Tire sidewall rubber composition, preparation method therefor, and tire

Abstract

The present invention relates to the technical field of rubber products. Disclosed are a tire sidewall rubber composition, a preparation method therefor, and a tire, for solving the problem in the prior art of affecting the sense organ of a human body and even harming the health of the human body by order and VOC molecules released by a tire. The tire sidewall rubber composition comprises coordination polymerization diene rubber, a nano material of a porous structure, and an inorganic reinforcing filler; the addition amount of said nano material is 2-10% of the mass of the coordination polymerization diene rubber, and the mass of the inorganic reinforcing filler is 35-75% of the mass of the coordination polymerization diene rubber. A specific technological process comprises: adding the coordination polymerization diene rubber, the inorganic reinforcing filler, said nano material and other auxiliary agents into an internal mixer for first-stage mixing to obtain first-stage master batch; and adding the first-stage master batch and a vulcanizing agent into the internal mixer for second-stage mixing, and discharging the rubber. The method is simple in process, and said nano material is added into the tire sidewall rubber composition, thereby reducing the odor of the rubber material and the volatilization of the VOC molecules.

Description

Sidewall rubber composition, preparation method thereof, and tire Technical Field

[0001] The present invention relates to the technical field of rubber products, in particular to a sidewall rubber composition, a preparation method thereof, and a tire. Background Art

[0002] Tires are a composite of rubber and various additives, produced by mixing and kneading a variety of chemical raw materials. The rubber and additives used in tire production contain odor and VOC molecules. During the blending and vulcanization process, heat and shear forces release these odors and VOCs. Simultaneously, various chemical reactions occur, generating various small molecules that also release odor and VOCs during use.

[0003] The most harmful pentane trialdehydes to the human body include benzene, toluene, xylene, ethylbenzene, styrene, formaldehyde, acetaldehyde, and acrolein. When their odor is detectable, their concentration is dozens of times higher than the standard, posing a serious threat to the human body. Some amines and sulfur-containing compounds, even at extremely low levels, can have a distinctly pungent odor, affecting the senses and causing discomfort. They can even damage the respiratory tract and endanger human health.

[0004] Existing odor removal processes include masking, heat devolatilization, and natural odor removal. Masking directly adds fragrance compounds during the production process, blending various scents to reduce the odor of the rubber compound. This only addresses the symptoms, not the root cause. Furthermore, the odor of the resulting mixture varies significantly among different demographics, potentially causing psychological and physiological aversion in some users. Heat devolatilization, performed at high temperatures, accelerates volatilization to reduce VOCs and odor molecules in the product. However, high-temperature treatment not only reduces product performance to varying degrees, but is also energy-intensive, investment-intensive, and environmentally unfriendly. Natural odor removal extends product storage time, allowing the tire to reach a balanced odor emission state at room temperature, thereby reducing the odor of new products. However, this increases the difficulty of inventory and transportation. To effectively reduce the odor of tire rubber compounds, research should prioritize areas with high exposure to the natural environment, such as the sidewalls, to reduce odor while maintaining tire performance. Summary of the Invention

[0005] In view of this, the present invention provides a sidewall rubber composition and a tire prepared therefrom to solve the technical problem that tires release odor and VOC molecules, affecting human senses and even endangering human health.

[0006] In order to solve the above technical problems, the present invention adopts the following technical solutions:

[0007] The present invention provides a sidewall rubber composition, comprising a coordination polymerized diene rubber, a porous structure nanomaterial and an inorganic reinforcing filler; wherein,

[0008] The added amount of the porous structure nanomaterial is 2-10% of the mass of the coordination polymerized diene rubber, and the added amount of the inorganic reinforcing filler is 35-75% of the mass of the coordination polymerized diene rubber.

[0009] Preferably, in the above-mentioned sidewall rubber composition, the addition amount of the coordinated polymerized diene rubber is 1-100% of the total mass of the raw materials of the sidewall rubber composition, and the coordinated polymerized diene rubber is one or a mixture of several of cis-1,4-polybutadiene polymer, cis-1,4-polyisoprene polymer, and high vinyl butadiene polymer.

[0010] Preferably, in the above-mentioned sidewall rubber composition, the raw material of the porous structure nanomaterial is inorganic silicate and is prepared by a hydrothermal synthesis method.

[0011] Preferably, in the above-mentioned sidewall rubber composition, the pH value of the porous structure nanomaterial is 10-11.5, the weight loss when heated at 80°C is 0-4.5%, the ash content is 82-86%, and the density is 1-2 g / cm 3 .

[0012] Preferably, in the above-mentioned sidewall rubber composition, the inorganic reinforcing filler is one or more of carbon black, white carbon black, silicate, and clay.

[0013] Preferably, in the above-mentioned sidewall rubber composition, the carbon black is selected from one or a mixture of N100, N200, N300, N500, N600, N700, bio-based carbon black.

[0014] Preferably, the above-mentioned sidewall rubber composition further comprises a plasticizer, a silane coupling agent, stearic acid, a chemical antioxidant, a protective wax and a vulcanizing agent; wherein,

[0015] The amount of the plasticizer added is 1-20% of the mass of the coordination polymerized diene rubber, the amount of the silane coupling agent added is 1-4% of the mass of the coordination polymerized diene rubber, the amount of the stearic acid added is 1.5-6% of the mass of the coordination polymerized diene rubber, the amount of the chemical antioxidant added is 1-10% of the mass of the coordination polymerized diene rubber, and the amount of the protective wax and the vulcanizing agent added are both 1-8% of the mass of the coordination polymerized diene rubber.

[0016] Preferably, in the above-mentioned sidewall rubber composition, the plasticizer is one or a mixture of environmentally friendly cyclohexane oil, environmentally friendly alkane oil, environmentally friendly aromatic oil, and bio-based oil.

[0017] Preferably, in the above-mentioned sidewall rubber composition, the silane coupling agent is one or more of bis[3-(triethoxysilyl)propyl]tetrasulfide, bis-[(triethoxysilyl)-propyl]disulfide, and γ-mercaptopropyltrimethoxysilane.

[0018] Preferably, in the above-mentioned sidewall rubber composition, the vulcanizing agent includes oil-extended sulfur powder and an accelerator; wherein,

[0019] The amount of the oil-extended sulfur powder added is 1-7% of the mass of the coordination polymerized diene rubber, and the amount of the accelerator added is 1-7% of the mass of the coordination polymerized diene rubber.

[0020] Preferably, in the above-mentioned sidewall rubber composition, the accelerator is one or more of N-tert-butyl-2-benzothiazole sulfenamide, N-cyclohexyl-2-benzothiazole sulfenamide, N-oxydiethylene-2-benzothiazole sulfenamide, and N-oxydiethylenethiocarbamoyl-N´-oxydiethylenesulfenamide.

[0021] Preferably, the present invention also provides a method for preparing a sidewall rubber composition, comprising the following steps:

[0022] S1: non-productive mixing: adding the coordination polymerized diene rubber, inorganic reinforcing filler, porous structure nanomaterial, plasticizer, silane coupling agent, stearic acid, chemical antioxidant, and protective wax to an internal mixer for mixing, cooling, and obtaining a masterbatch;

[0023] S2: Production mixing: Add the masterbatch and vulcanizing agent into the internal mixer at the same time, perform two-stage mixing and discharge.

[0024] Preferably, in the preparation method of the above-mentioned sidewall rubber composition, the non-productive mixing temperature is 100-140°C, the time is 5-20 min, the upper push pin pressure is 0.3-0.6 MPa, the productive mixing upper push pin pressure is 0.15-0.5 MPa, and the rubber is discharged when the temperature reaches 110-135°C.

[0025] Preferably, the present application also provides a tire, which is prepared using the above-mentioned sidewall rubber composition and preparation method.

[0026] The present invention provides a sidewall rubber composition, a preparation method thereof, and a tire. Compared with the prior art, the present invention has the following advantages:

[0027] (1) The present invention mixes coordination polymerized diene rubber, porous structure nanomaterials, and inorganic reinforcing fillers, and volatilizes small molecules in the rubber composite material through physical and chemical adsorption, thereby reducing the odor of the tire and the volatilization of VOC molecules, and solving the problem that tire odor affects human senses and harms human health;

[0028] (2) The tire of the present invention can significantly reduce the odor of the tire rubber compound by adding only 2-10% of the total amount of the sidewall rubber composition to the modified inorganic silicate porous structure nanomaterial. That is, only adding a very small amount of porous structure nanomaterial can solve the technical problem of releasing odors and VOC molecules that are harmful to human health and affect sensory organs during tire production. At the same time, a small amount of porous structure nanomaterial will not harm human health and the environment.

[0029] (3) The odor-improving porous structure nanomaterial added to the tire sidewall rubber composition of the present invention has the advantages of abundant raw materials, low cost, and simple synthesis method. DETAILED DESCRIPTION

[0030] Below in detail embodiments of the present invention, the example of described embodiment is shown in the accompanying drawings, wherein identical or similar reference numerals represent identical or similar elements or elements with identical or similar functions throughout. The embodiment described below by reference to the accompanying drawings is exemplary, is only used to explain the present invention, and is not to be construed as limiting the present invention. In the embodiment, if no specific technology or condition is indicated, it is carried out according to the technology or condition described in the document in this area or according to the product specification. Reagents used or instruments are not indicated by manufacturers, and are conventional products that can be obtained commercially.

[0031] Some embodiments of the present invention provide a sidewall rubber composition comprising a coordination polymerized diene rubber, a porous structure nanomaterial, and an inorganic reinforcing filler.

[0032] In some embodiments of the present invention, the amount of the porous structure nanomaterial added is 2-10% of the mass of the coordination polymerized diene rubber, and the amount of the inorganic reinforcing filler added is 35-75% of the mass of the coordination polymerized diene rubber.

[0033] In some embodiments of the present invention, the amount of the coordinated polymerized diene rubber added is 1-100% of the total mass of the raw materials of the sidewall rubber composition, and the coordinated polymerized diene rubber is a mixture of one or more of cis-1,4-polybutadiene polymer, cis-1,4-polyisoprene polymer, and high-vinyl butadiene polymer. The rubber is easier to polymerize and is preferably a mixture of cis-1,4-polybutadiene polymer and cis-1,4-polyisoprene polymer, wherein polyisoprene is well compatible with all rubbers.

[0034] In some embodiments of the present invention, the raw material of the porous structure nanomaterial is inorganic silicate and is prepared by a hydrothermal synthesis method. The hydrothermal synthesis method is to add the evenly stirred inorganic silicate raw material to a stainless steel reactor at 130-200°C for crystallization reaction for 7-45 hours. After natural cooling, the product is filtered and washed with water to a pH of 10-11.5, and then dried at 70-90°C for 2-5 hours to obtain the porous structure nanomaterial. This method is simple and inexpensive, and the prepared porous structure nanomaterial has better chemical and thermal stability.

[0035] In some embodiments of the present invention, the pH value of the porous structure nanomaterial is 10-11.5, the weight loss at 80°C is 0-4.5%, the ash content is 82-86%, and the density is 1-2 g / cm 3 .

[0036] In some embodiments of the present invention, the inorganic reinforcing filler is one or more of carbon black, white carbon black, silicate, and clay, preferably carbon black, which has strong chemical activity on its surface, can produce good bonding with rubber, and improve the mechanical properties, aging resistance and adhesion properties of the vulcanized rubber; the carbon black is selected from one or more of N100, N200, N300, N500, N600, N700, and a mixture of bio-based carbon black, preferably N500 carbon black, bio-based carbon black, and more preferably bio-based carbon black, which uses renewable materials as raw materials and is manufactured through biological, chemical and physical methods. It is a green energy and a filler that can improve the performance of vulcanized rubber.

[0037] In some embodiments of the present invention, the sidewall rubber composition further includes a plasticizer, a silane coupling agent, stearic acid, a chemical antioxidant, a protective wax, and a vulcanizing agent.

[0038] In some embodiments of the present invention, the amount of plasticizer added is 1-20% of the mass of the coordinated polymerized diene rubber, the amount of silane coupling agent added is 1-4% of the mass of the coordinated polymerized diene rubber, the amount of stearic acid added is 1.5-6% of the mass of the coordinated polymerized diene rubber, the amount of chemical antioxidant added is 1-10% of the mass of the coordinated polymerized diene rubber, and the amount of protective wax and vulcanizing agent added is 1-8% of the mass of the coordinated polymerized diene rubber.

[0039] In some embodiments of the present invention, the plasticizer is one or a mixture of environmentally friendly cycloparaffin oil, environmentally friendly alkane oil, environmentally friendly aromatic oil, and bio-based oil, preferably bio-based oil and environmentally friendly alkane oil, and more preferably environmentally friendly alkane oil, which is beneficial to improving the processing performance of the rubber.

[0040] In some embodiments of the present invention, the silane coupling agent is one or more of bis[3-(triethoxysilyl)propyl]tetrasulfide, bis-[(triethoxysilyl)-propyl]disulfide, and γ-mercaptopropyltrimethoxysilane, which can not only improve the mechanical properties of the rubber compound, but also improve the heat resistance, water resistance and weather resistance of the rubber compound. Preferably, it is bis-[(triethoxysilyl)-propyl]disulfide, which can form physical adsorption with the rubber molecular chain, increase the interaction between the inorganic reinforcing filler and the rubber, and improve the mechanical properties of the rubber compound.

[0041] In some embodiments of the present invention, the vulcanizing agent includes oil-extended sulfur powder and an accelerator. The amount of the oil-extended sulfur powder added is 1-7% of the mass of the coordinated polymerized diene rubber, and the amount of the accelerator added is 1-7% of the mass of the coordinated polymerized diene rubber, which is beneficial to improving the mechanical properties of the rubber. The accelerator is one or more of N-tert-butyl-2-benzothiazolesulfenamide, N-cyclohexyl-2-benzothiazolesulfenamide, N-oxydiethylene-2-benzothiazolesulfenamide, and N-oxydiethylenethiocarbamoyl-N'-oxydiethylenesulfenamide, preferably N-cyclohexyl-2-benzothiazolesulfenamide, which is beneficial to shortening the vulcanization time, reducing the amount of sulfur powder used, and lowering the vulcanization temperature, thereby improving production efficiency and reducing costs.

[0042] Some embodiments of the present invention further provide a method for preparing a sidewall rubber composition, comprising the following steps:

[0043] S1: Non-productive mixing: The coordination polymerized diene rubber, inorganic reinforcing filler, porous structure nanomaterial, plasticizer, silane coupling agent, stearic acid, chemical antioxidant, and protective wax are added to an internal mixer at 100-140° C. and mixed for a period of time. The upper pusher pressure is set to 0.3-0.6 MPa. After mixing for 5-20 minutes, the mixture is naturally cooled to obtain a masterbatch.

[0044] S2: Production mixing: The first stage masterbatch and the vulcanizing agent are added into the internal mixer at the same time for second stage mixing. The upper ejector pressure is set to 0.15-0.5 MPa. When the temperature reaches 110-135°C, the glue is discharged.

[0045] In some embodiments of the present invention, a tire is further provided. The tire is prepared using the above-mentioned sidewall rubber composition and preparation method.

[0046] The technical solutions provided by the present invention are described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of the present invention. Example 1

[0047] The sidewall rubber composition of this embodiment includes the following components in parts by weight: 30 parts of cis-1,4-polybutadiene polymer, 70 parts of cis-1,4-polyisoprene polymer, 2 parts of porous structure nanomaterial, 35 parts of N500 carbon black, 1 part of environmentally friendly cyclohexane oil, 1 part of bis-[(triethoxysilyl)-propyl] disulfide, 1.5 parts of stearic acid, 1 part of chemical antioxidant, 1 part of protective wax, 7 parts of oil-extended sulfur powder, and 1 part of accelerator.

[0048] The sidewall rubber composition is prepared according to the following method, which includes the following steps:

[0049] S1: Non-productive mixing: cis-1,4-polybutadiene polymer, cis-1,4-polyisoprene polymer, porous structure nanomaterial, N500 carbon black, environmentally friendly cyclohexane oil, bis-[(triethoxysilyl)-propyl] disulfide, stearic acid, chemical antioxidant, and protective wax were added to an internal mixer at 100°C for mixing. The upper bolt pressure was set to 0.3 MPa. After mixing for 5 minutes, the mixture was naturally cooled to obtain a masterbatch.

[0050] S2: Production mixing: The first stage masterbatch, oil-extended sulfur powder and accelerator are added to an internal mixer for second stage mixing. The upper ejector pressure is set to 0.15 MPa. When the temperature reaches 110°C, the glue is discharged. Example 2

[0051] The sidewall rubber composition of this embodiment includes the following components in parts by weight: 50 parts of cis-1,4-polybutadiene polymer, 50 parts of cis-1,4-polyisoprene polymer, 5 parts of porous structure nanomaterial, 55 parts of bio-based carbon black, 10 parts of bio-based oil, 2.5 parts of bis-[(triethoxysilyl)-propyl] disulfide, 3.5 parts of stearic acid, 5 parts of chemical antioxidant, 4 parts of protective wax, 4 parts of oil-extended sulfur powder, and 4 parts of accelerator.

[0052] The sidewall rubber composition is prepared according to the following method, which includes the following steps:

[0053] S1: Non-productive mixing: cis-1,4-polybutadiene polymer, cis-1,4-polyisoprene polymer, porous structure nanomaterials, bio-based carbon black, bio-based oil, bis-[(triethoxysilyl)-propyl] disulfide, stearic acid, chemical antioxidant, and protective wax were added to an internal mixer at 120°C for mixing. The upper bolt pressure was set to 0.4 MPa. After mixing for 8 minutes, the mixture was naturally cooled to obtain a masterbatch.

[0054] S2: Production mixing: The first stage masterbatch, oil-extended sulfur powder and accelerator are added into an internal mixer for second stage mixing. The upper ejector pressure is set to 0.25 MPa. When the temperature reaches 120°C, the glue is discharged. Example 3

[0055] The sidewall rubber composition of this embodiment includes the following components in parts by weight: 50 parts of cis-1,4-polybutadiene polymer, 50 parts of cis-1,4-polyisoprene polymer, 10 parts of porous structure nanomaterial, 75 parts of N500 carbon black, 20 parts of environmentally friendly cyclohexane oil, 4 parts of bis-[(triethoxysilyl)-propyl] disulfide, 6 parts of stearic acid, 10 parts of chemical antioxidant, 8 parts of protective wax, 1 part of oil-extended sulfur powder, and 7 parts of accelerator.

[0056] The sidewall rubber composition is prepared according to the following method, which includes the following steps:

[0057] S1: Non-productive mixing: cis-1,4-polybutadiene polymer, cis-1,4-polyisoprene polymer, porous structure nanomaterial, N500 carbon black, environmentally friendly cyclohexane oil, bis-[(triethoxysilyl)-propyl] disulfide, stearic acid, chemical antioxidant, and protective wax were added to an internal mixer at 140°C for mixing. The upper bolt pressure was set to 0.6 MPa. After mixing for 20 minutes, the mixture was naturally cooled to obtain a masterbatch.

[0058] S2: Production mixing: The first stage masterbatch, oil-extended sulfur powder and accelerator are added to an internal mixer for second stage mixing. The upper ejector pressure is set to 0.5 MPa. When the temperature reaches 135°C, the glue is discharged. Example 4

[0059] The sidewall rubber composition of this embodiment includes the following components in parts by weight: 50 parts of high-vinyl butadiene polymer, 50 parts of cis-1,4-polyisoprene polymer, 6 parts of porous structure nanomaterial, 70 parts of N500 carbon black, 9 parts of environmentally friendly cyclohexane oil, 3 parts of bis-[(triethoxysilyl)-propyl] disulfide, 4 parts of stearic acid, 6 parts of chemical antioxidant, 5 parts of protective wax, 3 parts of oil-extended sulfur powder, and 5 parts of accelerator.

[0060] The sidewall rubber composition is prepared according to the following method, which includes the following steps:

[0061] S1: Non-productive mixing: High vinyl butadiene polymer, cis-1,4-polyisoprene polymer, porous structure nanomaterial, N500 carbon black, environmentally friendly cyclohexane oil, bis-[(triethoxysilyl)-propyl] disulfide, stearic acid, chemical antioxidant, and protective wax were added to an internal mixer at 135°C for mixing. The upper bolt pressure was set to 0.5 MPa. After mixing for 16 minutes, the mixture was naturally cooled to obtain a masterbatch.

[0062] S2: Production mixing: The first stage masterbatch, oil-extended sulfur powder and accelerator are added into an internal mixer for second stage mixing. The upper ejector pressure is set to 0.4 MPa. When the temperature reaches 130°C, the rubber is discharged.

[0063] Comparative Example 1

[0064] The difference between this comparative example and Example 1 is that the coordination polymerized diene rubber in the sidewall rubber composition is replaced with natural rubber, as follows:

[0065] The sidewall rubber composition of this comparative example includes the following components in parts by weight: 100 parts of natural rubber, 2 parts of porous structure nanomaterial, 35 parts of N500 carbon black, 1 part of environmentally friendly cyclohexane oil, 1 part of bis-[(triethoxysilyl)-propyl] disulfide, 1.5 parts of stearic acid, 1 part of chemical antioxidant, 1 part of protective wax, 7 parts of oil-extended sulfur powder, and 1 part of accelerator.

[0066] The sidewall rubber composition is prepared according to the following method, which includes the following steps:

[0067] S1: Non-productive mixing: cis-1,4-polybutadiene polymer, cis-1,4-polyisoprene polymer, porous structure nanomaterial, N500 carbon black, environmentally friendly cyclohexane oil, bis-[(triethoxysilyl)-propyl] disulfide, stearic acid, chemical antioxidant, and protective wax were added to an internal mixer at 100°C for mixing. The upper bolt pressure was set to 0.3 MPa. After mixing for 5 minutes, the mixture was naturally cooled to obtain a masterbatch.

[0068] S2: Production mixing: The first stage masterbatch, oil-extended sulfur powder and accelerator are added to an internal mixer for second stage mixing. The upper ejector pressure is set to 0.15 MPa. When the temperature reaches 110°C, the glue is discharged.

[0069] Comparative Example 2

[0070] The difference between this comparative example and Example 2 lies in the amount of porous structure nanomaterial added to the sidewall rubber composition, which is as follows:

[0071] The sidewall rubber composition of this comparative example includes the following components in parts by weight: 50 parts of cis-1,4-polybutadiene polymer, 50 parts of cis-1,4-polyisoprene polymer, 1 part of porous structure nanomaterial, 55 parts of bio-based carbon black, 10 parts of bio-based oil, 2.5 parts of bis-[(triethoxysilyl)-propyl] disulfide, 3.5 parts of stearic acid, 5 parts of chemical antioxidant, 4 parts of protective wax, 4 parts of oil-extended sulfur powder, and 4 parts of accelerator.

[0072] The sidewall rubber composition is prepared according to the following method, which includes the following steps:

[0073] S1: Non-productive mixing: cis-1,4-polybutadiene polymer, cis-1,4-polyisoprene polymer, porous structure nanomaterials, bio-based carbon black, bio-based oil, bis-[(triethoxysilyl)-propyl] disulfide, stearic acid, chemical antioxidant, and protective wax were added to an internal mixer at 120°C for mixing. The upper bolt pressure was set to 0.4 MPa. After mixing for 8 minutes, the mixture was naturally cooled to obtain a masterbatch.

[0074] S2: Production mixing: The first stage masterbatch, oil-extended sulfur powder and accelerator are added into an internal mixer for second stage mixing. The upper ejector pressure is set to 0.25 MPa. When the temperature reaches 120°C, the glue is discharged.

[0075] Comparative Example 3

[0076] The difference between this comparative example and Example 3 is that only coordinated polymerized diene rubber and inorganic reinforcing filler are added to the sidewall rubber composition, specifically as follows:

[0077] The sidewall rubber composition of this comparative example includes the following components in parts by weight: 50 parts of cis-1,4-polybutadiene polymer, 50 parts of cis-1,4-polyisoprene polymer, 75 parts of N500 carbon black, 20 parts of environmentally friendly cyclohexane oil, 4 parts of bis-[(triethoxysilyl)-propyl] disulfide, 6 parts of stearic acid, 10 parts of chemical antioxidant, 8 parts of protective wax, 1 part of oil-extended sulfur powder, and 7 parts of accelerator.

[0078] The sidewall rubber composition is prepared according to the following method, which includes the following steps:

[0079] S1: Non-productive mixing: Add cis-1,4-polybutadiene polymer, cis-1,4-polyisoprene polymer, N500 carbon black, environmentally friendly naphthenic oil, bis-[(triethoxysilyl)-propyl] disulfide, stearic acid, chemical antioxidant, and protective wax into an internal mixer at 140°C for mixing. The upper ram pressure is set to 0.6 MPa. After mixing for 20 minutes, cool naturally to obtain a masterbatch.

[0080] S2: Production mixing: The first stage masterbatch, oil-extended sulfur powder and accelerator are added to an internal mixer for second stage mixing. The upper ejector pressure is set to 0.5 MPa. When the temperature reaches 135°C, the glue is discharged.

[0081] Comparative Example 4

[0082] The difference between this comparative example and Example 3 lies in the temperature and pressure of the non-productive mixing, which are as follows:

[0083] The sidewall rubber composition of this comparative example includes the following components in parts by weight: 50 parts of cis-1,4-polybutadiene polymer, 50 parts of cis-1,4-polyisoprene polymer, 10 parts of porous structure nanomaterial, 75 parts of N500 carbon black, 20 parts of environmentally friendly cyclohexane oil, 4 parts of bis-[(triethoxysilyl)-propyl] disulfide, 6 parts of stearic acid, 10 parts of chemical antioxidant, 8 parts of protective wax, 1 part of oil-extended sulfur powder, and 7 parts of accelerator.

[0084] The sidewall rubber composition is prepared according to the following method, which includes the following steps:

[0085] S1: Non-productive mixing: cis-1,4-polybutadiene polymer, cis-1,4-polyisoprene polymer, porous structure nanomaterial, N500 carbon black, environmentally friendly cyclohexane oil, bis-[(triethoxysilyl)-propyl] disulfide, stearic acid, chemical antioxidant, and protective wax were added to an internal mixer at 85°C for mixing. The upper bolt pressure was set to 0.2 MPa. After mixing for 20 minutes, the mixture was naturally cooled to obtain a masterbatch.

[0086] S2: Production mixing: The first stage masterbatch, oil-extended sulfur powder and accelerator are added to an internal mixer for second stage mixing. The upper ejector pressure is set to 0.5 MPa. When the temperature reaches 135°C, the glue is discharged.

[0087] Comparative Example 5

[0088] The difference between this comparative example and Example 4 lies in the temperature and pressure of the productive mixing, which are as follows:

[0089] The sidewall rubber composition of this comparative example includes the following components in parts by weight: 50 parts of high-vinyl butadiene polymer, 50 parts of cis-1,4-polyisoprene polymer, 6 parts of porous structure nanomaterial, 70 parts of N500 carbon black, 9 parts of environmentally friendly cyclohexane oil, 3 parts of bis-[(triethoxysilyl)-propyl] disulfide, 4 parts of stearic acid, 6 parts of chemical antioxidant, 5 parts of protective wax, 3 parts of oil-extended sulfur powder, and 5 parts of accelerator.

[0090] The sidewall rubber composition is prepared according to the following method, which includes the following steps:

[0091] S1: Non-productive mixing: High vinyl butadiene polymer, cis-1,4-polyisoprene polymer, porous structure nanomaterial, N500 carbon black, environmentally friendly cyclohexane oil, bis-[(triethoxysilyl)-propyl] disulfide, stearic acid, chemical antioxidant, and protective wax were added to an internal mixer at 135°C for mixing. The upper bolt pressure was set to 0.5 MPa. After mixing for 16 minutes, the mixture was naturally cooled to obtain a masterbatch.

[0092] S2: Production mixing: Add the first stage masterbatch, oil-extended sulfur powder and accelerator into an internal mixer for second stage mixing. Set the upper ejector pressure to 0.1 MPa. When the temperature reaches 90°C, discharge the glue.

[0093] The rubber compounds prepared in Examples 1-4 and Comparative Examples 1-5 were vulcanized at 151° C. for 30 min and then subjected to relevant performance tests. The results are shown in Table 1.

[0094] Table 1

[0095]

[0096] The rubber materials prepared in Examples 1-4 and Comparative Examples 1-5 were aged at 100° C. for 48 h and then subjected to relevant performance tests. The results are shown in Table 2.

[0097] Table 2

[0098]

[0099] It can be seen from the above embodiments that the present invention provides a sidewall rubber composition, a method for preparing the sidewall rubber composition using a mixing process, and a tire.

[0100] It should be noted that the test results for Comparative Example 1 and Example 1 in Tables 1 and 2 show that the sidewall rubber composition in Comparative Example 1 contains natural rubber but does not contain the coordinated polymerized diene rubber of Example 1. This results in the rubber prepared in Comparative Example 1 exhibiting lower hardness, 300% modulus, and elongation at break after vulcanization or aging than the rubber prepared in Example 1, demonstrating that the coordinated polymerized diene rubber used in the present invention is more conducive to improving the mechanical properties of rubber. The test results for Example 1 and Comparative Example 1 in Tables 1 and 2 show that the sidewall rubber composition of the present invention exhibits superior performance.

[0101] It should be further explained that, from the comparison of the test results of Comparative Example 2-3 and Example 2-3 in Table 1 and Table 2, it can be seen that the performance of the rubber prepared by the sidewall rubber composition provided by the present invention is better, and a small amount of odor improver porous structure nanomaterial is added in Example 2-3 of the present invention, and the odor of the obtained rubber is smaller, while the amount of porous structure nanomaterial added in Comparative Example 2 exceeds the range provided by the present invention, and no porous structure nanomaterial is added in Comparative Example 3, and the fragrance level of the obtained rubber is high. The higher the fragrance level, the worse the odor, which shows that the rubber prepared in Comparative Example 2-3 has a poor odor and the odor emitted is a pungent amine odor, and the rubber prepared in Example 2-3 of the present invention has a good odor and the odor emitted is a slight fragrance. In Examples 2-3 of the present invention, while ensuring the excellent performance of the rubber prepared by the sidewall rubber composition of the present invention, only 3% of the porous structure nanomaterial by weight of the total weight of the sidewall rubber composition is added to reduce the odor of the rubber and the volatilized VOC molecules, thereby solving the problem that tire odor affects human senses and harms human health. In addition, the added porous structure nanomaterial has the advantages of abundant raw materials, low cost, and simple synthesis method.

[0102] In addition, from the comparison of the test results of Comparative Examples 4-5 and Examples 3-4 in Tables 1 and 2, it can be seen that the rubber prepared by the preparation method of the sidewall rubber composition of the present invention has better performance. The temperature and pressure when preparing the sidewall rubber composition of Comparative Examples 4-5 are beyond the range provided by the present invention, and the prepared rubber has poor performance. The hardness and elongation at break of the rubber prepared in Examples 3-4 are higher, indicating that the rubber has better flexural resistance; the 300% modulus stress value is larger, indicating that the crosslinking density of the rubber is large, and the rubber of the present invention has better performance.

[0103] In summary, the rubber and tire prepared by the sidewall rubber composition of the present invention and the preparation method provided by the present invention have better mechanical properties and flexural resistance. Compared with the prior art, the preparation process of the present invention is simple and green and environmentally friendly, the rubber has good performance and low odor, and solves the problem that tire odor affects human senses and even harms human health. At the same time, adding a small amount of odor improver will not harm human health and the environment, follows the principle of "green and environmental protection", and reduces the odor of the rubber and the volatilization of VOC molecules.

[0104] Throughout this specification, reference to terms such as "one embodiment," "some embodiments," "examples," "specific examples," or "some examples" means that the specific features, structures, materials, or characteristics described in conjunction with that embodiment or example are included in at least one embodiment or example of the present invention. Throughout this specification, schematic representations of these terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.

[0105] Although the embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and are not to be construed as limitations on the present invention. A person skilled in the art may change, modify, replace and modify the above embodiments within the scope of the present invention without departing from the principles and purpose of the present invention.

Claims

1. A sidewall rubber composition, characterized in that: Including coordination polymerized diene rubber, porous structure nanomaterials and inorganic reinforcing fillers; The added amount of the porous structure nano material is 2-10% of the mass of the coordinated polymerized diene rubber, and the added amount of the inorganic reinforcing filler is 35-75% of the mass of the coordinated polymerized diene rubber.

2. The sidewall rubber composition according to claim 1, characterized in that: The addition amount of the coordinated polymerized diene rubber is 1-100% of the total mass of the raw materials of the sidewall rubber composition, and the coordinated polymerized diene rubber is one or a mixture of cis-1,4-polybutadiene polymer, cis-1,4-polyisoprene polymer, and high-vinyl butadiene polymer.

3. The sidewall rubber composition according to claim 1, characterized in that: The raw material of the porous structure nano material is inorganic silicate and is prepared by a hydrothermal synthesis method.

4. The sidewall rubber composition according to claim 1 or 3, characterized in that: The pH value of the porous structure nanomaterial is 10-11.5, the heating loss at 80°C is 0-4.5%, the ash content is 82-86%, and the density is 1-2g / cm 3 .

5. The sidewall rubber composition according to claim 1, characterized in that: The inorganic reinforcing filler is one or more of carbon black, white carbon black, silicate and clay; The carbon black is selected from one of N100, N200, N300, N500, N600, N700, bio-based carbon black or a mixture of several thereof.

6. The sidewall rubber composition according to claim 1, characterized in that: It also includes plasticizers, silane coupling agents, stearic acid, chemical antioxidants, protective waxes and vulcanizing agents; The amount of the plasticizer added is 1-20% of the mass of the coordination polymerized diene rubber, the amount of the silane coupling agent added is 1-4% of the mass of the coordination polymerized diene rubber, the amount of the stearic acid added is 1.5-6% of the mass of the coordination polymerized diene rubber, the amount of the chemical antioxidant added is 1-10% of the mass of the coordination polymerized diene rubber, and the amount of the protective wax and the vulcanizing agent added are both 1-8% of the mass of the coordination polymerized diene rubber; The plasticizer is one or a mixture of environmentally friendly naphthenic oil, environmentally friendly alkane oil, environmentally friendly aromatic oil, and bio-based oil; The silane coupling agent is one or more of bis[3-(triethoxysilyl)propyl]tetrasulfide, bis-[(triethoxysilyl)-propyl]disulfide, and γ-mercaptopropyltrimethoxysilane.

7. The sidewall rubber composition according to claim 6, characterized in that: The vulcanizing agent includes oil-extended sulfur powder and an accelerator; The amount of the oil-extended sulfur powder added is 1-7% of the mass of the coordination polymerized diene rubber, and the amount of the accelerator added is 1-7% of the mass of the coordination polymerized diene rubber; The accelerator is one or more of N-tert-butyl-2-benzothiazole sulfenamide, N-cyclohexyl-2-benzothiazole sulfenamide, N-oxydiethylene-2-benzothiazole sulfenamide, and N-oxydiethylenethiocarbamoyl-N'-oxydiethylene sulfenamide.

8. A method for preparing the sidewall rubber composition according to any one of claims 1 to 7, characterized in that: The following steps are involved: S1: non-productive mixing: adding the coordination polymerized diene rubber, inorganic reinforcing filler, porous structure nanomaterial, plasticizer, silane coupling agent, stearic acid, chemical antioxidant, and protective wax to a first stage of internal mixer for mixing, cooling, and obtaining a masterbatch; S2: productive mixing: adding the masterbatch and the vulcanizing agent into the internal mixer at the same time, mixing in the second stage, and removing the glue.

9. The method for preparing the sidewall rubber composition according to claim 8, characterized in that: The non-productive mixing temperature is 100-140°C, the time is 5-20min, the upper push bolt pressure is 0.3-0.6Mpa, and the productive mixing upper push bolt pressure is 0.15-0.5Mpa. The glue is discharged when the temperature reaches 110-135°C.

10. A tire, characterized in that: The invention comprises the side wall rubber composition according to any one of claims 1 to 7 and / or the side wall rubber composition prepared by the method according to any one of claims 8 to 9.

Images