Biological base oil anti-precipitation new energy tread rubber composition, preparation method thereof and tire

Abstract

The invention discloses a bio-based oil anti-precipitation new energy tread rubber composition, a preparation method thereof and a tire, and belongs to the technical field of new energy automobile tires. According to the technical scheme, the solvent extraction weight loss rate of the biological base oil anti-precipitation new energy tread rubber composition is less than or equal to 3.5%; the bio-based oil anti-precipitation new energy tread rubber composition comprises solution polymerized styrene-butadiene rubber, white carbon black, bio-based oil and polyethylene glycol. The bio-based oil is soybean oil or a derivative thereof with an iodine value less than or equal to 40; the molecular weight of the polyethylene glycol is 3000 to 6000. The bio-based oil is applied to the aspect of the new energy automobile tire tread rubber composition, solves the problems that the compatibility of bio-based oil and solution polymerized styrene-butadiene rubber is poor and the bio-based oil is separated out when the bio-based oil is used in a solution polymerized styrene-butadiene rubber system in the prior art, and further influences the rubber processing performance and the rubber performance, and can prevent an oil phase from migrating and separating out.

Description

Technical Field

[0001] The present invention belongs to the technical field of new energy vehicle tires, and in particular relates to a bio-based oil precipitation-proof new energy tread rubber composition, a preparation method thereof, and a tire. Background Art

[0002] As new energy electric vehicles gain increasing market share, low-temperature endurance is a growing concern. Conventional tires experience a 50% loss in rolling resistance at low temperatures, significantly increasing energy consumption. Research has shown that this loss is closely related to the glass transition temperature of the tread compound. Bio-based rubber extenders, compared to petroleum-based extenders, have significantly lower glass transition temperatures, significantly improving low-temperature tire performance.

[0003] Rubber filler oil is an essential raw material in the tire production process, which can improve the processing performance and physical properties of the rubber compound. Currently, the most commonly used are petroleum-based plasticizers such as environmentally friendly aromatic oils and naphthenic oils. However, with the widespread attention paid to ecological and environmental issues, facing the problem of non-renewable petroleum resources, the use of bio-based oils such as soybean oil to gradually replace petroleum-based plasticizers is of great significance. The raw rubber system of existing new energy tire tread formulation technology is mainly solution-polymerized styrene-butadiene rubber, and plasticizers are generally environmentally friendly aromatic oils or naphthenic oils. Using bio-based oils to replace environmentally friendly aromatic oils or naphthenic oils can solve the above-mentioned ecological and environmental problems and the problem of non-renewable petroleum resources.

[0004] However, the use of bio-based oil in new energy tire tread formulations has the following problems: the weakly polar bio-based oil has poor compatibility with the more polar modified solution-polymerized styrene-butadiene rubber and is prone to precipitation during the storage of the rubber components, thereby affecting the processing performance and rubber properties. Summary of the Invention

[0005] In view of the shortcomings of the existing technology, the technical problem to be solved by the present invention is that the existing solution-polymerized styrene-butadiene rubber system uses bio-based oil, which has the problem of poor compatibility between the bio-based oil and the solution-polymerized styrene-butadiene rubber, and the precipitation of the bio-based oil, which in turn affects the processing performance and performance of the rubber. A bio-based oil anti-precipitation new energy tread rubber composition, a preparation method thereof, and a tire are proposed, which can prevent the migration and precipitation of the oil phase.

[0006] In order to solve the technical problem, the technical solution adopted by the present invention is:

[0007] On one hand, the present invention provides a bio-based oil precipitation-resistant new energy tread rubber composition, wherein the solvent extraction weight loss rate of the bio-based oil precipitation-resistant new energy tread rubber composition is ≤3.5%;

[0008] The bio-based oil precipitation-proof new energy tread rubber composition comprises: solution-polymerized styrene-butadiene rubber, white carbon black, bio-based oil, and polyethylene glycol;

[0009] The bio-based oil is soybean oil or its derivatives with an iodine value of ≤40; and the molecular weight of the polyethylene glycol is 3000-6000.

[0010] Preferably, the solution-polymerized styrene-butadiene rubber is 1-3 single-end or double-end modified styrene-butadiene random copolymers, and the modified groups are ethoxy groups or amino groups.

[0011] Preferably, the solution polymerized styrene-butadiene rubber includes one or two solution polymerized styrene-butadiene rubbers with medium to high glass transition temperatures and one or two solution polymerized styrene-butadiene rubbers with low glass transition temperatures.

[0012] Preferably, the styrene content of the medium-high glass transition temperature solution-polymerized styrene-butadiene rubber is 20%-40%, and the styrene content of the low glass transition temperature solution-polymerized styrene-butadiene rubber is 10%-20%.

[0013] Preferably, the composition comprises, by weight, 60-120 parts of white carbon black, 1-25 parts of bio-based oil, 1-10 parts of polyethylene glycol, 100 parts of solution-polymerized styrene-butadiene rubber, 5-10 parts of silane coupling agent, 3-5 parts of active agent, 5-7 parts of antioxidant, and 3-6 parts of vulcanizing agent and accelerator.

[0014] Preferably, the specific surface area of ​​white carbon black is 90-200m 2 / g;

[0015] The silane coupling agent is at least one of bis-(propyltriethoxysilane) tetrasulfide, bis-(propyltriethoxysilane) disulfide, and mercaptopropyltriethoxysilane; the activator includes 1-2 parts of stearic acid and 1-3 parts of zinc oxide; the antioxidant includes 1-3 parts of antioxidant 4020, 1-2 parts of antioxidant RD, and 1-3 parts of wax; the vulcanizing agent is 1-2 parts of ordinary sulfur, and the accelerator includes 1-3 parts of DPG and 1-3 parts of CZ.

[0016] Preferably, the solvent extraction weight loss rate of the bio-based oil anti-precipitation new energy tread rubber composition is obtained through a compatibility test, and the compatibility test includes: weighing a sample of a fixed regular shape, the weight is M1, and then placing it in an extraction device for extraction at room temperature. After sufficient extraction, the sample is taken out and weighed, the weight is M2, and the extraction weight loss rate is calculated as 1-M2 / M1.

[0017] Another aspect of the present invention provides a method for preparing a bio-based oil precipitation-resistant new energy tread rubber composition according to any of the above technical solutions, comprising a masterbatch preparation step, wherein the masterbatch preparation step comprises:

[0018] Add solution polymerized styrene-butadiene rubber, white carbon black, silane coupling agent, polyethylene glycol, surfactant and antioxidant into a closed rubber mixer, mix to 110°C, add bio-based oil after pulling the plug, mix to 135°C and hold for 180s, mix evenly and then discharge the rubber to obtain a masterbatch.

[0019] Preferably, the method includes a second stage final rubber preparation step, which includes: adding a first stage masterbatch, a vulcanizing agent, and an accelerator into a closed rubber mixer, mixing them evenly, and then discharging the rubber to obtain the final rubber.

[0020] The present invention also provides a tire, wherein the tread rubber composition of the tire is the bio-based oil precipitation-proof new energy tread rubber composition of any of the above technical solutions.

[0021] Compared with the prior art, the present invention has the following beneficial effects:

[0022] The present invention provides a new energy tread rubber composition that prevents precipitation of bio-based oil. Polyethylene glycol (PEG) is used as an intermediate between the bio-based oil and silica to bridge the bio-based oil and silica. The terminal hydroxyl groups of PEG can form strong hydrogen bonds with the silanol groups on the surface of silica, and the long-chain ether bonds (-O-) can generate intermolecular forces (van der Waals forces and polar adsorption) with the ester groups and carboxyl groups of the bio-based oil, forming a stable "silica-PEG-bio-based oil" network to prevent the migration and precipitation of the oil phase.

[0023] The present invention provides a method for preparing a new energy tread rubber composition with bio-based oil and anti-oil precipitation. In the mixing process, the order of adding materials is limited, PEG and silica are first reacted, and long chains are coated on silica to enhance its dispersion. After the temperature reaches 110°C, the bio-based oil is added, and the bio-based oil molecules are combined with the dispersed silica and the PEG molecules on its surface to form a "silica-PEG-bio-based oil" stable network to prevent oil precipitation. In addition, the mixing temperature is maintained within 135°C to prevent excessively high temperatures from destroying the stable network structure and weakening the anti-oil precipitation effect. DETAILED DESCRIPTION

[0024] The following is a detailed and complete description of the technical solutions in the specific embodiments of the present invention. Obviously, the described embodiments are only some specific implementation methods of the overall technical solution of the present invention, and are not all implementation methods. Based on the overall concept of the present invention, all other embodiments obtained by ordinary skill in the art fall within the scope of protection of the present invention.

[0025] On one hand, the present invention provides a bio-based oil precipitation-resistant new energy tread rubber composition, wherein the solvent extraction weight loss rate of the bio-based oil precipitation-resistant new energy tread rubber composition is ≤3.5%.

[0026] A lower solvent extraction weight loss indicates better bio-based oil curing. In a preferred embodiment, the solvent extraction weight loss of the bio-based oil-resistant new energy tread rubber composition is determined through a compatibility test. The compatibility test comprises weighing a fixed, regularly shaped sample to a weight of M1, placing it in an extraction apparatus for extraction at room temperature, and removing it after sufficient extraction to weigh M2. The extraction weight loss is then calculated as 1-M2 / M1. The extraction solvent is an organic solvent such as acetone.

[0027] The bio-based oil precipitation-resistant new energy tread rubber composition comprises solution-polymerized styrene-butadiene rubber.

[0028] In a preferred embodiment, the solution-polymerized styrene-butadiene rubber comprises one to three single-end or dual-end modified styrene-butadiene random copolymers, wherein the modified groups are ethoxy or amine groups. In a preferred embodiment, the solution-polymerized styrene-butadiene rubber comprises one to two first solution-polymerized styrene-butadiene rubbers having a medium-high glass transition temperature and one to two second solution-polymerized styrene-butadiene rubbers having a low glass transition temperature; the medium-high glass transition temperature solution-polymerized styrene-butadiene rubbers have a styrene content of 20% to 40%, and the low glass transition temperature solution-polymerized styrene-butadiene rubbers have a styrene content of 10% to 20%.

[0029] Although non-polar long carbon chains account for a larger proportion in the overall soybean oil molecule, both ester groups (-COOR) and double bonds contribute to polarity. The modified groups in the modified solution-polymerized styrene-butadiene rubber make the molecular weight of the solution-polymerized styrene-butadiene rubber more polar, which can further improve the compatibility. At the same time, a low-styrene-modified solution-polymerized styrene-butadiene rubber (first solution-polymerized styrene-butadiene rubber) with a styrene content of 10%-20% is preferred, which can take into account both rolling resistance and wear properties. A medium-high styrene-modified solution-polymerized styrene-butadiene rubber (second solution-polymerized styrene-butadiene rubber) with a styrene content of 20%-40% is preferred to increase the glass transition temperature, balance the wet-slip performance, and compensate for the problem of decreased wet-slip performance caused by bio-based oil.

[0030] It can be understood that the styrene content of the medium-to-high glass transition temperature solution-polymerized styrene-butadiene rubber can also be 22%, 24%, 26%, 28%, 30%, 35% and any point value within the range; the styrene content of the low glass transition temperature solution-polymerized styrene-butadiene rubber in the solution-polymerized styrene-butadiene rubber can also be 12%, 14%, 16%, 18% and any point value within the range.

[0031] The bio-based oil anti-precipitation new energy tread rubber composition includes white carbon black. In a preferred embodiment, the specific surface area of ​​the white carbon black is 90-200m 2 / g, ensuring the formula's wet slip and rolling resistance performance.

[0032] Bio-based oil anti-precipitation The new energy tread rubber composition includes bio-based oil.

[0033] Replacing environmentally friendly aromatic or naphthenic oils with bio-based oils can address these ecological and environmental issues and the non-renewable nature of petroleum resources. However, using bio-based oils in new energy tire tread formulations containing the aforementioned solution-polymerized styrene-butadiene rubber presents the following challenges: The weakly polar bio-based oils are poorly compatible with the more polar modified solution-polymerized styrene-butadiene rubber and are prone to precipitation during storage, thus affecting processing performance and compound properties.

[0034] The bio-based oil-preventive new energy tread rubber composition includes polyethylene glycol. This invention uses polyethylene glycol (PEG) as an intermediate between the bio-based oil and silica, bridging the two. The terminal hydroxyl groups of PEG form strong hydrogen bonds with the silica surface silanol groups, while the long-chain ether bonds (-O-) generate intermolecular forces (van der Waals forces and polar adsorption) with the ester and carboxyl groups of the bio-based oil, forming a stable "silica-PEG-bio-based oil" network that prevents oil phase migration and precipitation.

[0035] Specifically, polyethylene glycol (PEG) is used as a "chemical bridge" between the bio-based oil and silica. On the one hand, the terminal hydroxyl groups of PEG form strong hydrogen bonds with the silanol groups on the silica surface, enhancing interfacial bonding. Simultaneously, the long PEG molecular chains adsorb onto the silica surface, forming a coating. On the other hand, the lone electron pair of the PEG ether bond (-O-) interacts with the electron-deficient carbon of the bio-based oil ester group (-C=O), forming hydrogen bonds (bond energies of 5–30 kJ / mol) with the bio-based oil carboxyl group (-COOH), "anchoring" the bio-based oil around the PEG molecular chain and reducing its free migration. The long PEG chains coat the silica surface and entangle the bio-based oil molecules, strengthening the bond through van der Waals forces. This creates a spatially stable "silica-PEG-bio-based oil" network within the rubber matrix, slowing the diffusion of oil molecules to the surface and preventing bio-based oil precipitation. This enables a "one formula for multiple oil sources," reduces supply chain risks for tire manufacturers, and addresses the standardization challenges associated with the diversity of bio-based oils.

[0036] This invention addresses the poor compatibility of low-polarity bio-based oils with modified styrene-butadiene rubber (SBBR) by proposing a bio-based oil-PEG-silica carbon black stabilization network technology. This technology uses a PEG intermediate to enhance the interaction between the bio-based oil and silica particles, solidifying the bio-based oil and preventing precipitation, thus overcoming the limitations of bio-based oil sources. This technology addresses the poor compatibility of low-polarity bio-based oils with SBBR formulations; lowers the glass transition temperature of tread rubber for new energy vehicles, improving low-temperature performance; strengthens the application of bio-based materials, reduces carbon emissions, and promotes sustainable resource and environmental development; broadens the application range of soybean oil, improves the interchangeability of bio-based oils, and facilitates standardized production processes in tire factories, reducing supply chain risks.

[0037] Bio-based oil is soybean oil or its derivatives with an iodine value of ≤40, containing long-chain fatty acid hydrocarbon groups, ester groups, and several double bonds. The soybean oil molecule contains a large proportion of non-polar long carbon chains, which has poor compatibility with modified solution-polymerized styrene-butadiene. Each soybean oil molecule has 3-4 carbon-carbon double bonds (C=C), which serve as active sites for modifying the soybean oil and reducing its unsaturation, which can improve its compatibility with solution-polymerized styrene-butadiene to a certain extent. The present invention uses bio-based oil to replace petroleum-based rubber process oil, which can reduce carbon emissions and promote sustainable development.

[0038] The molecular weight of polyethylene glycol is 3000-6000. The ether bond (-O-) of PEG and the soybean oil ester group (-COO-) generate a dipole interaction. The long PEG chain wraps around the soybean oil alkyl chain to generate van der Waals force, forming a random coil arrangement. At the same time, the hydroxyl group of PEG terminal group forms a strong hydrogen bond with the silanol group on the surface of silica. The long chain ether bond covers the silica surface to enhance the dispersion of silica. If the molecular weight of polyethylene glycol is too low, the ether chain is shortened. On the one hand, it will weaken the interaction site with the soybean oil molecular chain and weaken the interaction force with the soybean oil alkyl chain. On the other hand, it will reduce the coverage area with silica, reduce the entire network effect, and weaken the curing effect. If the molecular weight of polyethylene glycol is too large, the molecular chain mobility is poor, and after combining with the soybean oil molecules, a large steric hindrance is formed, which affects the dispersion of silica and causes the rubber performance to deteriorate.

[0039] It is understood that the molecular weight of polyethylene glycol can also be 3500, 4000, 4500, 5000, 5500 and any point value within the range.

[0040] In a preferred embodiment, the composition comprises, by weight, 60-120 parts of white carbon black, 1-25 parts of bio-based oil, 1-10 parts of polyethylene glycol, 100 parts of solution-polymerized styrene-butadiene rubber, 5-10 parts of silane coupling agent, 3-5 parts of active agent, 5-7 parts of antioxidant, and 3-6 parts of vulcanizing agent and accelerator.

[0041] It is understandable that the amount of silica can also be 70 parts, 80 parts, 90 parts, 100 parts, 110 parts, and any value therein, the amount of bio-based oil can also be 5 parts, 10 parts, 15 parts, 20 parts, and any value therein, and the amount of polyethylene glycol can also be 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, and any value therein.

[0042] The silane coupling agent is at least one of bis-(propyltriethoxysilane) tetrasulfide, bis-(propyltriethoxysilane) disulfide, and mercaptopropyltriethoxysilane; the activator includes 1-2 parts of stearic acid and 1-3 parts of zinc oxide; the antioxidant includes 1-3 parts of antioxidant 4020, 1-2 parts of antioxidant RD, and 1-3 parts of wax; the vulcanizing agent is 1-2 parts of ordinary sulfur, and the accelerator includes 1-3 parts of DPG and 1-3 parts of CZ.

[0043] Another aspect of the present invention provides a method for preparing a bio-based oil precipitation-resistant new energy tread rubber composition according to any of the above technical solutions, comprising a masterbatch preparation step, wherein the masterbatch preparation step comprises:

[0044] Add solution polymerized styrene-butadiene rubber, white carbon black, silane coupling agent, polyethylene glycol, surfactant and antioxidant into a closed rubber mixer, mix to 110°C, add bio-based oil after pulling the plug, mix to 135°C and hold for 180s, mix evenly and then discharge the rubber to obtain a masterbatch.

[0045] The above mixing process limits the order of adding materials. PEG and silica are allowed to react first, and the long-chain silica is coated to enhance its dispersion. Soybean oil is added after the temperature reaches 110°C. At this time, the soybean oil molecules combine with the already dispersed silica and its surface PEG molecules to form a "silica-PEG-bio-based oil" stable network to prevent oil precipitation. In addition, the mixing temperature is maintained within 135°C to prevent excessively high temperatures from destroying the stable network structure and weakening the anti-precipitation effect.

[0046] In a preferred embodiment, the method comprises the following steps: adding a first-stage masterbatch, a vulcanizing agent, and an accelerator into a closed rubber mixer, mixing the masterbatch evenly, and then discharging the masterbatch to obtain the final rubber.

[0047] The present invention also provides a tire, wherein the tread rubber composition of the tire is the bio-based oil precipitation-proof new energy tread rubber composition of any of the above technical solutions.

[0048] In order to more clearly and in detail introduce the bio-based oil anti-precipitation new energy tread rubber composition, its preparation method and tire provided by the embodiments of the present invention, the following description will be made in conjunction with specific embodiments.

[0049] Example 1

[0050] The bio-based oil anti-precipitation new energy tread rubber composition includes, by weight, 80 parts of white carbon black, 15 parts of bio-based oil, 5 parts of PEG (molecular weight 4000), 30 parts of the first solution-polymerized styrene-butadiene rubber (calculated on dry rubber), 70 parts of the second solution-polymerized styrene-butadiene rubber (calculated on dry rubber), 6.4 parts of silane coupling agent, 1.5 parts of stearic acid, 2 parts of zinc oxide, 2 parts of antioxidant 4020, 1.5 parts of antioxidant RD, 2 parts of wax, 1.5 parts of ordinary sulfur, 1.0 parts of accelerator CZ, and 1.2 parts of accelerator DPG.

[0051] The bio-based oil is soybean oil with an iodine value of ≤40; the styrene content of the first solution-polymerized styrene-butadiene rubber is 35%; the styrene content of the second solution-polymerized styrene-butadiene rubber is 15%; and the silane coupling agent is liquid silane coupling agent Si69.

[0052] The preparation method of the bio-based oil precipitation-resistant new energy tread rubber composition comprises the following steps:

[0053] Preparation of a masterbatch: Add the solution-polymerized styrene-butadiene rubber, white carbon black, silane coupling agent, PEG, stearic acid, zinc oxide, antioxidant 4020, antioxidant RD, and wax to a closed rubber mixer according to the above weight ratio, mix to 110° C., add bio-based oil after removing the plug, mix to 135° C. and hold for 180 seconds, mix evenly, and then discharge the glue to obtain a masterbatch;

[0054] Preparation of the second-stage final rubber: add the above-mentioned first-stage masterbatch, ordinary sulfur, accelerator CZ and accelerator DPG into a closed rubber mixer, mix evenly and then discharge the rubber to obtain the final rubber.

[0055] Example 2

[0056] The bio-based oil anti-precipitation new energy tread rubber composition comprises, by weight, 60 parts of white carbon black, 5 parts of bio-based oil, 2 parts of PEG (molecular weight 3000), 30 parts of the first solution-polymerized styrene-butadiene rubber (calculated on dry rubber), 40 parts of the second solution-polymerized styrene-butadiene rubber (calculated on dry rubber), 30 parts of the third solution-polymerized styrene-butadiene rubber (calculated on dry rubber), 5 parts of silane coupling agent, 1.5 parts of stearic acid, 2 parts of zinc oxide, 2 parts of antioxidant 4020, 1.5 parts of antioxidant RD, 2 parts of wax, 1.5 parts of ordinary sulfur, 1.2 parts of accelerator CZ, and 1.2 parts of accelerator DPG.

[0057] Among them, the bio-based oil is soybean oil with an iodine value of ≤40; the styrene content of the first solution polymerized styrene butadiene rubber is 35%; the styrene content of the second solution polymerized styrene butadiene rubber is 20%, and the styrene content of the third solution polymerized styrene butadiene rubber is 15%; the silane coupling agent is liquid silane coupling agent Si69.

[0058] The preparation method of the bio-based oil precipitation-resistant new energy tread rubber composition comprises the following steps:

[0059] Preparation of a masterbatch: Add the solution-polymerized styrene-butadiene rubber, white carbon black, silane coupling agent, PEG, stearic acid, zinc oxide, antioxidant 4020, antioxidant RD, and wax to a closed rubber mixer according to the above weight ratio, mix to 110° C., add bio-based oil after removing the plug, mix to 135° C. and hold for 180 seconds, mix evenly, and then discharge the glue to obtain a masterbatch;

[0060] Preparation of the second-stage final rubber: add the above-mentioned first-stage masterbatch, ordinary sulfur, accelerator CZ and accelerator DPG into a closed rubber mixer, mix evenly and then discharge the rubber to obtain the final rubber.

[0061] Example 3

[0062] The bio-based oil anti-precipitation new energy tread rubber composition includes, by weight, 120 parts of white carbon black, 25 parts of bio-based oil, 8 parts of PEG (molecular weight 6000), 40 parts of the first solution-polymerized styrene-butadiene rubber (calculated on dry rubber), 60 parts of the second solution-polymerized styrene-butadiene rubber (calculated on dry rubber), 9.6 parts of silane coupling agent, 1.5 parts of stearic acid, 2 parts of zinc oxide, 2 parts of antioxidant 4020, 1.5 parts of antioxidant RD, 2 parts of wax, 1.5 parts of ordinary sulfur, 1.0 parts of accelerator CZ, and 2 parts of accelerator DPG.

[0063] The bio-based oil is soybean oil with an iodine value of ≤40; the styrene content of the first solution-polymerized styrene-butadiene rubber is 35%; the styrene content of the second solution-polymerized styrene-butadiene rubber is 15%; and the silane coupling agent is liquid silane coupling agent Si69.

[0064] The preparation method of the bio-based oil precipitation-resistant new energy tread rubber composition comprises the following steps:

[0065] Preparation of a masterbatch: Add the solution-polymerized styrene-butadiene rubber, white carbon black, silane coupling agent, PEG, stearic acid, zinc oxide, antioxidant 4020, antioxidant RD, and wax to a closed rubber mixer according to the above weight ratio, mix to 110° C., add bio-based oil after removing the plug, mix to 135° C. and hold for 180 seconds, mix evenly, and then discharge the glue to obtain a masterbatch;

[0066] Preparation of the second-stage final rubber: add the above-mentioned first-stage masterbatch, ordinary sulfur, accelerator CZ and accelerator DPG into a closed rubber mixer, mix evenly and then discharge the rubber to obtain the final rubber.

[0067] Comparative Example 1

[0068] The bio-based oil anti-precipitation new energy tread rubber composition comprises, by weight, 80 parts of white carbon black, 15 parts of bio-based oil, 30 parts of the first solution-polymerized styrene-butadiene rubber (calculated on dry rubber), 70 parts of the second solution-polymerized styrene-butadiene rubber (calculated on dry rubber), 6.4 parts of a silane coupling agent, 1.5 parts of stearic acid, 2 parts of zinc oxide, 2 parts of an antioxidant 4020, 1.5 parts of an antioxidant RD, 2 parts of wax, 1.5 parts of ordinary sulfur, 1.5 parts of an accelerator CZ, and 2.0 parts of an accelerator DPG.

[0069] The bio-based oil is soybean oil with an iodine value of ≤40; the styrene content of the first solution-polymerized styrene-butadiene rubber is 35%; the styrene content of the second solution-polymerized styrene-butadiene rubber is 15%; and the silane coupling agent is liquid silane coupling agent Si69.

[0070] The preparation method of the bio-based oil precipitation-resistant new energy tread rubber composition comprises the following steps:

[0071] Preparation of a masterbatch: Add the solution-polymerized styrene-butadiene rubber, white carbon black, silane coupling agent, stearic acid, zinc oxide, antioxidant 4020, antioxidant RD, and wax to a closed rubber mixer according to the above weight ratio, mix to 110° C., add bio-based oil after removing the plug, mix to 135° C. and hold for 180 seconds. After mixing evenly, discharge the rubber to obtain a masterbatch;

[0072] Preparation of the second-stage final rubber: add the above-mentioned first-stage masterbatch, ordinary sulfur, accelerator CZ and accelerator DPG into a closed rubber mixer, mix evenly and then discharge the rubber to obtain the final rubber.

[0073] Comparative Example 2

[0074] The bio-based oil anti-precipitation new energy tread rubber composition includes, by weight, 80 parts of white carbon black, 15 parts of heavy naphthenic oil, 30 parts of the first solution-polymerized styrene-butadiene rubber (calculated on dry rubber), 70 parts of the second solution-polymerized styrene-butadiene rubber (calculated on dry rubber), 6.4 parts of a silane coupling agent, 1.5 parts of stearic acid, 2 parts of zinc oxide, 2 parts of an antioxidant 4020, 1.5 parts of an antioxidant RD, 2 parts of wax, 1.5 parts of ordinary sulfur, 1.5 parts of an accelerator CZ, and 2.0 parts of an accelerator DPG.

[0075] The styrene content of the first solution-polymerized styrene-butadiene rubber is 35%; the styrene content of the second solution-polymerized styrene-butadiene rubber is 15%; and the silane coupling agent is liquid silane coupling agent Si69.

[0076] The preparation method of the bio-based oil precipitation-resistant new energy tread rubber composition comprises the following steps:

[0077] Preparation of a masterbatch: Add the solution-polymerized styrene-butadiene rubber, white carbon black, silane coupling agent, stearic acid, zinc oxide, antioxidant 4020, antioxidant RD, and wax to a closed rubber mixer according to the above weight ratio, mix to 110° C., add bio-based oil after removing the plug, mix to 135° C. and hold for 180 seconds. After mixing evenly, discharge the rubber to obtain a masterbatch;

[0078] Preparation of the second-stage final rubber: add the above-mentioned first-stage masterbatch, ordinary sulfur, accelerator CZ and accelerator DPG into a closed rubber mixer, mix evenly and then discharge the rubber to obtain the final rubber.

[0079] Comparative Example 3

[0080] The bio-based oil anti-precipitation new energy tread rubber composition comprises, by weight, 80 parts of white carbon black, 15 parts of bio-based oil, 5 parts of PEG (molecular weight 2000), 30 parts of the first solution-polymerized styrene-butadiene rubber (calculated on dry rubber), 70 parts of the second solution-polymerized styrene-butadiene rubber (calculated on dry rubber), 6.4 parts of a silane coupling agent, 1.5 parts of stearic acid, 2 parts of zinc oxide, 2 parts of an antioxidant 4020, 1.5 parts of an antioxidant RD, 2 parts of wax, 1.5 parts of ordinary sulfur, 1.0 parts of an accelerator CZ, and 1.2 parts of an accelerator DPG.

[0081] The bio-based oil is soybean oil with an iodine value of ≤40; the styrene content of the first solution-polymerized styrene-butadiene rubber is 35%; the styrene content of the second solution-polymerized styrene-butadiene rubber is 15%; and the silane coupling agent is liquid silane coupling agent Si69.

[0082] The preparation method of the bio-based oil precipitation-resistant new energy tread rubber composition comprises the following steps:

[0083] Preparation of a masterbatch: Add the solution-polymerized styrene-butadiene rubber, white carbon black, silane coupling agent, PEG, stearic acid, zinc oxide, antioxidant 4020, antioxidant RD, and wax to a closed rubber mixer according to the above weight ratio, mix to 110° C., add bio-based oil after removing the plug, mix to 135° C. and hold for 180 seconds, mix evenly, and then discharge the glue to obtain a masterbatch;

[0084] Preparation of the second-stage final rubber: add the above-mentioned first-stage masterbatch, ordinary sulfur, accelerator CZ and accelerator DPG into a closed rubber mixer, mix evenly and then discharge the rubber to obtain the final rubber.

[0085] Comparative Example 4

[0086] The bio-based oil anti-precipitation new energy tread rubber composition includes, by weight, 80 parts of white carbon black, 15 parts of bio-based oil, 5 parts of PEG (molecular weight 7000), 30 parts of the first solution-polymerized styrene-butadiene rubber (calculated on dry rubber), 70 parts of the second solution-polymerized styrene-butadiene rubber (calculated on dry rubber), 6.4 parts of silane coupling agent, 1.5 parts of stearic acid, 2 parts of zinc oxide, 2 parts of antioxidant 4020, 1.5 parts of antioxidant RD, 2 parts of wax, 1.5 parts of ordinary sulfur, 1.0 parts of accelerator CZ, and 1.2 parts of accelerator DPG.

[0087] The bio-based oil is soybean oil with an iodine value of ≤40; the styrene content of the first solution-polymerized styrene-butadiene rubber is 35%; the styrene content of the second solution-polymerized styrene-butadiene rubber is 15%; and the silane coupling agent is liquid silane coupling agent Si69.

[0088] The preparation method of the bio-based oil precipitation-resistant new energy tread rubber composition comprises the following steps:

[0089] Preparation of a masterbatch: Add the solution-polymerized styrene-butadiene rubber, white carbon black, silane coupling agent, PEG, stearic acid, zinc oxide, antioxidant 4020, antioxidant RD, and wax to a closed rubber mixer according to the above weight ratio, mix to 110° C., add bio-based oil after removing the plug, mix to 135° C. and hold for 180 seconds, mix evenly, and then discharge the glue to obtain a masterbatch;

[0090] Preparation of the second-stage final rubber: add the above-mentioned first-stage masterbatch, ordinary sulfur, accelerator CZ and accelerator DPG into a closed rubber mixer, mix evenly and then discharge the rubber to obtain the final rubber.

[0091] Comparative Example 5

[0092] The bio-based oil anti-precipitation new energy tread rubber composition includes, by weight, 80 parts of white carbon black, 15 parts of bio-based oil, 5 parts of PEG (molecular weight 4000), 30 parts of the first solution-polymerized styrene-butadiene rubber (calculated on dry rubber), 70 parts of the second solution-polymerized styrene-butadiene rubber (calculated on dry rubber), 6.4 parts of silane coupling agent, 1.5 parts of stearic acid, 2 parts of zinc oxide, 2 parts of antioxidant 4020, 1.5 parts of antioxidant RD, 2 parts of wax, 1.5 parts of ordinary sulfur, 1.0 parts of accelerator CZ, and 1.2 parts of accelerator DPG.

[0093] The bio-based oil is soybean oil with an iodine value of ≤40; the styrene content of the first solution-polymerized styrene-butadiene rubber is 35%; the styrene content of the second solution-polymerized styrene-butadiene rubber is 15%; and the silane coupling agent is liquid silane coupling agent Si69.

[0094] The preparation method of the bio-based oil precipitation-resistant new energy tread rubber composition comprises the following steps:

[0095] Preparation of a masterbatch: Add the above-mentioned solution-polymerized styrene-butadiene rubber, white carbon black, silane coupling agent, PEG, stearic acid, zinc oxide, antioxidant 4020, antioxidant RD, wax, and bio-based oil to a closed rubber mixer according to the above-mentioned weight ratio, mix to 110°C, remove the plug, mix to 135°C and hold for 180 seconds, mix evenly, and then discharge the glue to obtain a masterbatch;

[0096] Preparation of the second-stage final rubber: add the above-mentioned first-stage masterbatch, ordinary sulfur, accelerator CZ and accelerator DPG into a closed rubber mixer, mix evenly and then discharge the rubber to obtain the final rubber.

[0097] Performance Testing

[0098] The final rubber mixes obtained in Example 1 and Comparative Examples 1 and 2 were subjected to a weight loss test, an oil precipitation natural environment observation test, a rubber tensile property test, and a dynamic mechanical property test. The test results are shown in Table 1.

[0099] The extraction weight loss rate test is carried out as follows: a fixed regular shape sample (3g-5g) is weighed (M1) and placed in an extraction device for extraction. After 4 hours, it is taken out and weighed (M2). The extraction weight loss rate is calculated as 1-M2 / M1;

[0100] Rubber composition surface observation method: Store the sample at room temperature and observe and record the state of oil phase precipitation on the sample surface over time;

[0101] The tensile properties of the rubber compound are tested in accordance with GB / T528;

[0102] The dynamic mechanical properties were tested using ISO 4664-1:2005, with an initial strain of 7%, a dynamic strain of 1%, a frequency of 10 Hz, and a temperature of 70 °C. The hysteresis loss was characterized by tan δ.

[0103] Table 1 Final rubber mix performance test table obtained from the embodiments and comparative examples

[0104]

[0105]

[0106] As can be seen from the results in Table 1, Examples 1, 2, and 3 are the rubber compositions provided by the present invention, and no oil film precipitates on the surface. Comparative Example 1 does not have PEG added, and a clear oil film or even oil droplets precipitate on the surface, resulting in a decrease in performance. Compared with Comparative Example 2, which uses heavy naphthenic oil, although some performance is still sacrificed, the difference is not large, and the examples are better than Comparative Example 2. Most importantly, carbon emissions are reduced while meeting the rubber performance requirements, achieving sustainable development. Comparative Examples 3 and 4 use PEG below and above the limit range, respectively. Comparative Example 3 has a small amount of oily matter precipitated, and although Comparative Example 4 does not precipitate an oil film, its performance, especially rolling resistance, is significantly reduced due to poor dispersion. Comparative Example 5 uses oil and other materials during processing, which affects dispersion, resulting in a decrease in rubber performance, especially rolling resistance, and a slightly oily feel on the rubber surface.

Claims

1. A bio-based oil precipitation-proof new energy tread rubber composition, characterized in that: The solvent extraction weight loss rate of the bio-based oil precipitation-proof new energy tread rubber composition is ≤3.5%; The bio-based oil precipitation-proof new energy tread rubber composition comprises: solution-polymerized styrene-butadiene rubber, white carbon black, bio-based oil, and polyethylene glycol; The bio-based oil is soybean oil or its derivatives with an iodine value of ≤40; the molecular weight of the polyethylene glycol is 3000-6000.

2. The bio-based oil precipitation-proof new energy tread rubber composition according to claim 1, characterized in that: The solution-polymerized styrene-butadiene rubber is 1-3 single-end or double-end modified styrene-butadiene random copolymers, and the modified groups are ethoxy groups or amino groups.

3. The bio-based oil precipitation-proof new energy tread rubber composition according to claim 2, characterized in that: The solution polymerized styrene butadiene rubber comprises one or two solution polymerized styrene butadiene rubbers with medium to high glass transition temperatures and one or two solution polymerized styrene butadiene rubbers with low glass transition temperatures.

4. The bio-based oil precipitation-resistant new energy tread rubber composition according to claim 3, characterized in that: The styrene content of the medium-high glass transition temperature solution-polymerized styrene-butadiene rubber is 20%-40%, and the styrene content of the low glass transition temperature solution-polymerized styrene-butadiene rubber is 10%-20%.

5. The bio-based oil precipitation-resistant new energy tread rubber composition according to claim 1, characterized in that: Calculated by weight, the composition comprises 60-120 parts of white carbon black, 1-25 parts of bio-based oil, 1-10 parts of polyethylene glycol, 100 parts of solution-polymerized styrene-butadiene rubber, 5-10 parts of silane coupling agent, 3-5 parts of active agent, 5-7 parts of antioxidant, and 3-6 parts of vulcanizing agent and accelerator.

6. The bio-based oil precipitation-resistant new energy tread rubber composition according to claim 5, characterized in that: The specific surface area of ​​the white carbon black is 90-200m 2 / g; The silane coupling agent is at least one of bis-(propyltriethoxysilane) tetrasulfide, bis-(propyltriethoxysilane) disulfide, and mercaptopropyltriethoxysilane; the activator includes 1-2 parts of stearic acid and 1-3 parts of zinc oxide; the antioxidant includes 1-3 parts of antioxidant 4020, 1-2 parts of antioxidant RD, and 1-3 parts of wax; the vulcanizing agent is 1-2 parts of ordinary sulfur, and the accelerator includes 1-3 parts of DPG and 1-3 parts of CZ.

7. The bio-based oil precipitation-resistant new energy tread rubber composition according to claim 1, characterized in that: The solvent extraction weight loss rate of the bio-based oil anti-precipitation new energy tread rubber composition is obtained through a compatibility test. The compatibility test includes: weighing a sample of a fixed regular shape, the weight is M1, then placing it in an extraction device for extraction at room temperature, taking it out after sufficient extraction and weighing it, the weight is M2, and calculating the extraction weight loss rate 1-M2 / M1.

8. The method for preparing the bio-based oil precipitation-resistant new energy tread rubber composition according to any one of claims 1 to 7, characterized in that: The method comprises a masterbatch preparation step, wherein the masterbatch preparation step comprises: Add solution polymerized styrene-butadiene rubber, white carbon black, silane coupling agent, polyethylene glycol, surfactant and antioxidant into a closed rubber mixer, mix to 110°C, add bio-based oil after pulling the plug, mix to 135°C and hold for 180s, mix evenly and then discharge the rubber to obtain a masterbatch.

9. The method for preparing the bio-based oil precipitation-resistant new energy tread rubber composition according to claim 8, characterized in that: The method comprises the steps of preparing a second-stage final rubber, wherein the second-stage final rubber preparation step comprises: adding a first-stage masterbatch, a vulcanizing agent and an accelerator into a closed rubber mixer, mixing the masterbatch evenly and then discharging the masterbatch to obtain the final rubber.

10. A tire, characterized in that: The tire tread rubber composition is the bio-based oil precipitation-resistant new energy tread rubber composition described in any one of items 1-7.

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