Preparation method of modified white carbon black, modified white carbon black, and masterbatch and vulcanized rubber prepared thereby

Abstract

The application discloses a preparation method of modified white carbon black, modified white carbon black, and prepared masterbatch and vulcanized rubber. The preparation method of the modified white carbon black comprises the following steps: uniformly mixing silane coupling agent, sorbitan fatty acid ester surfactant, organic solvent and white carbon black to obtain the modified white carbon black. The application uses specific surfactant sorbitan fatty acid ester and silane coupling agent, modifies the white carbon black organic solvent dispersion liquid in a high-speed dispersion machine, and prepares the masterbatch filled with the white carbon black by liquid-phase compounding technology of the rubber solution, so as to prepare the rubber vulcanized rubber from the masterbatch. Compared with the traditional dry mixing technology or the wet mixing technology using the coupling agent alone, the dispersion of the white carbon black in the rubber matrix is better, the dynamic performance, heat generation and wear resistance of the rubber compound are improved, and the prepared vulcanized rubber can be used for preparing the tread rubber, so that the rolling resistance and heat generation of the tire are reduced.

Description

Technical Field

[0001] This invention relates to the field of rubber nanocomposite materials, and more specifically, to a method for preparing modified silica, the modified silica and the resulting masterbatch and vulcanizate. Background Technology

[0002] Silica is the second most used reinforcing filler in the rubber industry after carbon black. Reinforcing tires with silica can significantly reduce rolling resistance and improve their wet skid resistance. Therefore, green tire tread compounds are mainly made by filling rubber with silica. Because silica has a large number of hydroxyl groups on its surface, it is prone to agglomeration and has poor affinity with rubber. Therefore, a key to preparing silica / rubber nanocomposites is to improve the dispersion of silica in the rubber matrix.

[0003] Organosilane coupling agents have excellent modifying and dispersing effects on silica and are widely used for silica modification. The modification process typically employs an in-situ dry method, where the silane coupling agent modifies the silica simultaneously during the mixing of fillers and rubber. In-situ modification achieves good dispersion of silica, but the modified silica still exhibits some agglomeration, leading to difficulties in material intake, high energy consumption, and dust pollution during mixing. Wet processes do not present these problems and are also beneficial for filler dispersion. Furthermore, suitable dispersants are beneficial for silica dispersion; the combined use of dispersants and coupling agents can potentially achieve even better dispersion results.

[0004] Therefore, this study investigates a method for modifying silica in the organic phase, seeking inexpensive, readily available, and effective dispersing agents to enhance the dispersion of silica in the rubber matrix, effectively improve the dynamic mechanical properties of the rubber compound, and prepare rubber compositions with better application prospects in the tire industry. Summary of the Invention

[0005] In order to solve the technical problems existing in the prior art, the present invention provides a method for preparing modified silica, modified silica, and the resulting masterbatch and vulcanized rubber.

[0006] This invention provides a method for preparing modified silica, which further improves the dispersion of silica in a rubber matrix. Compared with modification by using silane coupling agent alone, the Payne effect of the compound obtained by combining modified silica and rubber is significantly reduced, and the silica is more uniformly dispersed.

[0007] This invention modifies silica in an organic phase by using a combination of specific surfactants and silane coupling agents and employing the dispersion and mixing action of a high-speed disperser. The modified silica slurry is directly used to compound with a rubber solution, and after solvent removal and drying, a modified silica masterbatch is obtained. Various minor ingredients, compounding agents, and vulcanizing agents are added to the masterbatch, mixed evenly, and vulcanized to obtain the vulcanized rubber.

[0008] This invention utilizes inexpensive Span series surfactants (such as Span 20 / 40 / 60 / 80) to improve the uniformity of silica dispersion in organic solvents and maintain its stability, reducing the surface energy of silica. The modified silica disperses better in the rubber matrix, further improving the dynamic properties of the rubber compound. This invention forms a silica slurry by high-speed dispersion and mixing of a silane coupling agent, silica, and organic reagents. During this process, a specific surfactant is added for further homogenization, ultimately yielding a uniform and stable silica slurry that can be used for liquid-phase compounding with rubber solutions to prepare wet-process masterbatches. The entire process of this invention is simple and efficient, resulting in good silica modification, significantly improved dispersibility in the rubber matrix, improved overall performance of the composite material, reduced fatigue compression heat generation, significantly reduced rolling resistance, and improved wear resistance.

[0009] One objective of this invention is to provide a method for preparing modified silica, comprising:

[0010] The modified silica was obtained by uniformly mixing silane coupling agent, sorbitan fatty acid ester surfactant, organic solvent, and silica; and then high-speed dispersion and mixing were carried out in a high-speed disperser.

[0011] In a preferred embodiment of the present invention,

[0012] First, the silane coupling agent is dissolved in an organic solvent, then silica is added and mixed evenly to obtain a silica slurry; then, sorbitan fatty acid ester surfactant is added to the obtained silica slurry and mixed evenly to obtain the modified silica.

[0013] After adding silica, disperse the silica in a high-speed disperser at a speed of 1800-2200 r / min for 5-30 min, preferably 10-20 min.

[0014] After adding the dehydrated sorbitan fatty acid ester surfactant, the mixture is rotated at 1800-2200 r / min and then redispersed for 3-10 min, preferably 5-7 min.

[0015] In a preferred embodiment of the present invention,

[0016] The silica mentioned is commercially available precipitated or fumed silica commonly used in this field, with a specific surface area of ​​50–300 m². 2 / g, preferably 100-200m 2 / g; oil absorption value 0.3~3ml / g, preferably 0.5~1.5ml / g;

[0017] The silane coupling agent is a conventional organosilane coupling agent in the art, preferably one of bis-[γ-(triethoxysilane)propyl]tetrasulfide (Si69), bis-[γ-(triethoxysilane)propyl]disulfide (Si75), 3-thiocyanopropyltriethoxysilane, γ-mercaptopropyltriethoxysilane (KH580), γ-aminopropyltriethoxysilane (KH550), and γ-methacryloyloxypropyltrimethoxysilane (KH570);

[0018] The organic solvent is a good solvent for rubber, preferably at least one of aliphatic hydrocarbon solvents and aromatic hydrocarbon solvents; the aliphatic hydrocarbon solvent is at least one of solvent oil, cycloalkanes, substituted cycloalkanes, straight-chain alkanes, and branched-chain alkanes; preferably cycloalkanes or n-alkanes; more preferably C6-C7 cycloalkanes or n-alkanes; the aromatic hydrocarbon solvent is at least one of benzene, toluene, and xylene.

[0019] In a preferred embodiment of the present invention,

[0020] The mass ratio of silica to organic solvent is 1:(3-99); preferably 1:(6-19); more preferably 1:(8-10); and / or,

[0021] The amount of silane coupling agent used is 3% to 20% of the mass of silica; preferably 10% to 12%.

[0022] In a preferred embodiment of the present invention,

[0023] The sorbitan fatty acid ester surfactant is sorbitan monooleate, which is one of sorbitan monolaurate (S-20), sorbitan monopalmitate (S-40), sorbitan monostearate (S-60), and sorbitan monooleate (S-80).

[0024] In a preferred embodiment of the present invention,

[0025] The amount of sorbitan monooleate surfactant used is 0.5% to 13% of the mass of silica; preferably 1% to 10%.

[0026] The second objective of this invention is to provide a modified silica prepared by the above method.

[0027] The third objective of this invention is to provide a masterbatch.

[0028] The masterbatch is prepared by uniformly mixing a rubber solution and the above-mentioned modified silica slurry and then removing the solvent;

[0029] The rubber solution is a solution-polymerized rubber solution or a solution obtained by dissolving rubber in a solvent; the solution-polymerized rubber is solution-polymerized styrene-butadiene rubber (SSBR) or other solution-polymerized rubbers; the rubber includes, but is not limited to, natural rubber, cis-butadiene rubber, butyl rubber or combinations thereof, with a molecular weight range of 50,000 to 5,000,000, preferably 100,000 to 2,000,000; the solvent for dissolving the rubber is a good solvent for rubber, preferably cyclohexane or n-hexane.

[0030] The concentration range of the rubber solution is 5–30 wt%; preferably 12–15 wt%.

[0031] The mass ratio of rubber in the rubber solution to silica in the modified silica is 1:(0.3-1.2); preferably 1:(0.5-0.8).

[0032] The fourth objective of this invention is to provide a method for preparing masterbatch, comprising:

[0033] The rubber solution and the modified silica are mixed evenly at the stated mass ratio, and the solvent is removed to obtain the masterbatch; wherein the solvent removal can be carried out by any method known in the art.

[0034] The fifth objective of this invention is to provide a vulcanizate.

[0035] The vulcanized rubber is obtained by uniformly mixing and vulcanizing the components including the masterbatch, activator, antioxidant, accelerator and vulcanizing agent;

[0036] The activator, antioxidant, accelerator and vulcanizing agent mentioned are all conventional rubber additives, and the dosages are all conventional dosages;

[0037] The vulcanization process adopts conventional rubber vulcanization conditions, with the preferred vulcanization temperature being 150℃~170℃ and the vulcanization time to the positive vulcanization point being [missing information].

[0038] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0039] This invention employs a combination of Span series surfactants and silane coupling agents to modify silica in an organic solvent. The Span series surfactants improve the uniformity of silica dispersion and maintain its stability in the organic solvent, reducing the surface energy of silica. The modified silica disperses better in the rubber matrix. Compared to using silane coupling agents alone, the combined use of both improves the silica modification effect, significantly reduces the Payne effect, improves the dynamic properties of the composite material, reduces compression heat generation, and significantly lowers rolling resistance. The modified silica is then compounded with a rubber solution in a liquid phase, followed by solvent removal and drying to obtain a silica-filled wet-process masterbatch. Compared to in-situ modification, the liquid-phase compounding process shortens subsequent compounding time, significantly reduces compounding energy consumption, and improves the combined effect.

[0040] This invention utilizes the shearing and dispersing action of a high-speed disperser to obtain a uniform and stable modified silica slurry, which is suitable for liquid-phase composite processes.

[0041] The entire process of this invention is simple and efficient. It utilizes the strong shearing and dispersing effects of a high-speed disperser, the coupling effect of a silane coupling agent, and the amphiphilicity of Span to modify silica. The resulting modified silica exhibits good dispersibility in a rubber matrix, improving the dynamic properties of the composite material, reducing compression fatigue heat generation, decreasing rolling resistance, and enhancing wear resistance. The rubber composition of this invention, when used to prepare tread rubber, can reduce tire rolling resistance, decrease heat generation, and improve the energy efficiency and fuel economy of tires. Attached Figure Description

[0042] Figure 1 The graphs show the storage modulus of the rubber compounds in Examples 1-2 and Comparative Examples 1-2 as a function of strain.

[0043] Figure 2 The graphs show the variation of the loss factor of the vulcanized rubber in Examples 1-2 and Comparative Examples 1-2 as a function of strain.

[0044] Figure 3 The graphs show the storage modulus of the rubber compounds in Examples 3-4 and Comparative Examples 3-4 as a function of strain.

[0045] Figure 4 The graphs show the variation of the loss factor of the vulcanized rubber in Examples 3-4 and Comparative Examples 3-4 as a function of strain.

[0046] Figure 5 The graphs show the storage modulus of the rubber compounds in Examples 5 and Comparative Examples 5-6 as a function of strain.

[0047] Figure 6 The graphs show the variation of the loss factor with strain for the vulcanized rubbers of Examples 5 and Comparative Examples 5-6. Detailed Implementation

[0048] The present invention will now be described in detail with reference to the accompanying drawings and embodiments. It should be noted that the following embodiments are only used to further illustrate the present invention and should not be construed as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made by those skilled in the art based on the content of the present invention are still within the scope of protection of the present invention.

[0049] The raw materials used in the examples and comparative examples were all commercially available.

[0050] The main raw material specifications are as follows:

[0051]

[0052]

[0053] The relevant performance testing standards and instruments for the examples and comparative examples are shown in Table 1:

[0054] Table 1. Relevant performance testing methods and instruments

[0055] Test Project Test Standards Equipment Name Specifications and Models Manufacturer RPA test * Rubber Processing Analyzer RPA2000 American ALPHA Company Tensile test GB / T528-1998 tensile testing machine AL-7000 High-speed rail testing company Tear test GB / T529-1999 tensile testing machine AL-7000 High-speed rail testing company Compression generates heat GB / T1687-1993 Dynamic compression fatigue testing machine RH-3000N High-speed rail testing company Akron wear GB / T1689-1998 Akron Grinding Mill MZ-4061 Jiangdu Mingzhu Test Machinery Factory Roller wear GB / T9867-2008 Roller abrasion testing machine GT7012-A High-speed rail testing company

[0056] *RPA test method: Compound rubber at 60°C, 1Hz, strain 0.28–200%; vulcanized rubber at 60°C, 10Hz, strain range 0.28–42%. All parts mentioned in the examples and comparative examples are by weight.

[0057] Example 1

[0058] 900 parts of cyclohexane, 10 parts of Si75, and 100 parts of silica were added sequentially to a high-speed disperser. The speed was maintained at 2000 r / min, and the mixture was dispersed for 5 min. Then, 2 parts of Span 80 were added, and the mixture was dispersed for 5 min. The product was then discharged to obtain modified silica.

[0059] The mass ratio of rubber in the rubber solution to silica in the modified silica is 1:0.8. The above silica slurry is mixed with a 12% SSBR4602 cyclohexane solution and stirred until homogeneous. The solvent is removed by hot water at 95°C or higher, and the mixture is dried to obtain the masterbatch.

[0060] The above-mentioned masterbatch, 3 parts zinc oxide, 2 parts stearic acid, and 2 parts antioxidant 4020 were mixed evenly in an internal mixer. After being discharged and left to stand for 8 hours, 1.7 parts accelerator CZ, 1.8 parts accelerator DPG, and 1.7 parts sulfur were then mixed in on an open mill. After standing for 12 hours, the mixture was vulcanized to the correct vulcanization temperature on a 150°C flat vulcanizing machine to obtain vulcanized rubber.

[0061] Example 2

[0062] 900 parts of cyclohexane, 10 parts of Si75, and 100 parts of silica were added sequentially to a high-speed disperser. The speed was maintained at 2000 r / min, and the mixture was dispersed for 5 min. Then, 10 parts of Span 80 were added, and the mixture was dispersed for 5 min. The mixture was then discharged to obtain modified silica.

[0063] The mass ratio of rubber in the rubber solution to silica in the modified silica is 1:0.8. The above silica slurry is mixed with a 12% SSBR4602 cyclohexane solution and stirred until homogeneous. The solvent is removed by hot water at 95°C or higher, and the mixture is dried to obtain the masterbatch.

[0064] The above-mentioned masterbatch, 3 parts zinc oxide, 2 parts stearic acid, and 2 parts antioxidant 4020 were mixed evenly in an internal mixer. After being discharged and left to stand for 8 hours, 1.7 parts accelerator CZ, 1.8 parts accelerator DPG, and 1.7 parts sulfur were then mixed in on an open mill. After standing for 12 hours, the mixture was vulcanized to the correct vulcanization temperature on a flat vulcanizing plate at 150°C to obtain vulcanized rubber.

[0065] Example 3

[0066] 800 parts of cyclohexane, 9.6 parts of Si75, and 80 parts of silica were added sequentially to a high-speed disperser. The speed was maintained at 2000 r / min, and the mixture was dispersed for 10 min. Then, 1 part of Span 40 was added, and the mixture was dispersed for 5 min. The product was then discharged to obtain modified silica.

[0067] The mass ratio of rubber in the rubber solution to silica in the modified silica is 1:0.8. The above silica slurry is mixed with a 12% SSBR6430 cyclohexane solution and stirred until homogeneous. The solvent is removed by hot water at 95°C or higher, and the mixture is dried to obtain the masterbatch.

[0068] The above-mentioned masterbatch, 3 parts zinc oxide, 2 parts stearic acid, and 2 parts antioxidant 4020 were mixed evenly in an internal mixer. After being discharged and left to stand for 8 hours, 1.7 parts accelerator CZ, 1.8 parts accelerator DPG, and 1.7 parts sulfur were then mixed in on an open mill. After standing for 12 hours, the mixture was vulcanized to the correct vulcanization temperature on a flat vulcanizing plate at 150°C to obtain vulcanized rubber.

[0069] Example 4

[0070] 800 parts of cyclohexane, 9.6 parts of Si75, and 80 parts of silica were added sequentially to a high-speed disperser. The speed was maintained at 2000 r / min, and the mixture was dispersed for 10 min. Then, 4 parts of Span 40 were added, and the mixture was dispersed for another 5 min. The product was then discharged to obtain modified silica.

[0071] The mass ratio of rubber in the rubber solution to silica in the modified silica is 1:0.8. The above silica slurry is mixed with a 12% SSBR6430 cyclohexane solution and stirred until homogeneous. The solvent is removed by hot water at 95°C or higher, and the mixture is dried to obtain the masterbatch.

[0072] The above-mentioned masterbatch, 3 parts zinc oxide, 2 parts stearic acid, and 2 parts antioxidant 4020 were mixed evenly in an internal mixer. After being discharged and left to stand for 8 hours, 1.7 parts accelerator CZ, 1.8 parts accelerator DPG, and 1.7 parts sulfur were then mixed in on an open mill. After standing for 12 hours, the mixture was vulcanized to the correct vulcanization temperature on a flat vulcanizing plate at 150°C to obtain vulcanized rubber.

[0073] Example 5

[0074] 720 parts of n-hexane, 9 parts of Si69, and 90 parts of silica were added sequentially to a high-speed disperser. The speed was maintained at 2000 r / min, and the mixture was dispersed for 10 min. Then, 2 parts of Span 80 were added, and the mixture was dispersed for another 5 min. The product was then discharged to obtain modified silica.

[0075] The mass ratio of rubber in the rubber solution to silica in the modified silica is 1:0.5. The above silica slurry is mixed with a 15% SSBR6430 cyclohexane solution and stirred until homogeneous. The solvent is removed by hot water at 95°C or higher, and the mixture is dried to obtain the masterbatch.

[0076] The above-mentioned masterbatch, 3 parts zinc oxide, 2 parts stearic acid, and 2 parts antioxidant 4020 were mixed evenly in an internal mixer. After being discharged and left to stand for 8 hours, 1.7 parts accelerator CZ, 1.8 parts accelerator DPG, and 1.7 parts sulfur were then mixed in on an open mill. After standing for 12 hours, the mixture was vulcanized to the correct vulcanization temperature on a flat vulcanizing plate at 150°C to obtain vulcanized rubber.

[0077] Comparative Example 1

[0078] Compared with Examples 1-2, Comparative Example 1 is a wet glue without Span 80.

[0079] 900 parts of cyclohexane, 10 parts of Si75, and 100 parts of silica were added sequentially to a high-speed disperser. The dispersion was carried out at a speed of 2000 r / min for 10 min, and then discharged to obtain modified silica.

[0080] The mass ratio of rubber in the rubber solution to silica in the modified silica is 1:0.8. The above silica slurry is mixed with a 12% SSBR4602 cyclohexane solution and stirred until homogeneous. The solvent is removed by hot water at 95°C or higher, and the mixture is dried to obtain the masterbatch.

[0081] The above-mentioned masterbatch, 3 parts zinc oxide, 2 parts stearic acid, and 2 parts antioxidant 4020 were mixed evenly in an internal mixer. After being discharged and left to stand for 8 hours, 1.7 parts accelerator CZ, 1.8 parts accelerator DPG, and 1.7 parts sulfur were then mixed in on an open mill. After standing for 12 hours, the mixture was vulcanized to the correct vulcanization temperature on a flat vulcanizing plate at 150°C to obtain vulcanized rubber.

[0082] Comparative Example 2

[0083] Compared with Examples 1-2, Comparative Example 2 is a dry adhesive without the addition of Span 80.

[0084] On a two-roll mill, 80 parts of silica and 8 parts of Si75 were added to 100 parts of SSBR4602 and mixed evenly. Then, 3 parts of zinc oxide, 2 parts of stearic acid, and 2 parts of antioxidant 4020 were added and mixed evenly in an internal mixer. After the mixture was discharged and left to stand for 8 hours, 1.7 parts of accelerator CZ, 1.8 parts of accelerator DPG, and 1.7 parts of sulfur were added on the two-roll mill. After standing for 12 hours, the mixture was vulcanized on a flat vulcanizing plate at 150°C until it reached the correct vulcanization temperature to obtain vulcanized rubber.

[0085] Comparative Example 3

[0086] Compared with Examples 3-4, Comparative Example 3 was a wet glue without the addition of Span 40.

[0087] In a high-speed disperser, 800 parts of cyclohexane, 9.6 parts of Si75, and 80 parts of silica were added sequentially, maintaining a speed of 2000 r / min and dispersing for 15 min. The material was then discharged. The silica slurry was mixed with a 12% SSBR6430 cyclohexane solution at a mass ratio of rubber to silica in the rubber solution of 1:0.8. The solvent was removed using hot water above 95℃, and the mixture was dried to obtain the masterbatch. The masterbatch, 3 parts of zinc oxide, 2 parts of stearic acid, and 2 parts of antioxidant 4020 were mixed evenly in an internal mixer. After discharge and resting for 8 hours, 1.7 parts of accelerator CZ, 1.8 parts of accelerator DPG, and 1.7 parts of sulfur were added on an open mill. After resting for 12 hours, the mixture was vulcanized at 150℃ on a flat vulcanizing plate until positive vulcanization was achieved, yielding the vulcanized rubber.

[0088] Comparative Example 4

[0089] Compared with Examples 3-4, Comparative Example 4 is a dry adhesive without the addition of Span 40.

[0090] On a two-roll mill, 80 parts of silica and 9.6 parts of Si75 were added to 100 parts of SSBR6430 and mixed evenly. Then, 3 parts of zinc oxide, 2 parts of stearic acid, and 2 parts of antioxidant 4020 were added and mixed evenly in an internal mixer. After the mixture was discharged and left to stand for 8 hours, 1.7 parts of accelerator CZ, 1.8 parts of accelerator DPG, and 1.7 parts of sulfur were added on the two-roll mill. After standing for 12 hours, the mixture was vulcanized on a flat vulcanizing plate at 150°C until it reached the correct vulcanization temperature to obtain vulcanized rubber.

[0091] Comparative Example 5

[0092] The difference from Example 5 is that Comparative Example 5 is a wet glue without Span 80.

[0093] In a high-speed disperser, 720 parts of n-hexane, 9 parts of Si69, and 90 parts of silica were added sequentially, and the dispersion was maintained at 2000 r / min for 15 min to obtain modified silica. The silica slurry was mixed with a 15% SSBR6430 cyclohexane solution at a mass ratio of rubber to silica in the rubber solution of 1:0.5. The mixture was stirred until homogeneous, the solvent was removed using hot water above 95℃, and the mixture was dried to obtain the masterbatch.

[0094] The above-mentioned masterbatch, 3 parts zinc oxide, 2 parts stearic acid, and 2 parts antioxidant 4020 were mixed evenly in an internal mixer. After being discharged and left to stand for 8 hours, 1.7 parts accelerator CZ, 1.8 parts accelerator DPG, and 1.7 parts sulfur were then mixed in on an open mill. After standing for 12 hours, the mixture was vulcanized to the correct vulcanization temperature on a flat vulcanizing plate at 150°C to obtain vulcanized rubber.

[0095] Comparative Example 6

[0096] The difference from Example 5 is that Comparative Example 6 is a dry adhesive without the addition of Span 80.

[0097] On a two-roll mill, 50 parts of silica and 5 parts of Si69 were added to 100 parts of SSBR6430 and mixed evenly. Then, 3 parts of zinc oxide, 2 parts of stearic acid, and 2 parts of antioxidant 4020 were added and mixed evenly in an internal mixer. After the mixture was discharged and allowed to stand for 8 hours, 1.7 parts of accelerator CZ, 1.8 parts of accelerator DPG, and 1.7 parts of sulfur were added on the two-roll mill. After standing for 12 hours, the mixture was vulcanized on a flat vulcanizing plate at 150°C until it reached the correct vulcanization temperature, thus obtaining vulcanized rubber.

[0098] Table 2. Performance test results of vulcanizates from Examples 1-2 and Comparative Examples 1-2

[0099] Table 3. Performance test results of vulcanizates in Examples 3-4 and Comparative Examples 3-4

[0100] Example 3 Example 4 Comparative Example 3 Comparative Example 4 Tensile strength / MPa 25.2 27.1 23.3 23.5 Elongation at break / % 421 459 431 410 100% elongation / MPa 3.8 3.6 3.3 3.3 300% elongation / MPa 17.6 16.0 15.3 15.3 Tear strength (KN / m) 52 57 53 50 Heat generated by compression (°C) 25.6 24.1 26.5 27 <![CDATA[Akkron Abrasion (cm 3 / 1.61 km)]]> 0.078 0.085 0.082 0.091 <![CDATA[Roller wear (cm 3 )]]> 0.127 0.122 0.133 0.138 Shore A hardness 62 64 60 65

[0101] As can be seen from Table 2, the heat of compression in Examples 1-2 is lower than that in Comparative Examples 1-2, and the Akron wear and roller wear values ​​are not significantly different or have decreased. This indicates that the use of Span and coupling agent reduces the heat of compression of the material while maintaining the wear resistance basically unchanged or slightly improved.

[0102] from Figure 1 It is evident that the Payne effect in Examples 1 and 2 is significantly reduced, the dispersion of silica is more uniform, and there are fewer filler aggregates; from Figure 2 As can be seen, the loss factors of Examples 1 and 2 are significantly reduced, indicating that the vulcanized rubber has lower rolling resistance, reduced internal friction, and can better reduce energy consumption, thus meeting the needs of tire fuel saving.

[0103] As can be seen from Table 3, compared with Comparative Examples 3-4, the vulcanizates of Examples 3-4 showed improved 300% elongation, tensile strength and tear strength. At the same time, compression heat generation was reduced, roller wear and Akron wear values ​​decreased, and the wear resistance of the material was improved.

[0104] from Figure 3 It is evident that the Payne effect in Example 4 is weaker than that in Comparative Example 3, and the silica in Example 4 is more uniformly dispersed. Figure 4 This indicates that the dynamic loss tanδ value of the vulcanizates in Examples 3 and 4 decreased significantly, showing that the materials have significantly reduced rolling resistance.

[0105] Table 4. Performance test results of vulcanizates in Example 5 and Comparative Examples 5-6

[0106] Example 5 Comparative Example 5 Comparative Example 6 Tensile strength / MPa 22.0 19.9 18.2 Elongation at break / % 521 531 510 100% elongation / MPa 2.1 1.8 1.9 300% elongation / MPa 10.6 9.3 8.3 Tear strength (kN / m) 53 53 50 Heat generated by compression (°C) 19.4 20.5 21.6 <![CDATA[Akkron Abrasion (cm 3 / 1.61 km)]]> 0.121 0.134 0.131 <![CDATA[Roller wear (cm 3 / )]]> 0.137 0.143 0.148 Shore A hardness 42 40 45

[0107] Table 4 shows that Example 5, compared to Comparative Examples 5-6, has higher tensile strength and 300% elongation at a given point, lower heat of compression, and better abrasion resistance.

[0108] from Figure 5 , Figure 6 It can be seen that, compared with Comparative Examples 5 and 6, Example 5 has a weaker Payne effect and the lowest dynamic loss factor, indicating that the silica in Example 5 is more uniformly dispersed, the vulcanizate has lower rolling resistance, and can better reduce energy consumption during tire use.

[0109] This invention modifies silica in an organic phase by using a combination of Span surfactant and silane coupling agent, utilizing the dispersion and mixing action of a high-speed disperser, and then further blending it with a rubber solution to prepare a masterbatch. This invention significantly improves filler dispersion, reduces the Payne effect, results in lower heat generation in the vulcanized rubber, lower rolling resistance, and better wear resistance.

Claims

1. A method for preparing a modified white carbon black, characterized by The method comprises: The silane coupling agent is dissolved in an organic solvent, and white carbon black is added, and after uniform mixing, a white carbon black slurry is obtained; then a sorbitan fatty acid ester surfactant is added to the obtained white carbon black slurry, and after uniform mixing, the modified white carbon black is obtained; The sorbitan fatty acid ester surfactant is at least one of sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, and sorbitan monooleate; The silane coupling agent is one of bis-[gamma-(triethoxysil) propyl] tetrasulfide, bis-[gamma-(triethoxysil) propyl] disulfide, 3-thiocyanate propyl triethoxysilane, gamma-mercapto propyl triethoxysilane, gamma-aminopropyl triethoxysilane, and gamma-methacryloxy propyl trimethoxysilane; The mass ratio of white carbon black to organic solvent is 1:(3-99); the amount of silane coupling agent is 3%-20% of the mass of white carbon black; and the amount of sorbitan fatty acid ester surfactant is 0.5%-13% of the mass of white carbon black.

2. The method for preparing modified white carbon black according to claim 1, characterized in that: The organic solvent is at least one of aliphatic hydrocarbon solvent and aromatic hydrocarbon solvent.

3. The method for preparing modified white carbon black according to claim 1, characterized in that: The mass ratio of white carbon black to organic solvent is 1:(6-19); and / or, The amount of silane coupling agent is 10%-12% of the mass of white carbon black.

4. The method for preparing modified white carbon black according to claim 1, characterized in that: The mass ratio of white carbon black to organic solvent is 1:(8-10).

5. The method for preparing modified white carbon black according to claim 1, characterized in that: The amount of sorbitan fatty acid ester surfactant is 1%-10% of the mass of white carbon black.

6. Modified white carbon black prepared by the method according to any one of claims 1-5.

7. A master batch comprising the modified white carbon black according to claim 6, characterized in that: The master batch is prepared by uniformly mixing a rubber solution and a modified white carbon black slurry and then removing the solvent; The rubber solution is a solution of solution polymerized rubber or rubber dissolved in a solvent; The concentration of the rubber solution is in the range of 5-30 wt%; The mass ratio of rubber in the rubber solution to white carbon black in the modified white carbon black is 1:(0.3-1.2).

8. The master batch according to claim 7, characterized in that: The concentration of the rubber solution is in the range of 12-15 wt%; The mass ratio of rubber in the rubber solution to white carbon black in the modified white carbon black is 1:(0.5-0.8).

9. A process for the preparation of a masterbatch as claimed in claim 7 or 8, characterized in that The method comprises: The rubber solution and the modified white carbon black are uniformly mixed according to the mass ratio, and then the solvent is removed to obtain the master batch.

10. A vulcanized rubber comprising the master batch according to claim 7 or 8, characterized in that: The vulcanized rubber is obtained by uniformly mixing components including the master batch, an activator, an antioxidant, an accelerator, and a vulcanizing agent, and then vulcanizing.

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