10

[0102] Step 1, take 480g of natural rubber latex with a dry rubber content of 60% and put it into a 5L reactor, add 480g of water to dilute it to a dry rubber content of 30%, add 32.4g of stabilizer OP-10, stir it in an open state for 30 minutes, then add 120g of formic acid and 473.4g of hydrogen peroxide, react in a closed state in a 40°C water bath for 6 hours, stop the reaction, add ammonia water dropwise until the pH is 8, and obtain an epoxidized natural rubber latex with a dry rubber content of 17.35% and an epoxidation degree of 30;

[0103] Step 2: weigh 600 g of white carbon black solid, add 5400 g of water, stir and mix, pour into a colloid mill, stir at 70 Hz and 5 ° C for 10 minutes, add 60 g of bis-[γ-(triethoxysilyl)propyl] tetrasulfide and 20 g of fatty alcohol polyoxyethylene ether-9, continue stirring for 10 minutes and then stop the reaction to obtain white carbon black slurry;

[0104] Step 3, weighing 61.11g of natural rubber latex with a dry rubber content of 60%, 588.21g of the epoxidized natural rubber latex prepared in step 1, and 977.8g of the white carbon black slurry prepared in step 2, stirring at 200 rpm for 30 minutes, pouring into 2.5L of anhydrous ethanol to flocculate to obtain a rubber block, cutting the rubber block into pieces and soaking it in 1% sodium carbonate solution for 24 hours, then washing it with water to neutrality, and drying it in a 60°C oven to constant weight to obtain a wet-process prepared nanocomposite masterbatch;

[0105] Step 4: Weigh 190.5 parts by weight of the nanocomposite masterbatch prepared in step 3, 5 parts by weight of zinc oxide, 2 parts by weight of stearic acid, 1 part by weight of antioxidant 4010NA, 1.5 parts by weight of accelerator D, 2 parts by weight of accelerator CZ, and 2 parts by weight of sulfur. Put the nanocomposite masterbatch into a twin-screw extruder, set the screw temperature to 90°C, and hold for 5 minutes to obtain a masterbatch; add the masterbatch to an internal mixer, set the internal mixer temperature to 60°C, and the speed to 60r / min. After mixing for 1 minute, add zinc oxide, stearic acid, and antioxidant and mix for 2 minutes, discharge, and obtain a rubber mix. Discharge the rubber mix on an open mill with cooling water and reduce the temperature to room temperature, then add accelerators and sulfur in sequence on the open mill, cut left and right 3 times, make triangle packages three times, and roll three times to obtain a nanocomposite rubber material.

[0106] Embodiment 11

[0107] Step 1, take 480g of natural rubber latex with a dry rubber content of 60% and put it into a 5L reactor, add 480g of water to dilute it to a dry rubber content of 30%, add 32.4g of stabilizer OP-10, stir it in an open state for 30 minutes, then add 120g of formic acid and 473.4g of hydrogen peroxide, react in a closed state in a 40°C water bath for 6 hours, stop the reaction, add ammonia water dropwise until the pH is 8, and obtain an epoxidized natural rubber latex with a dry rubber content of 17.35% and an epoxidation degree of 30;

[0108] Step 2: weigh 600 g of white carbon black solid, add 5400 g of water, stir and mix, pour into a colloid mill, stir at 70 Hz and 5 ° C for 10 minutes, add 60 g of bis-[γ-(triethoxysilyl)propyl] tetrasulfide and 20 g of fatty alcohol polyoxyethylene ether-9, continue stirring for 10 minutes and then stop the reaction to obtain white carbon black slurry;

[0109] Step 3, weighing 61.11g of natural rubber latex with a dry rubber content of 60%, 588.21g of the epoxidized natural rubber latex prepared in step 1, and 977.8g of the white carbon black slurry prepared in step 2, stirring at 200 rpm for 30 minutes, pouring into 2.5L of anhydrous ethanol to flocculate to obtain a rubber block, cutting the rubber block into pieces and soaking it in 1% sodium carbonate solution for 24 hours, then washing it with water to neutrality, and drying it in a 60°C oven to constant weight to obtain a wet-process prepared nanocomposite masterbatch;

[0110] Step 4: Weigh 190.5 parts by weight of the nanocomposite masterbatch prepared in step 3, 5 parts by weight of zinc oxide, 2 parts by weight of stearic acid, 1 part by weight of antioxidant 4010NA, 1.5 parts by weight of accelerator D, 2 parts by weight of accelerator CZ, and 2 parts by weight of sulfur. Put the nanocomposite masterbatch into a twin-screw extruder, set the screw temperature to 90°C, and hold for 5 minutes to obtain a masterbatch; add the masterbatch to an internal mixer, set the internal mixer temperature to 60°C, and the speed to 60r / min. After mixing for 1 minute, add zinc oxide, stearic acid, and antioxidant and mix for 2 minutes, discharge, and obtain a rubber mix. Discharge the rubber mix on an open mill with cooling water and reduce the temperature to room temperature, then add accelerators and sulfur in sequence on the open mill, cut left and right 3 times, make triangle packages three times, and roll three times to obtain a nanocomposite rubber material.

[0111] Example 12

[0112] Step 1, take 480g of natural rubber latex with a dry rubber content of 60% and put it into a 5L reactor, add 480g of water to dilute it to a dry rubber content of 30%, add 32.4g of stabilizer OP-10, stir it in an open state for 30 minutes, then add 120g of formic acid and 473.4g of hydrogen peroxide, react in a closed state in a 40°C water bath for 0.5 hour, stop the reaction, add ammonia water dropwise until the pH is 8, and obtain an epoxidized natural rubber latex with a dry rubber content of 17.35% and an epoxidation degree of 10;

[0113] Step 2: weigh 600 g of white carbon black solid, add 5400 g of water, stir and mix, pour into a colloid mill, stir at 70 Hz and 5 ° C for 10 minutes, add 60 g of bis-[γ-(triethoxysilyl)propyl] tetrasulfide and 20 g of fatty alcohol polyoxyethylene ether-9, continue stirring for 10 minutes and then stop the reaction to obtain white carbon black slurry;

[0114] Step 3, weighing 61.11g of natural rubber latex with a dry rubber content of 60%, 588.21g of the epoxidized natural rubber latex prepared in step 1, and 977.8g of the white carbon black slurry prepared in step 2, stirring at 200 rpm for 30 minutes, pouring into 2.5L of anhydrous ethanol to flocculate to obtain a rubber block, cutting the rubber block into pieces and soaking it in 1% sodium carbonate solution for 24 hours, then washing it with water to neutrality, and drying it in a 60°C oven to constant weight to obtain a wet-process prepared nanocomposite masterbatch;

[0115] Step 4: Weigh 190.5 parts by weight of the nanocomposite masterbatch prepared in step 3, 5 parts by weight of zinc oxide, 2 parts by weight of stearic acid, 1 part by weight of antioxidant 4010NA, 1.5 parts by weight of accelerator D, 2 parts by weight of accelerator CZ, and 2 parts by weight of sulfur. Put the nanocomposite masterbatch into a twin-screw extruder, set the screw temperature to 80°C, and hold for 5 minutes to obtain a masterbatch; add the masterbatch to an internal mixer, set the internal mixer temperature to 60°C, and the speed to 60r / min. After mixing for 1 minute, add zinc oxide, stearic acid, and antioxidant and mix for 2 minutes, discharge, and obtain a rubber mix. Discharge the rubber mix on an open mill with cooling water and reduce the temperature to room temperature, then add accelerators and sulfur in sequence on the open mill, cut left and right 3 times, make triangle packages three times, and roll three times to obtain a nanocomposite rubber material.

[0116] Example 13

[0117] Step 1, take 480g of natural rubber latex with a dry rubber content of 60% and put it into a 5L reactor, add 480g of water to dilute it to a dry rubber content of 30%, add 32.4g of stabilizer OP-10, stir it in an open state for 30 minutes, then add 120g of formic acid and 473.4g of hydrogen peroxide, react in a closed state in a 40°C water bath for 17 hours, stop the reaction, add ammonia water dropwise until the pH is 8, and obtain an epoxidized natural rubber latex with a dry rubber content of 17.35% and an epoxidation degree of 50;

[0118] Step 2: weigh 600 g of white carbon black solid, add 5400 g of water, stir and mix, pour into a colloid mill, stir at 70 Hz and 5 ° C for 10 minutes, add 60 g of bis-[γ-(triethoxysilyl)propyl] tetrasulfide and 20 g of fatty alcohol polyoxyethylene ether-9, continue stirring for 10 minutes and then stop the reaction to obtain white carbon black slurry;

[0119] Step 3, weighing 61.11g of natural rubber latex with a dry rubber content of 60%, 588.21g of the epoxidized natural rubber latex prepared in step 1, and 977.8g of the white carbon black slurry prepared in step 2, stirring at 200 rpm for 30 minutes, pouring into 2.5L of anhydrous ethanol to flocculate to obtain a rubber block, cutting the rubber block into pieces and soaking it in 1% sodium carbonate solution for 24 hours, then washing it with water to neutrality, and drying it in a 60°C oven to constant weight to obtain a wet-process prepared nanocomposite masterbatch;

[0120] Step 4: Weigh 190.5 parts by weight of the nanocomposite masterbatch prepared in step 3, 5 parts by weight of zinc oxide, 2 parts by weight of stearic acid, 1 part by weight of antioxidant 4010NA, 1.5 parts by weight of accelerator D, 2 parts by weight of accelerator CZ, and 2 parts by weight of sulfur. Put the nanocomposite masterbatch into a twin-screw extruder, set the screw temperature to 80°C, and hold for 5 minutes to obtain a masterbatch; add the masterbatch to an internal mixer, set the internal mixer temperature to 60°C, and the speed to 60r / min. After mixing for 1 minute, add zinc oxide, stearic acid, and antioxidant and mix for 2 minutes, discharge, and obtain a rubber mix. Discharge the rubber mix on an open mill with cooling water and reduce the temperature to room temperature, then add accelerators and sulfur in sequence on the open mill, cut left and right 3 times, make triangle packages three times, and roll three times to obtain a nanocomposite rubber material.

[0121] Comparative Example 1

[0122] Step 1, weigh 600g of white carbon black solid, add 5400g of water, stir and mix, pour into a colloid mill, stir at 70Hz and 5°C for 10 minutes, add 60g of bis-[γ-(triethoxysilyl)propyl]tetrasulfide and 20g of fatty alcohol polyoxyethylene ether-9, continue stirring for 10 minutes and then stop the reaction to obtain white carbon black slurry;

[0123] Step 2: Weigh 203.7 g of natural rubber latex with a dry rubber content of 60% and 977.8 g of the white carbon black slurry prepared in step 1, stir them at 200 rpm for 30 minutes, pour them into 2.5 L of anhydrous ethanol and flocculate to obtain a rubber block, cut the rubber block into pieces, soak it in 1% sodium carbonate solution for 24 hours, wash it with water until it is neutral, put it in a 60°C oven and dry it to constant weight to obtain a wet-process prepared nanocomposite masterbatch;

[0124] Step 3, weigh 190.5 parts by weight of the nanocomposite masterbatch prepared in step 3, 5 parts by weight of zinc oxide, 2 parts by weight of stearic acid, 1 part by weight of antioxidant 4010NA, 1.5 parts by weight of accelerator D, 2 parts by weight of accelerator CZ, and 2 parts by weight of sulfur. Put the nanocomposite masterbatch into a twin-screw extruder, set the screw temperature to 80°C, and the residence time to 5 minutes to obtain a masterbatch; add the masterbatch to an internal mixer, set the internal mixer temperature to 60°C, and the speed to 60r / min. After mixing for 1 minute, add zinc oxide, stearic acid, and antioxidant and mix for 2 minutes, discharge the material, and obtain a rubber compound. Discharge the rubber compound on an open mill with cooling water and reduce the temperature to room temperature, then add accelerators and sulfur in sequence on the open mill, cut the left and right knives 3 times, make triangle packages three times, and roll three times to obtain a nanocomposite rubber material.

[0125] Comparative Example 2

[0126] Step 1, take 480g of natural rubber latex with a dry rubber content of 60% and put it into a 5L reactor, add 480g of water to dilute it to a dry rubber content of 30%, add 32.4g of stabilizer OP-10, stir it in an open state for 30 minutes, then add 120g of formic acid and 473.4g of hydrogen peroxide, react in a closed state in a 40°C water bath for 6 hours, stop the reaction, add ammonia water dropwise until the pH is 8, and obtain epoxidized natural rubber latex with a dry rubber content of 17.35% and an epoxidation degree of 30; pour the epoxidized natural rubber latex into 2.5L of anhydrous ethanol to flocculate to obtain a rubber block, cut the rubber block into pieces, soak it in a 1% sodium carbonate solution for 24 hours, wash it with water until it is neutral, put it in a 60°C oven and dry it to constant weight to obtain epoxidized natural rubber dry glue;

[0127] Step 2: Take 334 g of natural rubber latex with a dry rubber content of 60% and pour it into 1 L of anhydrous ethanol to flocculate to obtain a rubber block, cut the rubber block into pieces and soak it in a 1% sodium carbonate solution for 24 hours, then wash it with water until it is neutral, and put it in a 60°C oven to dry it to constant weight to obtain natural rubber dry glue;

[0128] Step 3: Weigh 30 parts by weight of the natural rubber dry glue prepared in step 2, 70 parts by weight of the epoxy natural rubber dry glue prepared in step 1, 80 parts by weight of white carbon black, 8 parts by weight of bis-[γ-(triethoxysilyl)propyl] tetrasulfide, 2.5 parts by weight of fatty alcohol polyoxyethylene ether-9, 5 parts by weight of zinc oxide, 2 parts by weight of stearic acid, 1 part by weight of antioxidant 4010NA, 1.5 parts by weight of accelerator D, 2 parts by weight of accelerator CZ, and 2 parts by weight of sulfur. The above raw materials in parts by weight are mixed in the following manner: dry rubber (epoxidized natural rubber dry rubber and natural rubber dry rubber) is put into an internal mixer, the temperature of the internal mixer is set to 60°C, the speed is 60r / min, zinc oxide, stearic acid, antioxidant are added after mixing for 1 minute, white carbon black and coupling agent are added three times after mixing for half a minute, each time with a half-minute interval, and the material is discharged to obtain a mixed rubber; the mixed rubber is put into a twin-screw extruder, the screw temperature is set to 80°C, the residence time is 5 minutes, and the rubber is obtained; the rubber is discharged on an open mill with cooling water and the temperature is reduced to room temperature, and then an accelerator and sulfur are added in sequence on the open mill, the left and right cutters are cut 3 times, the triangle packages are made three times, and the rolls are rolled three times to obtain a nano-composite rubber material. The transmission electron microscope image of the prepared nano-composite rubber material is shown in Figure 2.

[0129] Comparative Example 3

[0130] Step 1, take 480g of natural rubber latex with a dry rubber content of 60% and put it into a 5L reactor, add 480g of water to dilute it to a dry rubber content of 30%, add 32.4g of stabilizer OP-10, stir it in an open state for 30 minutes, then add 120g of formic acid and 473.4g of hydrogen peroxide, react in a closed state in a 40°C water bath for 6 hours, stop the reaction, add ammonia water dropwise until the pH is 8, and obtain an epoxidized natural rubber latex with a dry rubber content of 17.35% and an epoxidation degree of 30;

[0131] Step 2: weigh 600 g of white carbon black solid, add 5400 g of water, stir and mix, pour into a colloid mill, stir at 70 Hz and 5 ° C for 10 minutes, add 60 g of bis-[γ-(triethoxysilyl)propyl] tetrasulfide and 20 g of fatty alcohol polyoxyethylene ether-9, continue stirring for 10 minutes and then stop the reaction to obtain white carbon black slurry;

[0132] Step 3, weighing 61.11g of natural rubber latex with a dry rubber content of 60%, 588.21g of the epoxidized natural rubber latex prepared in step 1, and 977.8g of the white carbon black slurry prepared in step 2, stirring at 200 rpm for 30 minutes, pouring into 2.5L of anhydrous ethanol to flocculate to obtain a rubber block, cutting the rubber block into pieces and soaking it in 1% sodium carbonate solution for 24 hours, then washing it with water to neutrality, and drying it in a 60°C oven to constant weight to obtain a wet-process prepared nanocomposite masterbatch;

[0133] Step 4, weigh 190.5 parts by weight of the nanocomposite masterbatch prepared in step 3, 5 parts by weight of zinc oxide, 2 parts by weight of stearic acid, 1 part by weight of antioxidant 4010NA, 1.5 parts by weight of accelerator D, 2 parts by weight of accelerator CZ, and 2 parts by weight of sulfur. Put the masterbatch into an internal mixer, set the temperature of the internal mixer to 80°C, control the speed according to the temperature of the rubber compound, and stay for 5 minutes to obtain the masterbatch after heat treatment; set the temperature of the second stage internal mixer to 60°C and the speed to 60r / min, add the rubber compound thereto, mix for 1 minute, add zinc oxide, stearic acid, and antioxidant, mix for 2 minutes, and discharge. Discharge the rubber compound on an open mill with cooling water and reduce the temperature to room temperature, then add accelerators and sulfur in order on the open mill, cut left and right 3 times, make triangle packages three times, and roll three times to obtain a nanocomposite rubber material. The transmission electron microscope image of the prepared nanocomposite rubber material is shown in Figure 3.

[0134] Comparative Example 4

[0135] Step 1, take 480g of natural rubber latex with a dry rubber content of 60% and put it into a 5L reactor, add 480g of water to dilute it to a dry rubber content of 30%, add 32.4g of stabilizer OP-10, stir it in an open state for 30 minutes, then add 120g of formic acid and 473.4g of hydrogen peroxide, react in a closed state in a 40°C water bath for 6 hours, stop the reaction, add ammonia water dropwise until the pH is 8, and obtain epoxidized natural rubber latex with a dry rubber content of 17.35% and an epoxidation degree of 30; pour the epoxidized natural rubber latex into 2.5L of anhydrous ethanol to flocculate to obtain a rubber block, cut the rubber block into pieces, soak it in a 1% sodium carbonate solution for 24 hours, wash it with water until it is neutral, put it in a 60°C oven and dry it to constant weight to obtain epoxidized natural rubber dry glue;

[0136] Step 2: Take 334 g of natural rubber latex with a dry rubber content of 60% and pour it into 1 L of anhydrous ethanol to flocculate to obtain a rubber block, cut the rubber block into pieces and soak it in a 1% sodium carbonate solution for 24 hours, then wash it with water until it is neutral, and put it in a 60°C oven to dry it to constant weight to obtain natural rubber dry glue;

[0137] Step 3: Weigh 30 parts by weight of the natural rubber dry glue prepared in step 2, 70 parts by weight of the epoxy natural rubber dry glue prepared in step 1, 80 parts by weight of white carbon black, 8 parts by weight of bis-[γ-(triethoxysilyl)propyl] tetrasulfide, 2.5 parts by weight of fatty alcohol polyoxyethylene ether-9, 5 parts by weight of zinc oxide, 2 parts by weight of stearic acid, 1 part by weight of antioxidant 4010NA, 1.5 parts by weight of accelerator D, 2 parts by weight of accelerator CZ, and 2 parts by weight of sulfur. The above raw materials by weight are mixed in the following manner: the temperature of the internal mixer is set to 60°C, the speed is 60r / min, the rubber (natural rubber dry rubber and epoxy natural rubber dry rubber) is added thereto, after mixing for 1 minute, zinc oxide, stearic acid, and antioxidant are added and mixed for 30 seconds, half of the white carbon black and Si69 are added and mixed for 30 seconds, and the remaining white carbon black and Si69 are added and mixed for two minutes, and the material is discharged, and the sheet is produced on the open mill to obtain the mixed rubber; the mixed rubber is put into the internal mixer, the temperature is set to 80°C, the speed is adjusted according to the temperature of the rubber, and the residence time is 5 minutes to obtain the masterbatch; the masterbatch is produced on the open mill with cooling water and the temperature is reduced to room temperature, and then the accelerator and sulfur are added in order on the open mill, the left and right cuts are cut 3 times, the triangle package is made three times, and the roll is rolled three times to obtain the nano-composite rubber material. The transmission electron microscope image of the prepared nano-composite rubber material is shown in Figure 4.

[0138] The nanocomposite rubber materials prepared in the examples and comparative examples were left standing for 24 hours before being subjected to performance tests. The test standards and conditions are shown in Table 1, and the test results are shown in Tables 2 and 3.

[0139] Table 1

[0140]

[0141] In Table 1, M L is the minimum torque, M H is the maximum torque, T 10 is the scorch time, T 90 is the positive vulcanization time, and △Tg is the difference between the two glass transition temperatures in the DMA test.

[0142] Table 2

[0143]

[0144]

[0145] Table 3

[0146]

[0147]

[0148] The difference between Comparative Example 1 and Examples 1-7 is that the masterbatch of Comparative Example 1 does not contain epoxidized natural rubber latex. The performance data of Comparative Example 1 and Examples 1-7 in Table 2-3 show that compared with Comparative Example 1, the scorch time (T 10 ) shortens the curing time (T 90 ) is shortened, Tanδ is increased, compression fatigue temperature rise is increased, and Akron wear is reduced. It can be concluded that compared with natural rubber latex as a masterbatch, the present invention uses epoxidized natural rubber latex and natural rubber latex (the content of epoxidized natural rubber latex is 10-100%) as a masterbatch to improve wear resistance and anti-wet skid performance.

[0149] The difference between Comparative Example 2 and Example 5 is that the masterbatch is prepared by a dry method, while the masterbatch of Example 5 is prepared by a wet method and white carbon black is added thereto. The performance data of Comparative Example 2 and Example 5 in Table 2-3 show that the M of Example 5 is better than that of Comparative Example 2. L 、M H , T 10 , T 90 , compression fatigue temperature rise, Akron wear volume and ΔTg are all reduced. It can be concluded that, compared with the existing masterbatch preparation method, the masterbatch preparation method of the present invention can improve the compatibility of the two rubbers (ΔTg is reduced), can enhance the interface bonding between the filler and the rubber matrix to a certain extent, improve the dispersion of white carbon black in the rubber matrix, and thus improve the vulcanization performance, wear performance and anti-slip performance of the rubber material.

[0150] The difference between Comparative Example 3 and Example 5 is that Comparative Example 3 uses an internal mixer and an open mixer for mixing, while the present invention uses a twin-screw extruder. The performance data of Comparative Example 3 and Example 5 in Table 2-3 show that, relative to Comparative Example 3, Example 5 improves the torque difference, prolongs the scorch time, shortens the positive vulcanization time, improves Tanδ, and reduces the compression fatigue temperature rise and Akron wear. It can be concluded that, relative to the use of a conventional internal mixer, the present invention uses a twin-screw extruder to reduce rolling resistance, improve anti-wet skid performance and wear resistance, and at the same time, the reduced temperature rise indicates that the use of a twin-screw can make the white carbon black more evenly dispersed.

[0151] The difference between Comparative Example 4 and Example 5 is that Comparative Example 4 adopts a dry process and uses an internal mixer and an open mixer for mixing, while the present invention adopts a twin-screw extruder. The performance data of Comparative Example 4 and Example 5 in Table 2-3 show that, compared with Comparative Example 4, Example 5 improves M L and M H , prolonging the scorch time, shortening the vulcanization time, and at the same time increasing Tanδ, reducing the compression fatigue temperature rise, Akron wear and △Tg. It can be concluded that, compared with the dry process and conventional internal mixer, the method of the present invention can improve the compatibility of the two rubbers (△Tg reduction), can enhance the interface bonding between the filler and the rubber matrix to a certain extent, improve the dispersion of white carbon black in the rubber matrix, and thus reduce the rolling resistance and improve the vulcanization performance, wear performance and anti-slip performance of the rubber material.

[0152] In addition, according to the performance data of Examples 8-13 in Table 2, it can be concluded that as the processing temperature of the twin-screw extruder increases, the loss factor value of the rubber composite material obtained after processing decreases, the compression fatigue temperature rise decreases, and the wear performance is improved, indicating that high temperature can enhance the interface bonding between the filler and the rubber matrix to a certain extent, improve the dispersion of white carbon black in the rubber matrix, and improve the performance. The rubber composition obtained after processing with the increase of heat treatment temperature. As the epoxy degree increases, the scorch time of the rubber composite material obtained after processing does not change much, the positive vulcanization time and torque difference are shortened, the loss factor value increases, the compression fatigue temperature rise increases, and the wear performance is improved.

[0153] Compare Figure 1-4 It can be seen from the transmission electron microscope image that, compared with the preparation method of the comparative example, the white carbon black dispersion of the rubber composition prepared by the preparation method of the present invention is better.

[0154] Compare Figure 5-6 It can be seen that compared with conventional mixing using an internal mixer or an open mixer, the use of a twin-screw extruder in the present invention will not cause bulking problems during the preparation of the rubber composite material.

Claims

1. A nanocomposite masterbatch, characterized in that: The nanocomposite masterbatch is prepared by mixing and flocculating raw materials including the following components; the components and their weight parts are as follows: Calculated on the basis of dry rubber, latex 100 parts by weight; 40-120 parts by weight of white carbon black slurry, preferably 60-90 parts by weight; The latex comprises epoxidized natural rubber latex and natural rubber latex; based on dry rubber, the weight ratio of epoxidized natural rubber latex to natural rubber latex is 10-100:90-0, preferably 30-90:70-10; The mass content of white carbon black in the white carbon black slurry is 5-15%.

2. A method for preparing a nanocomposite masterbatch as claimed in claim 1, characterized in that: The preparation method comprises: at a temperature of 25-30° C., natural rubber latex, epoxidized natural rubber latex and white carbon black slurry are mixed to form a mixed system, the mixed system is flocculated with a sedimentation agent, and solids are collected to obtain the nano composite masterbatch.

3. The preparation method according to claim 2, characterized in that: The preparation method of the epoxidized natural rubber latex comprises: diluting the natural rubber latex with water, adding a stabilizer and mixing, then adding formic acid and hydrogen peroxide to react in a water bath at 40-50° C. under closed conditions, and after the reaction stops, adding ammonia water until the pH is 9-10 to obtain the epoxidized natural rubber latex; Preferably, the stabilizer is selected from one or more non-ionic active agents, preferably OP-10; or / and, Preferably, the epoxidation degree of the epoxidized natural rubber latex is 5-60, more preferably 10-35.

4. The preparation method according to claim 2, characterized in that: The preparation method of the white carbon black slurry comprises: adding water to the white carbon black and pouring the mixture into a colloid mill, stirring until the white carbon black is evenly dispersed, adding a coupling agent, and continuing to stir until the coupling agent is evenly dispersed to obtain the white carbon black slurry; Preferably, the stirring temperature is 5-10°C; or / and, Preferably, the coupling agent is selected from silane coupling agents; more preferably, the coupling agent is bis-[γ-(triethoxysilyl)propyl]tetrasulfide and fatty alcohol polyoxyethylene ether-9; or / and, Preferably, the weight of the coupling agent is 8-15 wt % of the weight of white carbon black.

5. The method for preparing the nanocomposite masterbatch according to claim 2, characterized in that: The precipitant is anhydrous ethanol; or / and, The volume ratio of the precipitant to the mixed system is 0.5-3:

1.

6. The method for preparing the nanocomposite masterbatch according to claim 2, characterized in that: The method further comprises cutting the nanocomposite masterbatch into pieces, soaking the pieces in a sodium carbonate solution, standing the pieces, washing the pieces with water until the pieces are neutral, and then drying the pieces at 55-70° C. until the pieces are constant in weight. Preferably, the mass concentration of the sodium carbonate solution is 1-3%.

7. A nanocomposite rubber material, characterized in that: The nanocomposite masterbatch is prepared by mixing raw materials including the nanocomposite masterbatch as claimed in claim 1.

8. The nanocomposite rubber material according to claim 7, characterized in that: The nanocomposite rubber material is prepared by mixing raw materials including the following components; the components and their weight parts are as follows: Nanocomposite masterbatch 190-200 parts by weight; The antioxidant is 0.5-5 parts by weight, preferably 1-3 parts by weight; The activator is 1-10 parts by weight, preferably 3-7 parts by weight; The accelerator is 1-8 parts by weight, preferably 2-6 parts by weight; The amount of the vulcanizing agent is 0.5-5 parts by weight, preferably 1-3 parts by weight.

9. A method for preparing a nanocomposite rubber material as claimed in claim 7 or 8, characterized in that: The preparation method comprises: heat-treating the nano-composite masterbatch by a twin-screw extruder to obtain a heat-treated masterbatch; wherein the screw temperature is 80-120° C. and the residence time is 1-6 minutes.

10. The method for preparing a nanocomposite rubber material according to claim 9, characterized in that: The method comprises mixing the heat-treated masterbatch with other raw materials.

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