Rubber wet-skid-resistant material as well as preparation method and application thereof

Abstract

The invention discloses a rubber wet-skid-resistant material as well as a preparation method and application thereof, and belongs to the field of rubber additives. The invention relates to a rubber wet-skid-resistant material, which is prepared from the following raw materials by weight: 30-50 parts of a styrene-alpha-methylstyrene copolymer; 8 to 15 parts of a modified terpolymer; the modified terpolymer is formed by copolymerizing a styrene monomer, a diene monomer and 2, 6-di-tert-butyl-4-vinylphenol. The invention relates to a preparation method of a rubber wet-skid-resistant material, which comprises the following steps: carrying out copolymerization reaction on a styrene monomer, a diene monomer and 2, 6-di-tert-butyl-4-vinylphenol to obtain a modified terpolymer, and mixing a styrene-alpha-methylstyrene copolymer with the modified terpolymer to obtain the rubber wet-skid-resistant material. The method has the effect of more comprehensively and effectively improving the wet skid resistance of the rubber.

Description

Technical Field

[0001] This application relates to the field of rubber additives, and in particular to a rubber anti-slip material, its preparation method, and its application. Background Technology

[0002] Anti-weather performance is a key indicator for evaluating the performance of tires and other rubber products. It is used to improve tire grip, especially wet grip, to ensure driving safety. In addition to optimizing the tread pattern and adjusting the tread grooves, anti-weather materials can also be added to improve the tire's anti-weather performance.

[0003] Anti-skid materials mainly include terpene resins, petroleum resins, and styrene resins. Tires mostly use styrene-butadiene rubber (SBR) as the base rubber. Styrene resins have similar compatibility properties with SBR, therefore, styrene resins are widely used as anti-skid materials in tire rubber.

[0004] Although adding styrene resin can improve tire grip, tire formulations cannot do without fillers such as carbon black and silica. In rubber systems containing carbon black and silica, the addition of styrene resin often significantly increases rolling resistance, affecting the driving experience and making it difficult to improve the balance between wet grip and low rolling resistance. Summary of the Invention

[0005] In order to improve the anti-slip ability of rubber while reducing its adverse effects on rolling resistance, this application provides a rubber anti-slip material, its preparation method and application.

[0006] Firstly, the rubber anti-slip material provided in this application adopts the following technical solution: A rubber anti-slip material, made from raw materials comprising the following parts by weight: 30-50 parts of styrene-α-methylstyrene copolymer; 8-15 parts of modified terpolymer; The modified terpolymer is copolymerized from styrene monomers, diene monomers and 2,6-di-tert-butyl-4-vinylphenol.

[0007] By adopting the above technical solution, styrene-α-methylstyrene copolymer, as an anti-slip material, can increase the hysteresis of rubber, thereby playing an anti-slip role. Based on styrene-α-methylstyrene copolymer, a modified terpolymer is added. The rigidity of the benzene ring of 2,6-di-tert-butyl-4-vinylphenol forms microscopic hard points, and the structure of the two ortho-tert-butyl groups facilitates embedding into the soft segments of the rubber material, making the rubber material moderately soft and hard, increasing the grip of the material surface. Furthermore, the phenolic hydroxyl groups enhance the polarity of the anti-slip material, providing hydrogen bonds for bonding with the filler system, forming anchoring points, and improving the dispersibility of fillers such as carbon black and silica, effectively suppressing the increase of rolling resistance in the rubber material. The copolymerization of 2,6-di-tert-butyl-4-vinylphenol with styrene monomers and diene monomers not only effectively solves the problem of easy migration of small molecule monomers in rubber, but also improves the distribution characteristics of 2,6-di-tert-butyl-4-vinylphenol, increasing its compatibility with styrene-α-methylstyrene copolymer, thereby promoting improved anti-slip ability.

[0008] Optionally, in the modified terpolymer, the molar ratio of styrene monomers, diene monomers and 2,6-di-tert-butyl-4-vinylphenol is 1:(0.6~0.8):(0.15~0.25).

[0009] By adopting the above technical solution, the proportions of styrene monomers, diene monomers, and 2,6-di-tert-butyl-4-vinylphenol are controlled to control the dispersion of 2,6-di-tert-butyl-4-vinylphenol in the modified terpolymer, improve the rigidity distribution of benzene rings, and maintain moderate toughness of the copolymer, thereby better combining with styrene-α-methylstyrene copolymer and playing an anti-slip role in rubber materials.

[0010] Optionally, in the modified terpolymer, the styrene monomer includes one of styrene, α-methylstyrene, p-methylstyrene, and o-methylstyrene.

[0011] By adopting the above technical solution, the styrene monomer provides rigid support for the benzene ring, balancing the hardness and softness of the modified terpolymer.

[0012] Optionally, in the modified terpolymer, the diene monomer includes one of butadiene and isoprene.

[0013] By adopting the above technical solution, the diene monomer can effectively increase the spacing between benzene rings, which also plays a role in balancing the hardness and softness of the modified terpolymer.

[0014] Optionally, in the modified terpolymer, the styrene monomer is p-methylstyrene, and the diene monomer is isoprene.

[0015] By adopting the above technical solution, and preferably combining p-methylstyrene and isoprene, which are compatible with the structural characteristics of 2,6-di-tert-butyl-4-vinylphenol, the prepared modified terpolymer can be more stably embedded in the chain segments of rubber materials, thereby improving the anti-slip properties of rubber materials.

[0016] Optionally, the styrene content in the styrene-α-methylstyrene copolymer is 30-60 wt%.

[0017] Secondly, the preparation method of the rubber anti-slip material provided in this application adopts the following technical solution: A method for preparing a rubber anti-slip material includes the following steps: Styrene monomers, diene monomers and 2,6-di-tert-butyl-4-vinylphenol were dispersed in a first solvent to obtain a reaction mixture. The catalyst is dispersed in a second solvent to obtain a catalyst mixture; At 10~20℃, the catalyst mixture was added dropwise to the reactant mixture. After the addition was complete, the reaction continued, then the reaction was terminated, filtered, and distilled under reduced pressure to obtain the modified terpolymer. Styrene-α-methylstyrene copolymer was mixed with modified terpolymer to obtain rubber anti-slip material.

[0018] By adopting the above technical solution, copolymerization is achieved through cationic polymerization to obtain copolymers with relatively small molecular weights, which helps to be compatible and combined with styrene-α-methylstyrene copolymers. The resulting anti-slip material can be better embedded in the rubber system, thus improving its anti-slip ability.

[0019] Optionally, the first solvent and the second solvent each independently comprise one or more of toluene, xylene, cyclohexane, methylcyclohexane, dioxane, and hydrogenated solvent oil.

[0020] Optionally, the catalyst includes one or more of boron trifluoride, boron trichloride, and aluminum trichloride.

[0021] Thirdly, this application provides the application of a rubber anti-slip material in rubber products.

[0022] In summary, this application has the following beneficial effects: 1. This application, based on styrene-α-methylstyrene copolymer as an anti-slip material, adds a modified terpolymer. The rigidity of the benzene ring of 2,6-di-tert-butyl-4-vinylphenol forms microscopic hard spots, and the structure of the two ortho-tert-butyl groups facilitates embedding into the soft segments of the rubber material, resulting in a moderately soft and hard rubber material that increases surface grip. Furthermore, the phenolic hydroxyl groups can form hydrogen bonds with the rubber system, improving the dispersibility of fillers such as carbon black and silica, effectively reducing the rolling resistance of the filled rubber material. The copolymerization of 2,6-di-tert-butyl-4-vinylphenol with styrene monomers and diene monomers not only effectively solves the problem of easy migration of small molecule monomers in rubber but also improves the distribution characteristics of 2,6-di-tert-butyl-4-vinylphenol, enhancing its compatibility with styrene-α-methylstyrene copolymer, thereby promoting improved anti-slip performance.

[0023] 2. In the modified terpolymer of this application, p-methylstyrene and isoprene are preferably combined, which is compatible with the structural characteristics of 2,6-di-tert-butyl-4-vinylphenol. The modified terpolymer prepared can be more stably embedded in the chain segments of rubber materials, thereby improving the anti-slip properties of rubber materials. Detailed Implementation

[0024] The following provides a further detailed description of this application.

[0025] Example 1

[0026] A rubber anti-slip material, made from the following raw materials in parts by weight: 30 parts of styrene-α-methylstyrene copolymer and 8 parts of modified terpolymer.

[0027] The styrene-α-methylstyrene copolymer was obtained from external sources. Specifically, the styrene content in the purchased styrene-α-methylstyrene copolymer was 30 wt%, and the glass transition temperature was 46.7 °C.

[0028] The modified terpolymer is a copolymer of styrene monomers, diene monomers and 2,6-di-tert-butyl-4-vinylphenol.

[0029] In this embodiment, the styrene monomer is styrene, and the diene monomer is isoprene.

[0030] A method for preparing a rubber anti-slip material includes the following steps: Styrene monomers, diene monomers, and 2,6-di-tert-butyl-4-vinylphenol were dispersed in a first solvent to obtain a reaction mixture; wherein the molar ratio of styrene monomers, diene monomers, and 2,6-di-tert-butyl-4-vinylphenol was 1:0.6:0.15; the mass of the first solvent added was 15 times the mass of the styrene monomers added, and the first solvent was xylene.

[0031] The catalyst is dispersed in a second solvent to obtain a catalyst mixture; the catalyst is specifically aluminum trichloride; the mass of the second solvent added is 100 times the mass of the catalyst added, and the second solvent is specifically xylene.

[0032] At 10°C, the catalyst mixture was added dropwise to the reactant mixture at a mass ratio of 1:10. The addition was completed in 30 minutes, and the reaction was continued for 3 hours. Then, 2 wt% sodium hydroxide solution was added to terminate the reaction. The mixture was filtered, and the organic phase was collected and subjected to vacuum distillation to obtain the modified terpolymer.

[0033] Styrene-α-methylstyrene copolymer and modified terpolymer were fed into a two-roll hot mill in parts by weight and mixed at 110°C for 4 minutes. The mixture was then granulated to obtain a rubber anti-slip material.

[0034] Example 2

[0035] A rubber anti-slip material, made from the following raw materials in parts by weight: 50 parts of styrene-α-methylstyrene copolymer and 15 parts of modified terpolymer.

[0036] The styrene-α-methylstyrene copolymer was obtained from external sources. Specifically, the styrene content in the purchased styrene-α-methylstyrene copolymer was 30 wt%, and the glass transition temperature was 46.7 °C.

[0037] The modified terpolymer is a copolymer of styrene monomers, diene monomers and 2,6-di-tert-butyl-4-vinylphenol.

[0038] In this embodiment, the styrene monomer is styrene, and the diene monomer is isoprene.

[0039] A method for preparing a rubber anti-slip material includes the following steps: Styrene monomers, diene monomers, and 2,6-di-tert-butyl-4-vinylphenol were dispersed in a first solvent to obtain a reaction mixture; wherein the molar ratio of styrene monomers, diene monomers, and 2,6-di-tert-butyl-4-vinylphenol was 1:0.8:0.25; the mass of the first solvent added was 15 times the mass of the styrene monomers added, and the first solvent was xylene.

[0040] The catalyst is dispersed in a second solvent to obtain a catalyst mixture; the catalyst is specifically aluminum trichloride; the mass of the second solvent added is 100 times the mass of the catalyst added, and the second solvent is specifically xylene.

[0041] At 20°C, the catalyst mixture was added dropwise to the reactant mixture at a mass ratio of 1:10. The addition was completed in 30 minutes, and the reaction was continued for 3 hours. Then, 2 wt% sodium hydroxide solution was added to terminate the reaction. The mixture was filtered, and the organic phase was collected and subjected to vacuum distillation to obtain the modified terpolymer.

[0042] Styrene-α-methylstyrene copolymer and modified terpolymer were fed into a two-roll hot mill in parts by weight and mixed at 110°C for 4 minutes. The mixture was then granulated to obtain a rubber anti-slip material.

[0043] Example 3

[0044] A rubber anti-slip material, the difference between this embodiment and Embodiment 1 is that the rubber anti-slip material is made from the following raw materials in parts by weight: 42 parts of styrene-α-methylstyrene copolymer and 11.5 parts of modified terpolymer.

[0045] In the preparation of the modified terpolymer, the molar ratio of styrene monomers, diene monomers and 2,6-di-tert-butyl-4-vinylphenol is 1:0.7:0.22.

[0046] Example 4

[0047] A rubber anti-slip material, the difference between this embodiment and embodiment 1 is that in the modified terpolymer, the styrene monomer is o-methylstyrene and the diene monomer is butadiene.

[0048] Example 5

[0049] A rubber anti-slip material, the difference between this embodiment and embodiment 1 is that in the modified terpolymer, the styrene monomer is p-methylstyrene and the diene monomer is isoprene.

[0050] Comparative Example 1 This comparative example uses styrene-α-methylstyrene copolymer as the rubber anti-slip material.

[0051] The styrene-α-methylstyrene copolymer was obtained from external sources. Specifically, the styrene content in the purchased styrene-α-methylstyrene copolymer was 30 wt%, and the glass transition temperature was 46.7 °C.

[0052] Comparative Example 2 A rubber anti-slip material, the difference between this comparative example and Example 1 is that the structure of the modified terpolymer is different.

[0053] Preparation method of modified terpolymer: Styrene monomers, diene monomers, and p-allylphenol are dispersed in a first solvent to obtain a reaction mixture; wherein the molar ratio of styrene monomers, diene monomers, and p-allylphenol is 1:0.6:0.15; the mass of the first solvent added is 15 times the mass of the styrene monomers added, and the first solvent is xylene; the styrene monomer is styrene, and the diene monomer is isoprene.

[0054] The catalyst is dispersed in a second solvent to obtain a catalyst mixture; the catalyst is specifically aluminum trichloride; the mass of the second solvent added is 100 times the mass of the catalyst added, and the second solvent is specifically xylene.

[0055] At 10°C, the catalyst mixture was added dropwise to the reactant mixture at a mass ratio of 1:10. The addition was completed in 30 minutes, and the reaction was continued for 3 hours. Then, 2 wt% sodium hydroxide solution was added to terminate the reaction. The mixture was filtered, and the organic phase was collected and subjected to vacuum distillation to obtain the modified terpolymer.

[0056] Styrene-α-methylstyrene copolymer and modified terpolymer were fed into a two-roll hot mill in parts by weight and mixed at 110°C for 4 minutes. The mixture was then granulated to obtain a rubber anti-slip material.

[0057] Comparative Example 3 A rubber anti-slip material, the difference between this comparative example and Example 1 is that an equal mass of modified binary copolymer is used instead of modified terpolymer.

[0058] Preparation method of modified binary copolymer: Styrene monomers and 2,6-di-tert-butyl-4-vinylphenol were dispersed in a first solvent to obtain a reaction mixture; wherein the molar ratio of styrene monomers to 2,6-di-tert-butyl-4-vinylphenol was 1.6:0.15; the mass of the first solvent added was 15 times the mass of the styrene monomers added, and the first solvent was xylene; the styrene monomer was styrene.

[0059] The catalyst is dispersed in a second solvent to obtain a catalyst mixture; the catalyst is specifically aluminum trichloride; the mass of the second solvent added is 100 times the mass of the catalyst added, and the second solvent is specifically xylene.

[0060] At 10°C, the catalyst mixture was added dropwise to the reactant mixture at a mass ratio of 1:10. The addition was completed in 30 minutes, and the reaction continued for 3 hours. Then, 2 wt% sodium hydroxide solution was added to terminate the reaction. The mixture was filtered, and the organic phase was collected and subjected to vacuum distillation to obtain the modified binary copolymer.

[0061] Styrene-α-methylstyrene copolymer and modified binary copolymer were fed into a two-roll hot mill in parts by weight and mixed at 110°C for 4 minutes. The mixture was then granulated to obtain a rubber anti-slip material.

[0062] Application examples Application of a rubber anti-slip material in rubber products, including tires.

[0063] Tires are made from raw materials comprising the following parts by weight: 100 parts of solution-polymerized styrene-butadiene rubber, 20 parts of butadiene rubber, 15 parts of carbon black, 60 parts of silica, 5.5 parts of silane coupling agent Si69, 5 parts of antioxidant 4010NA, 1.5 parts of sulfur, 2 parts of accelerator CZ, 2 parts of accelerator DPG, and 10 parts of rubber anti-slip material.

[0064] The rubber anti-skid material can be prepared by Examples 1-5, thereby producing tires for Application Examples 1-5 respectively.

[0065] Tire manufacturing methods: Solution-polymerized styrene-butadiene rubber and butadiene rubber were fed into an internal mixer and mixed at a temperature of 90°C. After mixing for 1 minute, rubber anti-slip material was added. After another minute, silane coupling agent, carbon black, and silica were added. After another minute, the remaining raw materials were added. The temperature was raised to 140°C and mixing was continued for 3 minutes. The rubber was then discharged and passed through a two-roll mill. After resting for 1 day, the rubber compound was fed into a flat vulcanizing machine for vulcanization.

[0066] Comparative application examples Tires were prepared using the raw material ratios and preparation methods described in the application examples, except that the rubber anti-skid materials were prepared from Comparative Examples 1 to 3, thus producing Comparative Application Examples 1 to 3.

[0067] Blank example Tires are prepared using the raw material ratios and preparation methods described in the application example, except that rubber anti-skid materials are not added to the raw materials of the tires.

[0068] Performance testing Filler dispersibility test: The rubber compounds obtained from test cases 1-5, comparative application cases 1-3, and blank cases were tested using an RPA rheometer. The temperature was set at 60℃, the strain scan range was 0.3%-100%, and the frequency was 1Hz. The dispersibility of the filler was reflected by the difference between the low strain modulus and the high strain modulus of the test results. The test results are shown in Table 1.

[0069] Dynamic mechanical testing: The vulcanizates obtained from test cases 1-5, comparative application cases 1-3, and blank cases were tested using a dynamic viscoelastic spectrum analyzer. The temperature range was -60℃ to 80℃, the heating rate was 3℃ / min, and the frequency was 10Hz. The loss factor tanδ at 0℃ and the loss factor tanδ at 60℃ were obtained. The test results are shown in Table 1.

[0070] Table 1

[0071] As shown in Table 1, based on the analysis of the filler dispersibility test results, the difference between the low strain modulus and the high strain modulus can reflect the Payne effect of the system. Since the high strain modulus of the rubber compounds in various application examples is similar, the Payne effect can be reflected by the size of the low strain modulus. The smaller the low strain modulus, the weaker the Payne effect, and the better the dispersibility of silica and carbon black fillers.

[0072] Based on the analysis of dynamic mechanical test results, the loss factor tanδ at 0℃ can reflect the tire's wet grip, i.e. its anti-slip ability. The larger the tanδ at 0℃, the stronger the anti-slip ability. The loss factor tanδ at 60℃ can reflect the rolling resistance. The larger the tanδ at 60℃, the greater the rolling resistance.

[0073] Comparing Application Example 1 with Comparative Application Example 1, it can be seen that adding a modified terpolymer to styrene-α-methylstyrene copolymer as an anti-skid material effectively improves the dispersibility of the filler. Further comparison with the blank example shows that adding styrene-α-methylstyrene copolymer to a rubber system containing carbon black and silica increases tanδ at 0℃, effectively improving the tire's anti-skid ability, but also significantly increases tanδ at 60℃, increasing rolling resistance and hindering smooth driving. However, with the addition of the modified terpolymer, while tanδ increases at 0℃, the increase at 60℃ narrows, reducing the adverse effects on rolling resistance and thus improving the driving experience.

[0074] Comparing Application Example 1 with Comparative Application Examples 2-3, it can be seen that the polymerization of styrene, isoprene, and 2,6-di-tert-butyl-4-vinylphenol enables the anti-slip material to exhibit significant anti-slip capabilities. However, if styrene, isoprene, and p-allylphenol are polymerized, the lack of intercalation characteristics of the two ortho-tert-butyl groups may result in suboptimal anti-slip capabilities and failure to suppress the increase in rolling resistance. Similarly, if only styrene and 2,6-di-tert-butyl-4-vinylphenol are copolymerized, the failure to balance the hardness and softness of the modified terpolymer may lead to insufficient compatibility of the modified terpolymer with styrene-α-methylstyrene copolymer, thus also affecting the anti-slip capabilities.

[0075] By comparing Application Example 1 with Application Examples 4-5, it can be seen that when p-methylstyrene is specifically selected as the styrene monomer and isoprene is specifically selected as the diene monomer, the material has the best anti-slip ability.

[0076] This specific embodiment is merely an explanation of this application and is not intended to limit it. After reading this specification, those skilled in the art can make modifications to this specific embodiment without contributing any inventive step, but such modifications are protected by patent law as long as they fall within the scope of the claims of this application.

Claims

1. A rubber anti-slip material, characterized in that: Made from the following ingredients in parts by weight: 30-50 parts of styrene-α-methylstyrene copolymer; 8-15 parts of modified terpolymer; The modified terpolymer is copolymerized from styrene monomers, diene monomers and 2,6-di-tert-butyl-4-vinylphenol.

2. The rubber anti-slip material according to claim 1, characterized in that: In the modified terpolymer, the molar ratio of styrene monomers, diene monomers, and 2,6-di-tert-butyl-4-vinylphenol is 1:(0.6~0.8):(0.15~0.25).

3. The rubber anti-slip material according to claim 1, characterized in that: In the modified terpolymer, the styrene monomers include one of styrene, α-methylstyrene, p-methylstyrene, and o-methylstyrene.

4. The rubber anti-slip material according to claim 1, characterized in that: In the modified terpolymer, the diene monomer includes one of butadiene and isoprene.

5. The rubber anti-slip material according to claim 1, characterized in that: In the modified terpolymer, the styrene monomer is p-methylstyrene, and the diene monomer is isoprene.

6. The rubber anti-slip material according to claim 1, characterized in that: In the styrene-α-methylstyrene copolymer, the styrene content is 30~60wt%.

7. A method for preparing a rubber anti-slip material according to any one of claims 1-6, characterized in that: Includes the following steps: Styrene monomers, diene monomers and 2,6-di-tert-butyl-4-vinylphenol were dispersed in a first solvent to obtain a reaction mixture. The catalyst is dispersed in a second solvent to obtain a catalyst mixture; At 10~20℃, the catalyst mixture was added dropwise to the reactant mixture. After the addition was complete, the reaction continued, then the reaction was terminated, filtered, and distilled under reduced pressure to obtain the modified terpolymer. Styrene-α-methylstyrene copolymer was mixed with modified terpolymer to obtain rubber anti-slip material.

8. The method for preparing a rubber anti-slip material according to claim 7, characterized in that: The first solvent and the second solvent each independently include one or more of toluene, xylene, cyclohexane, methylcyclohexane, dioxane, and hydrogenated solvent oil.

9. The method for preparing a rubber anti-slip material according to claim 7, characterized in that: The catalyst includes one or more of boron trifluoride, boron trichloride, and aluminum trichloride.

10. The application of a rubber anti-slip material according to any one of claims 1-6 in rubber products.

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