Vulcanized rubber composition, vulcanized rubber, preparation method of vulcanized rubber and tire

Abstract

The invention provides a vulcanized rubber composition, vulcanized rubber, a preparation method of the vulcanized rubber and a tire. The vulcanized rubber composition is prepared from the following components in parts by weight: 60 to 100 parts of butadiene styrene rubber, 20 to 40 parts of butadiene rubber, 120 to 140 parts of white carbon black, 3 to 12 parts of white carbon black grafted modified liquid butadiene rubber, 32 to 38 parts of plasticizing oil, 35 to 45 parts of wet-skid-resistant resin, 3 to 5 parts of white carbon black dispersing agent, 3 to 4 parts of zinc oxide, 1 to 3 parts of stearic acid and 1 to 2 parts of sulfur. The parts by weight of all the components in the vulcanized rubber composition are controlled within the range, so that the mutual synergistic effect of all the components can be improved, and the wet friction coefficient and the ice friction coefficient of vulcanized rubber can be further improved.

Description

Technical Field

[0001] This invention relates to the field of tire technology, and more specifically, to a vulcanizate composition, a vulcanizate, a method for preparing the same, and a tire. Background Technology

[0002] With the increasing frequency of extreme weather events globally and the significant rise in mixed rain and snow weather in winter, the performance limitations of traditional snow tires on wet, icy, and flooded roads are becoming increasingly apparent. According to EU road safety data, 37% of winter traffic accidents are caused by tire slippage due to wet tires, and braking distance on ice is 2-3 times longer than on dry surfaces. Therefore, improving the anti-wet and anti-icy performance of winter tire treads has become a pressing issue in the development of high-wet-resistant winter tires, particularly in the face of winter environments with both wet and icy surfaces.

[0003] Chinese patent application CN111440367A utilizes modified styrene-butadiene rubber to improve wet grip performance, but the content of silica is too low, failing to meet the current urgent requirements for wet grip performance. Therefore, current high wet grip winter tire formulations commonly use a large amount of silica to improve wet performance, but this sacrifices ice performance. Furthermore, to maintain hardness, a large amount of oil is added to reduce tread hardness, but this dilutes the percentage of tread rubber and easily forms an oil film on the tread, both of which affect the wet and ice friction coefficients of the tread rubber. Additionally, the large amount of silica used for reinforcement to improve wet performance also results in higher rolling resistance. Therefore, for the development of high wet grip winter tire tread formulations, how to further improve the wet and ice friction coefficients while preventing some plasticizer oil from migrating to the tread and affecting wet and ice performance has become an urgent problem to solve. Summary of the Invention

[0004] The main objective of this invention is to provide a vulcanizate composition, vulcanizate, its preparation method, and a tire, in order to solve the problem of low wet friction coefficient and ice friction coefficient of vulcanizates in the prior art.

[0005] To achieve the above objectives, according to one aspect of the present invention, a vulcanizate composition is provided, comprising, by weight: 60-100 parts of styrene-butadiene rubber, 20-40 parts of butadiene rubber, 120-140 parts of silica, 3-12 parts of silica-grafted modified liquid butadiene rubber, 32-38 parts of plasticizing oil, 35-45 parts of anti-slip resin, 3-5 parts of silica dispersant, 3-4 parts of zinc oxide, 1-3 parts of stearic acid, and 1-2 parts of sulfur.

[0006] Furthermore, the mass ratio of silica-grafted modified liquid butadiene rubber to plasticizer oil is (6~12):(32~36).

[0007] Furthermore, the mass ratio of silica to liquid butadiene rubber in silica-grafted modified liquid butadiene rubber is 1:(3~10); and / or, the number average molecular weight of liquid butadiene rubber in silica-grafted modified liquid butadiene rubber is 5000~18000 g / mol; and / or, the silica in silica-grafted modified liquid butadiene rubber exists in the form of silica aggregates, and the average particle size of silica aggregates is 260~350 nm.

[0008] Further, the plasticizing oil is selected from any one or more of environmentally friendly aromatic oils, naphthenic oils, and aromatic oils; and / or, the anti-slip resin is selected from any one or more of resin SA85, resin DCPD, and resin C9; and / or, by weight, the vulcanizate composition further includes: 8-12 parts of silane coupling agent, 4-6 parts of carbon black, 1-2 parts of protective wax, 3-5 parts of antioxidant, and 4-6 parts of accelerator; preferably, the silane coupling agent is selected from vinyl silane coupling agents and epoxy silanes. The coupling agent is selected from any one or more of the following: a coupling agent, a tetrathioether-based silane coupling agent, and an isocyanate-based propyl methoxysilane coupling agent; and / or, the silica dispersant is selected from any one or more of the following: ester-based silica dispersants, zinc soap-based silica dispersants, and fluorine-containing silica dispersants; and / or, the antioxidant is selected from antioxidant 4020 and / or antioxidant RD; and / or, the accelerator is selected from any one or more of the following: accelerator DPG, accelerator CZ, accelerator ZBEC, accelerator DM, and accelerator NS.

[0009] According to another aspect of the present invention, a method for preparing vulcanizate is provided, wherein the aforementioned vulcanizate composition is sequentially mixed, discharged, and vulcanized to obtain vulcanizate.

[0010] Further, the preparation method includes: Step S1, styrene-butadiene rubber, butadiene rubber, first part silica, silica dispersant, carbon black, first part silane coupling agent, silica graft-modified liquid butadiene rubber, first part plasticizing oil, first part anti-slip resin, first part accelerator, zinc oxide, stearic acid, antioxidant and protective wax are sequentially subjected to first mixing and first debinding to obtain a first compound; Step S2, the first compound, second part silica, second part silane coupling agent, second part plasticizing oil and second part anti-slip resin are sequentially subjected to second mixing and second debinding to obtain a second compound; Step S3, the second compound, sulfur and second accelerator are sequentially subjected to third mixing, third debinding and vulcanization to obtain a vulcanized rubber.

[0011] Furthermore, the preparation method of silica-grafted modified liquid cis-butadiene rubber includes: step S11, hydroxylating the end of the liquid cis-butadiene rubber to obtain hydroxyl-modified liquid cis-butadiene rubber; step S12, reacting the hydroxyl-modified liquid cis-butadiene rubber with a silane compound to obtain alkoxy-modified liquid cis-butadiene rubber; and step S13, reacting the alkoxy-modified liquid cis-butadiene rubber, silica, and water to obtain silica-grafted modified liquid cis-butadiene rubber.

[0012] Further, in step S11, hydrogen peroxide is used to hydroxylate the ends of the liquid cis-butadiene rubber; the hydroxylation treatment temperature is 50~70℃, and the hydroxylation treatment time is 2.5~4h; and / or, the temperature of the first reaction is 50~80℃; and / or, the time of the first reaction is 1.5~4h; and / or, the silane compound is a monofunctional silane compound; preferably, the monofunctional silane compound is selected from any one or more of monofunctional vinyl silane compounds, monofunctional epoxy silane compounds, and monofunctional isocyanate-propyl methoxy silane compounds; and / or, the temperature of the second reaction is 40~80℃; and / or, the time of the second reaction is 2.5~5.5h.

[0013] Further, the first mixing time is 250~350s; and / or, the first mixing temperature is 70~145℃; and / or, the first discharge temperature is 150~160℃; and / or, the second mixing time is 200~300s; and / or, the second mixing temperature is 70~145℃; and / or, the second discharge temperature is 145~155℃; and / or, the third mixing time is 80~120s; and / or, the third mixing temperature is 50~60℃; and / or, the third discharge temperature is 100~110℃; and / or, the first portion of silica and the second portion... The mass ratio of some silica is (80~100):(30~50); and / or, the mass ratio of the first silane coupling agent to the second silane coupling agent is (7~7.4):(3~3.4); and / or, the mass ratio of the first plasticizer to the second plasticizer is (18~20):(14~16); and / or, the mass ratio of the first anti-slip resin to the second anti-slip resin is (28~32):(8~12); and / or, the mass ratio of the first accelerator to the second accelerator is (1.7~2.3):(2~2.6).

[0014] According to another aspect of the present invention, a vulcanizate is provided, which is prepared by the aforementioned preparation method.

[0015] According to another aspect of the invention, a tire is provided that contains the aforementioned vulcanized rubber.

[0016] Applying the technical solution of this application, the addition of silica-grafted modified liquid butadiene rubber helps to enhance the dispersibility of silica in the rubber matrix. Liquid butadiene rubber, with its plasticizing properties, helps reduce the use of traditional plasticizers, thus avoiding oil film formation and improving tire grip performance under wet and icy conditions. Furthermore, the introduction of silica-grafted modified liquid butadiene rubber can increase the content of rubber segments and improve the hydrophilicity of the tread, further optimizing the tire's anti-slip performance. The good elasticity and anti-slip ability of styrene-butadiene rubber and butadiene rubber at low temperatures are enhanced by the addition of silica, which helps improve tire wear resistance and tear resistance. The addition of plasticizers helps improve tire softness and plasticity, the addition of anti-slip resin helps regulate the viscoelasticity of the rubber compound and improve the wet grip performance of the vulcanized rubber, and the addition of silica dispersant helps optimize the dispersion of silica in the rubber matrix, reducing agglomeration and thus improving the overall uniformity and mechanical properties of the formulation. Zinc oxide and stearic acid act as vulcanization activators, while sulfur acts as a vulcanization crosslinking agent. Together, they enable the vulcanizate composition to form a stable network structure during vulcanization, ensuring the mechanical strength and processing performance of the vulcanizate composition. Controlling the weight proportions of each component in the vulcanizate composition within the aforementioned range helps to enhance the synergistic effect between the components, thereby further improving the wet friction coefficient and ice friction coefficient of the vulcanizate. Attached Figure Description

[0017] The accompanying drawings, which form part of this application, are used to provide a further understanding of the invention. The illustrative embodiments of the invention and their descriptions are used to explain the invention and do not constitute an undue limitation of the invention. In the drawings:

[0018] Figure 1 The infrared spectrum of the silica-grafted modified liquid cis-butadiene rubber and related reactive components in Example 1 of this application is shown. Detailed Implementation

[0019] It should be noted that, unless otherwise specified, the embodiments and features described in this application can be combined with each other. The present invention will now be described in detail with reference to the embodiments.

[0020] As analyzed in the background section of this application, the existing technology has the problem of low wet friction coefficient and ice friction coefficient of vulcanizates. In order to solve this problem, this application provides a vulcanizate composition, vulcanizate, preparation method thereof, and tire.

[0021] In a typical embodiment of this application, a vulcanizate composition is provided, comprising, by weight: 60-100 parts of styrene-butadiene rubber, 20-40 parts of butadiene rubber, 120-140 parts of silica, 3-12 parts of silica-grafted modified liquid butadiene rubber, 32-38 parts of plasticizing oil, 35-45 parts of anti-slip resin, 3-5 parts of silica dispersant, 3-4 parts of zinc oxide, 1-3 parts of stearic acid, and 1-2 parts of sulfur.

[0022] In this application, the addition of silica-grafted modified liquid butadiene rubber (PPB) helps to enhance the dispersibility of silica in the rubber matrix. PPB, with its plasticizing properties, helps reduce the use of traditional plasticizers, thus preventing oil film formation and improving tire grip performance in wet and icy conditions. Furthermore, the introduction of silica-grafted modified PPB increases the rubber segment content and improves the hydrophilicity of the tread, further optimizing the tire's anti-skid performance. The good elasticity and anti-skid ability of styrene-butadiene rubber and butadiene rubber at low temperatures are enhanced by the addition of silica, which helps improve tire wear resistance and tear resistance. The addition of plasticizers helps improve tire softness and plasticity, the addition of anti-skid resin helps regulate the viscoelasticity of the compound and improve the wet grip performance of the vulcanized rubber, and the addition of silica dispersant helps optimize the dispersion of silica in the rubber matrix, reducing agglomeration and thus improving the overall uniformity and mechanical properties of the formulation. Zinc oxide and stearic acid act as vulcanization activators, while sulfur acts as a vulcanization crosslinking agent. Together, they enable the vulcanizate composition to form a stable network structure during vulcanization, ensuring the mechanical strength and processing performance of the vulcanizate composition. Controlling the weight proportions of each component in the vulcanizate composition within the aforementioned range helps to enhance the synergistic effect between the components, thereby further improving the wet friction coefficient and ice friction coefficient of the vulcanizate.

[0023] In some embodiments of this application, the mass ratio of the above-mentioned silica-grafted modified liquid butadiene rubber to plasticizer oil is (6~12):(32~36).

[0024] Controlling the mass ratio of silica-grafted modified liquid butadiene rubber to plasticizer oil within the above range helps to effectively improve the hydrophilicity and anti-skid properties of tires without sacrificing rubber hardness and tear resistance, and reduces the risk of tire slippage when driving on wet and icy surfaces.

[0025] In order to further reduce the wet friction coefficient and ice friction coefficient of the vulcanizate, in some embodiments of this application, the mass ratio of the above-mentioned silica-grafted modified liquid butadiene rubber to the plasticizer is 1:(2.6~6).

[0026] In some embodiments of this application, the mass ratio of silica to liquid butadiene rubber in the silica-grafted modified liquid butadiene rubber is 1:(3~10); and / or, the number average molecular weight of the liquid butadiene rubber in the silica-grafted modified liquid butadiene rubber is 5000~18000 g / mol; and / or, the silica in the silica-grafted modified liquid butadiene rubber exists in the form of silica aggregates, and the average particle size of the silica aggregates is 260~350 nm.

[0027] The plasticizing effect of liquid butadiene rubber helps maintain tire softness and improves its adaptability under low-temperature conditions. Silica, through its high surface energy, increases the coefficient of friction between the tire and the road surface, thereby achieving better handling and safety. Controlling the mass ratio of silica to liquid butadiene rubber in silica-grafted modified liquid butadiene rubber within the aforementioned range helps the liquid butadiene rubber form a graft layer on the silica surface, effectively improving the dispersion uniformity of silica in the rubber matrix, thus further reducing the amount of plasticizer oil used and further improving the wet and ice friction coefficients of the tire. Controlling the number-average molecular weight of liquid butadiene rubber within the aforementioned range helps control tire hardness and elasticity, improving low-temperature adaptability, thereby further reducing the wet and ice friction coefficients of the tire. Controlling the average particle size of silica aggregates in silica-grafted modified liquid butadiene rubber within the aforementioned range helps improve the structural stability of silica-grafted modified liquid butadiene rubber, enhancing tire wear resistance and tear resistance, and optimizing tire rolling resistance and wet performance.

[0028] In some embodiments of this application, the plasticizing oil is selected from any one or more of environmentally friendly aromatic oils, naphthenic oils, and aromatic oils; and / or, the anti-slip resin is selected from any one or more of resin SA85, resin DCPD, and resin C9; and / or, by weight, the vulcanizate composition further includes: 8-12 parts of silane coupling agent, 4-6 parts of carbon black, 1-2 parts of protective wax, 3-5 parts of antioxidant, and 4-6 parts of accelerator; preferably, the silane coupling agent is selected from vinyl silane coupling agent, epoxy silane coupling agent, and tetrathioether silane. The coupling agent (such as silane coupling agent Si-69) and isocyanate-based propyl methoxysilane coupling agent are selected from any one or more of the following: and / or, the silica dispersant is selected from any one or more of the following: ester silica dispersant, zinc soap silica dispersant, and fluorine-containing silica dispersant (such as silica dispersant TYC0544); and / or, the antioxidant is selected from antioxidant 4020 and / or antioxidant RD; and / or, the accelerator is selected from any one or more of the following: accelerator DPG, accelerator CZ, accelerator ZBEC, accelerator DM, and accelerator NS.

[0029] Controlling the types of plasticizers and anti-skid resins within the aforementioned range helps optimize tire anti-skid performance, ice performance, and anti-aging properties, while maintaining low rolling resistance. The addition of silane coupling agents helps enhance the chemical bond between silica and the rubber matrix, thereby improving tire wear resistance and tear resistance. The addition of antioxidants helps improve tire aging resistance. The addition of accelerators helps accelerate vulcanization. The addition of carbon black helps strengthen tire wear resistance. The addition of protective wax helps form a protective layer on the tire surface, preventing UV radiation and moisture erosion.

[0030] In order to extend the service life of tires and improve the efficiency of tire production, in some embodiments of this application, the antioxidant is a combination of antioxidant 4020 and antioxidant RD, and the mass ratio of antioxidant 4020 to antioxidant RD is (2.5~3.5):(0.5~1.5); and / or, the accelerator is a combination of accelerator DPG, accelerator CZ and accelerator ZBEC, and the mass ratio of accelerator DPG, accelerator CZ and accelerator ZBEC is (1.5~2.5):(1.5~2.5):(0.1~0.5).

[0031] In another typical embodiment of this application, a method for preparing vulcanizate is provided, wherein the aforementioned vulcanizate composition is sequentially mixed, discharged, and vulcanized to obtain vulcanizate.

[0032] The method for preparing the vulcanizate of this application is simple, low-cost, and suitable for large-scale production.

[0033] In some embodiments of this application, the above preparation method includes: step S1, sequentially mixing and debinding styrene-butadiene rubber, butadiene rubber, a first portion of silica, silica dispersant, carbon black, a first portion of silane coupling agent, silica-grafted modified liquid butadiene rubber, a first portion of plasticizing oil, a first portion of anti-slip resin, a first portion of accelerator, zinc oxide, stearic acid, antioxidant, and protective wax to obtain a first compound; step S2, sequentially mixing and debinding the first compound, a second portion of silica, a second portion of silane coupling agent, a second portion of plasticizing oil, and a second portion of anti-slip resin to obtain a second compound; step S3, sequentially mixing, debinding, and vulcanizing the second compound, sulfur, and a second accelerator to obtain a vulcanized rubber.

[0034] The mixing in step S1 helps improve the dispersibility of silica and carbon black in the rubber matrix; the addition of the second part silica and the second part silane coupling agent in step S2 helps to further deepen the dispersion of fillers; the addition of the second part plasticizing oil and the second part anti-skid resin helps to reduce the energy loss of the tire during rolling, thereby reducing rolling resistance and improving fuel efficiency and driving experience; in step S3, the addition of sulfur and the second accelerator for vulcanization completes the cross-linking reaction between rubber molecules, and solidifies the mechanical properties and chemical stability of the tire.

[0035] In some embodiments of this application, the speed of the internal mixer in the first mixing process is 60-90 rpm and the filling coefficient is 0.7-0.8; and / or, the speed of the internal mixer in the second mixing process is 60-80 rpm and the filling coefficient is 0.7-0.8; and / or, the speed of the internal mixer in the third mixing process is 60-80 rpm.

[0036] In some embodiments of this application, the preparation method of the above-mentioned silica-grafted modified liquid cis-butadiene rubber includes: step S11, hydroxylating the end of the liquid cis-butadiene rubber to obtain hydroxyl-modified liquid cis-butadiene rubber; step S12, reacting the hydroxyl-modified liquid cis-butadiene rubber with a silane compound to obtain alkoxy-modified liquid cis-butadiene rubber; and step S13, reacting the alkoxy-modified liquid cis-butadiene rubber, silica, and water to obtain silica-grafted modified liquid cis-butadiene rubber.

[0037] In step S11, the ends of the liquid cis-butadiene rubber are hydroxylated to introduce hydroxyl functional groups, which is beneficial for the subsequent introduction of alkoxy groups. In step S12, the hydroxyl groups at both ends of the hydroxy-modified liquid cis-butadiene rubber undergo a first reaction with a silane compound to introduce alkoxy groups at both ends of the liquid cis-butadiene rubber. In step S13, the alkoxy groups on the alkoxy-modified liquid cis-butadiene rubber first undergo hydrolysis to generate silanol groups, and then undergo a dehydration condensation reaction with the silanol groups on the surface of silica to obtain silica-grafted modified liquid cis-butadiene rubber.

[0038] In some embodiments of this application, the silane compound is a monofunctional silane compound; preferably, the monofunctional silane compound is selected from any one or more of monofunctional vinyl silane compounds, monofunctional epoxy silane compounds (such as KH560 silane compound), and monofunctional isocyanate-propyl methoxy silane compounds.

[0039] In some embodiments of this application, in step S11 above, hydrogen peroxide is used to hydroxylate the ends of the liquid cis-butadiene rubber; the hydroxylation temperature is 50~70°C, and the hydroxylation time is 2.5~4h; and / or, the temperature of the first reaction is 50~80°C; and / or, the time of the first reaction is 1.5~4h; and / or, the temperature of the second reaction is 40~80°C; and / or, the time of the second reaction is 2.5~5.5h.

[0040] In step S11, the hydroxyl radicals generated by hydrogen peroxide react with the active sites at the ends of the liquid cis-butadiene rubber to form stable hydroxyl functional groups. Controlling the temperature and time of the hydroxylation treatment within the aforementioned range helps promote the free radical reaction between the hydroxyl radicals and the active sites at the ends of the liquid cis-butadiene rubber, thereby improving the efficiency of the hydroxylation treatment. Controlling the temperature and time of the first reaction within the aforementioned range helps reduce the occurrence of side reactions. Controlling the temperature and time of the second reaction within the aforementioned range helps promote the formation of silica-grafted modified liquid cis-butadiene rubber.

[0041] In some embodiments of this application, hydrogen peroxide is used to hydroxylate the ends of liquid cis-butadiene rubber at a pH of 3 to 5.

[0042] By controlling the pH value within the above range, hydrogen peroxide can generate more hydroxyl radicals, which helps to accelerate the hydroxylation process.

[0043] To further improve the uniformity of the mixing of the components in the vulcanized rubber composition, thereby further improving the wet friction coefficient and ice friction coefficient of the tire, in some embodiments of this application, the first mixing time is 250~350s; and / or, the first mixing temperature is 70~145℃; and / or, the first discharge temperature is 150~160℃; and / or, the second mixing time is 200~300s; and / or, the second mixing temperature is 70~145℃; and / or, the second discharge temperature is 145~155℃; and / or, the third mixing time is 80~120s; and / or, the third mixing temperature is 50~60℃; and / or, the third discharge temperature is... The temperature of the adhesive is 100~110℃; and / or, the mass ratio of the first part of silica to the second part of silica is (80~100):(30~50); and / or, the mass ratio of the first part of silane coupling agent to the second part of silane coupling agent is (7~7.4):(3~3.4); and / or, the mass ratio of the first part of plasticizer oil to the second part of plasticizer oil is (18~20):(14~16); and / or, the mass ratio of the first part of anti-slip resin to the second part of anti-slip resin is (28~32):(8~12); and / or, the mass ratio of the first part of accelerator to the second part of accelerator is (1.7~2.3):(2~2.6).

[0044] In another typical embodiment of this application, a vulcanizate is provided, which is prepared by the aforementioned preparation method.

[0045] Since the above-mentioned vulcanized rubber is prepared using the preparation method of this application, the vulcanized rubber has a high wet friction coefficient and ice friction coefficient.

[0046] In another typical embodiment of this application, a tire is provided that contains the aforementioned vulcanized rubber.

[0047] Because the tire contains the vulcanized rubber of this application, the tire has excellent wet skid resistance and ice skid resistance.

[0048] The beneficial effects of this application will be further illustrated below with reference to the embodiments.

[0049] Example 1

[0050] Preparation of silica-grafted modified liquid cis-butadiene rubber: Hydrogen peroxide was used to hydroxylate the chain ends of liquid cis-butadiene rubber (number average molecular weight of 8500 g / mol) at pH 3.5 for 3 h at 65 °C to obtain hydroxylated liquid cis-butadiene rubber. A first reaction was carried out with a monofunctional epoxy silane compound (KH560 silane) and the hydroxylated modified liquid cis-butadiene rubber at 70 °C for 2.5 h to obtain alkoxy-modified liquid cis-butadiene rubber. A second reaction was carried out with the alkoxy-modified liquid cis-butadiene rubber and silica (average particle size of silica aggregates of 310 nm) in water at 50 °C for 4 h to obtain silica-grafted modified liquid cis-butadiene rubber, wherein the mass ratio of silica to liquid cis-butadiene rubber was 1:3.5.

[0051] By weight, the vulcanizate composition comprises: 60 parts of styrene-butadiene rubber SL553, 20 parts of styrene-butadiene rubber HPR850, 20 parts of butadiene rubber BR9000, and 130 parts of silica (specific surface area 165 m²). 2 / g), 10.4 parts of silane coupling agent Si-69, 3 parts of silica graft-modified liquid butadiene rubber, 5 parts of carbon black N339, 4 parts of silica dispersant TYC0544, 38 parts of plasticizing oil (environmentally friendly aromatic oil), 40 parts of anti-slip resin (resin SA85), 3.5 parts of zinc oxide, 2 parts of stearic acid, 1 part of antioxidant RD, 3 parts of antioxidant 4020, 1.5 parts of protective wax, 1.4 parts of sulfur, 2 parts of accelerator CZ, 2 parts of accelerator DPG, and 0.3 parts of accelerator ZBEC.

[0052] The vulcanizate is prepared using the above-mentioned vulcanizate composition, and the preparation steps include:

[0053] Set the internal mixer temperature to 80℃ and the speed to 70rpm, with the filling factor controlled at 0.75. Add 60 parts of styrene-butadiene rubber SL553, 20 parts of styrene-butadiene rubber HPR850, and 20 parts of butadiene rubber BR9000 to the internal mixer and mix for 40s. Then add 90 parts of silica, 4 parts of silica dispersant, 5 parts of carbon black, 7.2 parts of silane coupling agent, 3 parts of silica graft-modified liquid butadiene rubber, 23 parts of plasticizer oil, 30 parts of anti-slip resin, and accelerator DPG. Mix for 90s until the temperature rises to 140℃. Then lift the top plug and press it down. Mix at 145℃ for 120s. Then lift the top plug and add 3.5 parts of zinc oxide, 2.0 parts of stearic acid, 1 part of antioxidant RD, 3 parts of antioxidant 4020, and 1.5 parts of protective wax. Mix for 50s and control the temperature at 155℃ for the first discharge to obtain the first compound.

[0054] Set the internal mixer temperature to 75℃ and the speed to 70rpm, and control the filling coefficient at 0.78. Add the first compound to the internal mixer and mix for 40s. Then lift the top plug. Add 40 parts of silica, 3.2 parts of silane coupling agent, 15 parts of plasticizer oil, and 10 parts of anti-slip resin to the internal mixer and mix for 90s until the temperature rises to 140℃. Then lift the top plug and press the top plug back on. Mix at 145℃ for 120s. Then lift the top plug back on and press the top plug back on. Perform the second discharge at 150℃ to obtain the second compound.

[0055] The second compound was added to the internal mixer, the temperature was controlled at 55℃, the speed was 60rpm, and after mixing for 30s, the top plug was added. Then sulfur, accelerator CZ and accelerator ZBEC were added, and after mixing for 40s, the top plug was added to clean. After mixing for 30s, the mixture was discharged at 105℃ to obtain the third compound.

[0056] Add the third adhesive to the vulcanizing mold, control the vulcanizing machine temperature at 165℃, and vulcanize for the normal vulcanizing time according to the process, to obtain vulcanized adhesive.

[0057] Example 2

[0058] The difference from Example 1 is that the weight of the silica-grafted modified liquid butadiene rubber in the vulcanizate composition is 6 parts, and the weight of the environmentally friendly aromatic oil is 36 parts, resulting in the vulcanizate.

[0059] Example 3

[0060] The difference from Example 1 is that the weight of the silica-grafted modified liquid butadiene rubber in the vulcanizate composition is 9 parts, and the weight of the environmentally friendly aromatic oil is 34 parts, resulting in the vulcanizate.

[0061] Example 4

[0062] The difference from Example 1 is that the weight of the silica-grafted modified liquid butadiene rubber in the vulcanizate composition is 12 parts, and the weight of the environmentally friendly aromatic oil is 32 parts, resulting in the vulcanizate.

[0063] Example 5

[0064] The difference from Example 1 is that in the preparation of silica-grafted modified liquid cis-butadiene rubber, the mass ratio of silica to liquid cis-butadiene rubber is 1:3, and the final product is vulcanized rubber.

[0065] Example 6

[0066] The difference from Example 1 is that in the preparation of silica-grafted modified liquid cis-butadiene rubber, the mass ratio of silica to liquid cis-butadiene rubber is 1:10, and the final product is vulcanized rubber.

[0067] Example 7

[0068] The difference from Example 1 is that in the preparation of silica-grafted modified liquid cis-butadiene rubber, the mass ratio of silica to liquid cis-butadiene rubber is 1:2, and the final product is vulcanized rubber.

[0069] Example 8

[0070] The difference from Example 1 is that the number average molecular weight of the liquid cis-butadiene rubber in the preparation of silica-grafted modified liquid cis-butadiene rubber is 5000 g / mol, and the final product is vulcanized rubber.

[0071] Example 9

[0072] The difference from Example 1 is that the number average molecular weight of the liquid cis-butadiene rubber in the preparation of silica-grafted modified liquid cis-butadiene rubber is 18000 g / mol, and the final product is vulcanized rubber.

[0073] Example 10

[0074] The difference from Example 1 is that the number average molecular weight of the liquid cis-butadiene rubber in the preparation of silica-grafted modified liquid cis-butadiene rubber is 20,000 g / mol, and the final product is vulcanized rubber.

[0075] Example 11

[0076] The difference from Example 1 is that the average particle size of the silica aggregates in the preparation of silica-grafted modified liquid butadiene rubber is 260 nm, and the final product is vulcanized rubber.

[0077] Example 12

[0078] The difference from Example 1 is that the average particle size of the silica aggregates in the preparation of silica-grafted modified liquid butadiene rubber is 350 nm, and the final product is vulcanized rubber.

[0079] Example 13

[0080] The difference from Example 1 is that the average particle size of the silica aggregates in the preparation of silica-grafted modified liquid butadiene rubber is 400 nm, and the final product is vulcanized rubber.

[0081] Example 14

[0082] The difference from Example 1 is that, by weight, the vulcanizate composition comprises: 60 parts of styrene-butadiene rubber SL553, 20 parts of styrene-butadiene rubber HPR850, 20 parts of butadiene rubber BR9000, and 130 parts of silica (with a specific surface area of ​​165 m²). 2 / g), 3 parts of silica-grafted modified liquid butadiene rubber, 38 parts of environmentally friendly aromatic oil, 40 parts of resin SA85, 4 parts of silica dispersant TYC0544, 3.5 parts of zinc oxide, 2 parts of stearic acid, and 1.4 parts of sulfur.

[0083] The vulcanizate is prepared using the above-mentioned vulcanizate composition, and the preparation steps include:

[0084] Set the internal mixer temperature to 80℃ and the speed to 70rpm, with the filling factor controlled at 0.75. Add 60 parts of styrene-butadiene rubber SL553, 20 parts of styrene-butadiene rubber HPR850, and 20 parts of butadiene rubber BR9000 to the internal mixer and mix for 40s. Then add 90 parts of silica, 4 parts of silica dispersant, 5 parts of carbon black, 3 parts of silica grafted modified liquid butadiene rubber, 23 parts of plasticizer oil, and 30 parts of anti-slip resin and mix for 90s until the temperature rises to 140℃. Then lift the top plug and press the top plug on. Mix at 145℃ for 120s. Then lift the top plug and add 3.5 parts of zinc oxide and 2.0 parts of stearic acid. Mix for 50s and control the temperature at 155℃ for the first discharge to obtain the first compound.

[0085] Set the internal mixer temperature to 75℃ and the speed to 70rpm, and control the filling coefficient at 0.78. Add the first compound to the internal mixer and mix for 40s. Then lift the top plug. Add 40 parts of silica, 15 parts of plasticizer oil, and 10 parts of anti-slip resin to the internal mixer and mix for 90s until the temperature rises to 140℃. Then lift the top plug and press the top plug back on. Mix at 145℃ for 120s. Then lift the top plug back on and press the top plug back on. Perform the second discharge at 150℃ to obtain the second compound.

[0086] The second compound was added to the internal mixer, the temperature was controlled at 55℃, the speed was 60rpm, and after mixing for 30s, the top plug was added. Then sulfur was added, and after mixing for 40s, the top plug was added to clean it. After mixing for 30s, the internal mixer was controlled at 105℃ and the compound was discharged to obtain the third compound.

[0087] Add the third adhesive to the vulcanizing mold, control the vulcanizing machine temperature at 165℃, and vulcanize for the normal vulcanizing time according to the process, to obtain vulcanized adhesive.

[0088] Comparative Example 1

[0089] The difference from Example 1 is that the weight of the silica-grafted modified liquid butadiene rubber in the vulcanizate composition is 0 parts, and the weight of the environmentally friendly aromatic oil is 40 parts, resulting in the vulcanizate.

[0090] Comparative Example 2

[0091] The difference from Example 1 is that the grafting of silica and liquid butadiene rubber is omitted, and the silica is directly added to the vulcanizate composition to obtain the vulcanizate.

[0092] Performance testing

[0093] Processing properties: The extrusion rheological properties of the rubber composition are expressed as poor, medium, and good, respectively, indicating significant edge breakage, slight edge breakage, and no edge breakage during extrusion. The tests are conducted in accordance with the rheological testing standard HG / T 4300-2012.

[0094] Tensile stress-strain properties: expressed as tensile strength and elongation at break, and tested in accordance with the tensile stress-strain property test standard GB / T 528-2009;

[0095] Filler dispersion: Tested according to GB / T 6030-2006;

[0096] Shore hardness: Tested according to GB / T 531.1-2008;

[0097] Resilience: Tested according to GB / T 1681-2009;

[0098] DIN abrasion index: Tested according to GB / T 9867-2008;

[0099] Goodrich compression heat generation - bottom temperature rise: expressed as compression heat generation - bottom temperature rise, tested in accordance with GB / T 1687.3-2016;

[0100] TA shear strain performance: expressed by hysteresis loss performance index (tanδ) max @60℃ indicates that the test was conducted using an ARES-G2 rotational rheometer from Waters Technologies Inc., USA, with the test mode set to circumferential shear mode, strain range 0.1~60%, test temperature 60℃, and test frequency 10Hz.

[0101] LAT ice friction coefficient: The friction coefficient was tested using the LAT-100 abrasion and wet skid resistance testing machine. Ice friction coefficient test: Test temperatures were -15℃, -10℃, and -5℃, the load was 75N, and the test speed was 0.6Km / h. The test was conducted on an icy road surface, and the final data was the average of the three temperature points.

[0102] LAT wet friction coefficient: The friction coefficient was tested using the LAT-100 abrasion and wet skid resistance testing machine. Wet friction coefficient test: Test temperature 15℃, load 75N, test speed 1.5Km / h, slip angle 15°, and the test was conducted on a wet road surface.

[0103] The vulcanizates prepared in the examples and comparative examples were subjected to tests on processing properties, tensile strength, elongation at break, filler dispersion, Shore hardness, resilience, DIN abrasion index, Goodrich compression heat generation-bottom temperature rise, TA shear strain scan, LAT ice friction coefficient, and LAT wet friction coefficient. The test results for Comparative Example 1 and Examples 1-4 are shown in Table 1, the test results for Examples 5-9 are shown in Table 2, the test results for Examples 10-14 are shown in Table 3, and the test results for Comparative Example 2 are shown in Table 4.

[0104] Table 1

[0105]

[0106] Table 2

[0107]

[0108] Table 3

[0109]

[0110] Table 4

[0111]

[0112] Figure 1 The infrared spectra of silica-grafted modified liquid cis-butadiene rubber and related reactive components in Example 1 of this application are shown. In the infrared spectrum of liquid cis-butadiene rubber (LBR), 725 cm⁻¹ -1 911cm -1 and 963cm -1 These correspond to the characteristic peaks of cis-butadiene, vinyl and trans-butadiene, respectively, while 1436 cm⁻¹ -1 The characteristic vibrational peak of CH2 appears at 3300-3600 cm⁻¹ in the infrared spectrum of hydroxyl-modified liquid cis-butadiene rubber (GLBR). -1 The characteristic peaks representing the terminal hydroxyl groups indicate the successful modification of LBR, with hydroxyl groups introduced at both ends of the LBR; in the infrared spectrum of the silane compound (KH560), the peak at 910 cm⁻¹... -1The peak at 1190 cm⁻¹ is a characteristic vibrational peak for epoxy groups. -1 The absorption peak at 3300-3600 cm⁻¹ corresponds to the CO-Si bond vibration. In the infrared spectrum of alkoxy-modified liquid cis-butadiene rubber (SGLBR), this peak is located between 3300 and 3600 cm⁻¹. -1 The characteristic peak for terminal hydroxyl groups disappeared, while at 1190 cm⁻¹... -1 The presence of a characteristic peak for CO-Si at 1066 cm⁻¹ indicates that the terminal hydroxyl groups of GLBR and the epoxy groups of KH560 reacted, introducing methoxysilane structures at both ends of LBR; in the infrared spectrum of SiO₂, the peak at 1066 cm⁻¹ is significant. -1 The peak at 1190 cm⁻¹ represents the stretching vibration of the Si-O-Si bond. However, the infrared spectrum of the silica-grafted modified liquid cis-butadiene rubber (SGLBR), produced after the hydrolysis and condensation reaction of SiO₂ and GLBR, shows a peak at 1190 cm⁻¹. -1 The characteristic peak of CO-Si disappears at 1066 cm⁻¹, indicating that the methoxysilane structure of CO-Si undergoes hydrolysis to form Si-OH. -1 The appearance of the Si-O-Si vibrational absorption peak indicates that the silanol has undergone a condensation reaction to form Si-O-Si, which shows that the silica structure has been successfully introduced into both ends of the liquid cis-butadiene, and the silica grafting has been successful.

[0113] As can be seen from the above description, the embodiments of the present invention achieve the following technical effects:

[0114] In this application, the addition of silica-grafted modified liquid butadiene rubber (PPB) helps to enhance the dispersibility of silica in the rubber matrix. PPB, with its plasticizing properties, helps reduce the use of traditional plasticizers, thus preventing oil film formation and improving tire grip performance in wet and icy conditions. Furthermore, the introduction of silica-grafted modified PPB increases the rubber segment content and improves the hydrophilicity of the tread, further optimizing the tire's anti-skid performance. The good elasticity and anti-skid ability of styrene-butadiene rubber and butadiene rubber at low temperatures are enhanced by the addition of silica, which helps improve tire wear resistance and tear resistance. The addition of plasticizers helps improve tire softness and plasticity, the addition of anti-skid resin helps regulate the viscoelasticity of the compound and improve the wet grip performance of the vulcanized rubber, and the addition of silica dispersant helps optimize the dispersion of silica in the rubber matrix, reducing agglomeration and thus improving the overall uniformity and mechanical properties of the formulation. Zinc oxide and stearic acid act as vulcanization activators, while sulfur acts as a vulcanization crosslinking agent. Together, they enable the vulcanizate composition to form a stable network structure during vulcanization, ensuring the mechanical strength and processing performance of the vulcanizate composition. Controlling the weight proportions of each component in the vulcanizate composition within the aforementioned range helps to enhance the synergistic effect between the components, thereby further improving the wet friction coefficient and ice friction coefficient of the vulcanizate.

[0115] The above are merely embodiments of the present invention and are not intended to limit the invention. Those skilled in the art will recognize that the present invention can have various modifications and variations. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A vulcanizate composition, characterized in that, The vulcanizate composition comprises, by weight parts: 60-100 parts of styrene-butadiene rubber; 20-40 parts of butadiene rubber; 120-140 parts of silica; 3-12 parts of silica grafted modified liquid cis-butadiene rubber; 32-38 parts plasticizer oil; 35-45 parts of anti-slip resin; 3-5 parts of silica dispersant; 3-4 parts zinc oxide; 1 to 3 parts stearic acid; 1 to 2 parts sulfur.

2. The vulcanized rubber composition according to claim 1, characterized in that, The mass ratio of the silica-grafted modified liquid butadiene rubber to the plasticizer oil is (6~12):(32~36).

3. The vulcanizate composition according to claim 1 or 2, characterized in that, The mass ratio of silica to liquid butadiene rubber in the silica-grafted modified liquid butadiene rubber is 1:(3~10); and / or, the number average molecular weight of the liquid butadiene rubber in the silica-grafted modified liquid butadiene rubber is 5000~18000 g / mol; and / or, the silica in the silica-grafted modified liquid butadiene rubber exists in the form of silica aggregates, and the average particle size of the silica aggregates is 260~350 nm.

4. The vulcanizate composition according to any one of claims 1 to 3, characterized in that, The plasticizing oil is selected from any one or more of environmentally friendly aromatic oils, naphthenic oils, and aromatic oils; and / or, the anti-slip resin is selected from any one or more of resin SA85, resin DCPD, and resin C9; And / or, by weight, the vulcanizate composition further comprises: 8-12 parts of silane coupling agent; 4 to 6 parts carbon black; 1-2 parts of protective wax; 3-5 parts of anti-aging agent; 4-6 parts of accelerator; Preferably, the silane coupling agent is selected from any one or more of vinyl silane coupling agents, epoxy silane coupling agents, tetrathioether silane coupling agents, and isocyanate-propyl methoxy silane coupling agents; and / or, the silica dispersant is selected from any one or more of ester silica dispersants, zinc soap silica dispersants, and fluorine-containing silica dispersants; and / or, the antioxidant is selected from antioxidant 4020 and / or antioxidant RD; and / or, the accelerator is selected from any one or more of accelerator DPG, accelerator CZ, accelerator ZBEC, accelerator DM, and accelerator NS.

5. A method for preparing vulcanizate, characterized in that, The vulcanized rubber composition according to any one of claims 1 to 4 is sequentially mixed, discharged, and vulcanized to obtain the vulcanized rubber.

6. The preparation method according to claim 5, characterized in that, The preparation method includes: Step S1: Styrene-butadiene rubber, butadiene rubber, silica (part 1), silica dispersant, carbon black, silane coupling agent (part 1), silica graft-modified liquid butadiene rubber, plasticizer (part 1), anti-slip resin (part 1), accelerator (part 1), zinc oxide, stearic acid, antioxidant, and protective wax are sequentially mixed and discharged to obtain the first compound. Step S2: The first compound, the second part of silica, the second part of silane coupling agent, the second part of plasticizer oil, and the second part of anti-slip resin are sequentially mixed and then discharged to obtain the second compound. Step S3: The second compound rubber, sulfur, and the second accelerator are sequentially subjected to a third mixing, a third discharge, and the vulcanization to obtain the vulcanized rubber.

7. The preparation method according to claim 6, characterized in that, The preparation method of the silica-grafted modified liquid cis-butadiene rubber includes: Step S11: Hydroxylate the ends of the liquid cis-butadiene rubber to obtain hydroxylated liquid cis-butadiene rubber. Step S12: The hydroxyl-modified liquid cis-butadiene rubber is reacted with a silane compound to obtain alkoxy-modified liquid cis-butadiene rubber. Step S13: The alkoxy-modified liquid cis-butadiene rubber, silica, and water are subjected to a second reaction to obtain the silica-grafted modified liquid cis-butadiene rubber.

8. The preparation method according to claim 7, characterized in that, In step S11, hydrogen peroxide is used to hydroxylate the ends of the liquid cis-butadiene rubber; the temperature of the hydroxylation treatment is 50~70℃, and the time of the hydroxylation treatment is 2.5~4h. And / or, the temperature of the first reaction is 50~80℃; and / or, the time of the first reaction is 1.5~4h; And / or, the silane compound is a monofunctional silane compound; preferably, the monofunctional silane compound is selected from any one or more of monofunctional vinyl silane compounds, monofunctional epoxy silane compounds, and monofunctional isocyanate-propyl methoxy silane compounds; And / or, the temperature of the second reaction is 40~80℃; and / or, the time of the second reaction is 2.5~5.5h.

9. The preparation method according to any one of claims 6 to 8, characterized in that, The first mixing time is 250~350s; and / or, the temperature of the first mixing is 70~145℃; and / or, the temperature of the first discharge is 150~160℃. And / or, the second mixing time is 200~300s; and / or, the second mixing temperature is 70~145℃; and / or, the second dispensing temperature is 145~155℃; And / or, the third mixing time is 80~120s; and / or, the third mixing temperature is 50~60℃; and / or, the third dispensing temperature is 100~110℃; And / or, the mass ratio of the first portion of silica to the second portion of silica is (80~100):(30~50); and / or, the mass ratio of the first portion of silane coupling agent to the second portion of silane coupling agent is (7~7.4):(3~3.4); and / or, the mass ratio of the first portion of plasticizer oil to the second portion of plasticizer oil is (18~20):(14~16); and / or, the mass ratio of the first portion of anti-slip resin to the second portion of anti-slip resin is (28~32):(8~12); and / or, the mass ratio of the first portion of accelerator to the second portion of accelerator is (1.7~2.3):(2~2.6).

10. A vulcanizate, characterized in that, The vulcanizate is prepared by the preparation method according to any one of claims 5 to 9.

11. A tire, characterized in that, The tire contains the vulcanized rubber as described in claim 10.

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