Resin additive for tire rubber, tire rubber, preparation method and tire

Abstract

The invention discloses a resin additive for tire rubber, tire rubber, preparation method and tire, and relates to the field of tire rubber technology. The resin additive is composed of a modified polyolefin resin, a xylene resin, a polyester resin, an organic solvent, a modified tackifying resin and a blocked isocyanate curing agent in a weight ratio of 100: (5-20): (30-70): (200-400): (5-15): (1-2), and the unblocking temperature of the blocked isocyanate curing agent is 110-130°C. The anhydride-modified polyolefin is matched with a xylene resin having a hydroxyl group and an ether bond and a polyester resin, which can react and crosslink with the blocked isocyanate curing agent to form an interpenetrating network structure under high temperature, and the viscosity of the resin additive gradually increases, so that the bonding effect between the raw materials is better, and the risk of tire slag falling is greatly reduced.

Description

Technical Field

[0001] The invention relates to the technical field of tire rubber, and in particular to a resin additive for tire rubber, a tire rubber, a preparation method and a tire. Background Art

[0002] Tires are one of the most important components of a car. Their main function is to support the entire weight of the vehicle, bear the load of the car, transmit traction and braking torque, and ensure the adhesion between the wheels and the road. Tires are mostly made of rubber materials.

[0003] The main functions of resin in tire rubber include enhancing viscosity, preventing aging, improving processability and increasing strength. Phenolic resin commonly used in rubber rubber is a thermosetting resin with high viscosity, which increases with the extension of reaction time. The viscosity of phenolic resin is mainly related to its molecular weight and functional group density. The cross-linking links between molecules will continue to increase, forming longer molecular chains, thereby increasing the viscosity of the resin. However, as the reaction temperature increases, the viscosity of phenolic resin decreases, because at higher temperatures, the reaction rate will increase, and the chain transfer reaction will also increase, thereby reducing the molecular weight and cross-linking density of the reactants, resulting in a decrease in the viscosity of the resin. In order to ensure the bonding effect between the components in the rubber, the amount of resin added needs to be increased, but excessive resin additives may affect the physical properties and chemical stability of the rubber. It may change the cross-linking structure between rubber molecules, reduce the cohesion of the rubber, and during the use of the tire, when subjected to friction, external forces, etc., it is more likely to cause the surface material to fall off, that is, the situation of slag falling. At the same time, excessive resin additives may also affect the interaction between the rubber and other compounding ingredients, resulting in unbalanced material properties and increasing the risk of slag falling. Summary of the invention

[0004] The first technical problem to be solved by the present invention is: in view of the deficiencies in the prior art, a resin additive for tire rubber is provided, which reduces the risk of tire debris and improves tire quality.

[0005] To solve the above-mentioned first technical problem, the technical solution of the present invention is:

[0006] A resin additive for tire rubber material, the resin additive comprising a modified polyolefin resin, a xylene resin, a polyester resin, an organic solvent, a modified tackifying resin and a blocked isocyanate curing agent in a weight ratio of 100:(5-20):(30-70):(200-400):(5-15):(1-2), wherein the deblocking temperature of the blocked isocyanate curing agent is 110-130°C;

[0007] The preparation method of the modified tackifying resin is as follows: tackifying resin, diethylenetriamine and p-toluenesulfonic acid are added to toluene, and reacted at 60-80° C. for 2-4 hours to obtain the modified tackifying resin, wherein the molar ratio of the amine group in the diethylenetriamine to the active functional group of the tackifying resin is 0.5-2, the amount of toluene added accounts for 100-150% of the total volume of the tackifying resin and the diethylenetriamine, and the amount of p-toluenesulfonic acid added accounts for 0.5-2% of the mass of the tackifying resin;

[0008] The preparation method of the modified polyolefin resin comprises the following steps: adding polyolefin, methylcyclohexane, acid anhydride and diacyl peroxide in a weight ratio of 100: (300-500): (10-20): (2-5) into an autoclave, heating while stirring, reacting at 140-160° C. for 1-3 hours to obtain a reaction liquid, and cooling the reaction liquid to 40° C. to obtain the modified polyolefin resin.

[0009] Preferably, the preparation method of the polyester resin is as follows: under the catalysis of tetraisopropyl titanate, an aromatic dibasic acid, a diol and a polyamine are mixed, first reacted at a temperature of 180 to 200°C and a stirring speed of 120 to 180 r / min for 2 to 3 hours, then hydroquinone is added and reacted at 230 to 250°C and a stirring speed of 150 to 200 r / min for 1 to 2 hours, then the temperature is lowered to 150 to 170°C, antimony trioxide is added, and the reaction is carried out at a vacuum degree of -0.08 to -0.1 MPa for 3 to 5 hours to obtain a polyester resin, wherein the amount of tetraisopropyl titanate used accounts for 0.055 to 0.075% w / w of the total weight of the aromatic dibasic acid, diol and polyamine, and the amount of hydroquinone added accounts for 0.1 to 1.0% of the total weight of the aromatic dibasic acid, diol and polyamine. w / w, the amount of antimony trioxide added is 0.025-0.055% w / w of the total weight of the aromatic dibasic acid, diol and polyamine;

[0010] The organic solvent is any one of ethyl acetate, acetone, butanone, cyclohexanone, methyl isobutyl ketone, and cyclohexane, or a mixed solution of two or more thereof.

[0011] Preferably, the preparation method of the resin additive is: adding modified polyolefin resin, xylene resin, polyester resin, and modified tackifying resin to an organic solvent, heating to 30-50°C, stirring at 150-200rpm for 30-50min, continuing to add a blocked isocyanate curing agent, stirring at 120-140rpm for 40-60min, cooling to room temperature, and filtering through a 200-800 mesh filter to obtain the resin additive.

[0012] The second technical problem to be solved by the present invention is: to provide a tire rubber material in view of the deficiencies in the prior art, thereby reducing the risk of tire debris falling off and improving the quality of the tire.

[0013] To solve the above second technical problem, the technical solution of the present invention is:

[0014] A tire rubber material, comprising a tire base material, a composite coupling agent, composite carbon black, graphene oxide, an antioxidant, a dispersant, a resin additive and a vulcanizing agent in a weight ratio of 100: (1-5): (25-45): (5-15): (1-5): (0.5-3): (2-5): (1-3).

[0015] Preferably, the composite coupling agent is prepared by dissolving 3-aminopropyltrimethoxysilane and an olefin-based silane coupling agent in toluene, then adding metallic potassium and reacting at room temperature;

[0016] The molar ratio of the 3-aminopropyltrimethoxysilane to the olefin-based silane coupling agent is 1:1.05-1.1, the amount of metallic potassium added accounts for 1-3% w / w of the total weight of the 3-aminopropyltrimethoxysilane and the olefin-based silane coupling agent, and the ratio of the added volume of toluene to the total volume of the 3-aminopropyltrimethoxysilane and the olefin-based silane coupling agent is 10-30:1.

[0017] Preferably, the mass ratio of white carbon black to modified carbon black in the composite carbon black is 1-3:4-6.

[0018] Preferably, the preparation method of the modified carbon black comprises the following steps:

[0019] S1. Preprocessing

[0020] Dry the carbon black in a vacuum oven at 100-120°C for 2-4 hours to remove moisture and impurities;

[0021] S2. Oxidation treatment

[0022] Add the dried carbon black to the oxidizing solution, and stir the reaction at 50-70°C for 1-3 hours, wherein the oxidizing solution is one of hydrogen peroxide or potassium permanganate solution, the concentration of the oxidizing solution is 5%-15%wt, and the mass ratio of carbon black to hydrogen peroxide or potassium permanganate is 1:2-1:5;

[0023] S3. Coupling agent treatment

[0024] The oxidized carbon black is filtered and washed to neutrality, and then dispersed in a solution containing a coupling agent, and stirred at 60-80°C for 2-4 hours, wherein the coupling agent is one of a silane coupling agent or a titanate coupling agent, and the amount of the coupling agent is 2-8% w / w of the mass of the carbon black;

[0025] S4. Post-processing

[0026] The carbon black treated with the coupling agent is filtered and washed again, and then dried in a vacuum oven at 80-100° C. for 3-5 hours to obtain modified carbon black.

[0027] Preferably, the preparation method of the composite carbon black comprises the following steps:

[0028] S5, dispersing white carbon black and modified carbon black in ethanol or acetone, and ultrasonicating at 100-500W for 20-60min to obtain a mixed solution;

[0029] S6. Continue to add titanate coupling agent to the mixed solution, raise the temperature to 50-80°C and stir to react for 2-4h;

[0030] S7. Distill off ethanol or acetone at a temperature of 55-65°C and a pressure of less than 0.1 MPa to obtain composite carbon black.

[0031] Preferably, the amount of the titanate coupling agent added is 1-5% w / w of the total mass of the white carbon black and the modified carbon black, and the amount of the ethanol or acetone added is 2-3 times the total mass of the white carbon black and the modified carbon black.

[0032] The third technical problem to be solved by the present invention is: to provide a tire with good quality and not easy to fall off in view of the shortcomings of the prior art.

[0033] Due to the adoption of the above technical solution, the beneficial effects of the present invention are:

[0034] 1. The present invention introduces diethylenetriamine containing multiple functional groups into the tackifying resin molecule to form a branched molecular structure. The branched structure can make the arrangement between the molecular chains loose, reduce the friction between the molecular chains, and further reduce the viscosity of the tackifying resin, so that the resin additive can be better mixed with the other raw materials during the mixing process of the tire rubber compound, and the materials are mixed evenly, which is convenient for the bonding between the raw materials in the later stage; and the anhydride-modified polyolefin is matched with the xylene resin having hydroxyl groups and ether bonds and the polyester resin, which can react and cross-link with the blocked isocyanate curing agent under high temperature to form an interpenetrating network structure, and the viscosity of the resin additive gradually increases, so that the bonding effect between the raw materials is better, and the risk of tire slag falling is greatly reduced.

[0035] 2. The polarity of polyolefin itself is relatively weak, but its polarity increases after modification, which can significantly improve its compatibility with other raw materials in rubber compounds, enhance the interfacial bonding force of rubber compounds, and greatly improve the mechanical properties.

[0036] 3. Polyester resin can enhance the skeleton structure of the tire. It can be added to the tire cord layer as a reinforcing material, tightly combined with the rubber matrix, and enhance the cohesion and intermolecular force of the rubber. Its higher strength and modulus can effectively resist the tensile and bending stresses to which the tire is subjected during driving, which helps to maintain the shape of the tire and improve the load-bearing capacity of the tire. In the present invention, aromatic dibasic acids are used as the production raw materials of polyester resin. Due to the rigid structure of the benzene ring, the rigidity of the polyester resin molecular chain is increased. The enhancement of the rigidity of the molecular chain can improve the tensile strength, bending strength and modulus of the resin. This is like adding a solid support part to the "molecular skeleton" of the polyester resin, allowing the polyester resin to withstand greater external forces and enhancing the stability of the tire.

[0037] 4. The composite coupling agent obtained by the nucleophilic addition reaction of 3-aminopropyltrimethoxysilane and olefin-based silane coupling agent has a long silane chain with sulfur-containing group branches, which can reduce the generation of alcohols and COC volatiles during tire rubber mixing, avoid the appearance of a large number of voids in tire products, improve the quality of tires, and greatly reduce the possibility of tire debris.

[0038] 5. White carbon black and carbon black have different surface properties and different dispersibility in rubber matrix materials. The present invention improves the surface activity and dispersibility of carbon black by modifying the carbon black, and through the bridge effect of the titanate coupling agent, the dispersion of carbon black and white carbon black in the rubber matrix material is more uniform, and the bonding force between the carbon black and the rubber is enhanced, which helps to prevent local differences in tire performance caused by uneven dispersion, such as uneven changes in properties such as hardness and tensile strength, and improves the quality of the tire. DETAILED DESCRIPTION

[0039] The present invention will be further described below in conjunction with the embodiments. Example 1

[0040] Preparation of modified polyolefin resin: 100 g of polypropylene, 300 g of methylcyclohexane, 10 g of maleic anhydride and 2 g of diacyl peroxide were added into an autoclave, heated with stirring, reacted at 140° C. for 3 h, and cooled to 40° C. to obtain modified polyolefin resin.

[0041] Preparation of modified tackifying resin: terpene resin, diethylenetriamine (the molar ratio of amine group to active functional group of terpene resin is 0.5) and p-toluenesulfonic acid (accounting for 0.5% of the mass of tackifying resin) are added to toluene accounting for 100% of the total volume of terpene resin and diethylenetriamine, and reacted at 60°C for 4 hours to obtain the obtained product.

[0042] Preparation of polyester resin: Under the catalysis of tetraisopropyl titanate (accounting for 0.055% w / w of the total weight of phthalic acid, 1,6-hexanediol and ethylenediamine), phthalic acid, 1,6-hexanediol and ethylenediamine are mixed, first reacted at 180°C and stirring speed of 120r / min for 3h, 0.1% w / w of hydroquinone accounting for the total weight is added, and the reaction is carried out at 230°C and stirring speed of 150r / min for 2h, the temperature is lowered to 150°C, 0.025% w / w of antimony trioxide accounting for the total weight is added, and the reaction is carried out at a vacuum degree of -0.08MPa for 5h to obtain.

[0043] Take modified polyolefin resin, xylene resin, polyester resin, ethyl acetate, modified tackifying resin and blocked isocyanate curing agent (unblocking temperature 110°C) in a weight ratio of 100:5:30:200:5:1. Add modified polyolefin resin, xylene resin, polyester resin and modified tackifying resin to ethyl acetate, heat to 30°C, stir at 150rpm for 50min, add blocked isocyanate curing agent, stir at 120rpm for 60min, cool to room temperature, and filter through a 200-mesh filter to obtain resin additive. Example 2

[0044] Preparation of modified polyolefin resin: 100 g of polybutene, 400 g of methylcyclohexane, 15 g of maleic anhydride and 3.5 g of diacyl peroxide were added into an autoclave, heated with stirring, reacted at 150° C. for 2 h, and then cooled to 40° C. to obtain modified polyolefin resin.

[0045] Preparation of modified tackifying resin: The molar ratio of amine groups in diethylenetriamine to active functional groups of alkylphenol-formaldehyde resin is 1.2, p-toluenesulfonic acid accounts for 1.5% of the mass of alkylphenol-formaldehyde resin, the volume of toluene accounts for 125% of the total volume, and the product is prepared by reaction at 70°C for 3 hours.

[0046] Preparation of polyester resin: tetraisopropyl titanate 0.065% w / w, hydroquinone 0.5% w / w, antimony trioxide 0.035% w / w, reaction conditions are 190℃, 150r / min for 2.5h, after adding hydroquinone, react at 240℃, 170r / min for 1.5h, cool to 160℃, add antimony trioxide, vacuum degree -0.09MPa and react for 4h.

[0047] Take a mixed solution of modified polyolefin resin, xylene resin, polyester resin, acetone and butanone (mixed in equal volumes), modified tackifying resin and blocked isocyanate curing agent in a weight ratio of 100:12:50:300:10:1.5, stir at 35°C and 170rpm for 40min, add blocked isocyanate curing agent and stir at 130rpm for 50min, filter through a 500-mesh filter to obtain a resin additive, wherein the deblocking temperature of the blocked isocyanate curing agent is 120°C. Example 3

[0048] Preparation of modified polyolefin resin: 100 g of polyethylene, 500 g of methylcyclohexane, 20 g of maleic anhydride and 5 g of diacyl peroxide were added into an autoclave, heated with stirring, reacted at 160° C. for 1 h, and cooled to 40° C. to obtain modified polyolefin resin.

[0049] Preparation of modified tackifying resin: The molar ratio of amine groups in diethylenetriamine to active functional groups of β-terpene resin is 2, p-toluenesulfonic acid accounts for 2% of the mass of alkylphenol-formaldehyde resin, the volume of toluene accounts for 150% of the total volume, and the product is prepared by reaction at 80°C for 2h.

[0050] Preparation of polyester resin: tetraisopropyl titanate 0.075% w / w, hydroquinone 1.0% w / w, antimony trioxide 0.055% w / w, reaction conditions are 200℃, 180r / min for 2h, after adding hydroquinone, react at 250℃, 200r / min for 1h, cool to 170℃, add antimony trioxide, vacuum degree -0.09MPa and react for 4h.

[0051] Take a mixed solution of modified polyolefin resin, xylene resin, polyester resin, cyclohexanone, methyl isobutyl ketone and cyclohexane (mixed in equal volumes), modified tackifying resin and blocked isocyanate curing agent (unblocking temperature 130°C) in a weight ratio of 100:20:70:400:15:2. Add the modified polyolefin resin, xylene resin, polyester resin and modified tackifying resin to the mixed solution of cyclohexanone, methyl isobutyl ketone and cyclohexane, heat to 50°C, stir at 200rpm for 30min, add blocked isocyanate curing agent, stir at 140rpm for 40min, cool to room temperature, and filter through an 800-mesh filter to obtain the resin additive. Example 4

[0052] Tire base material (a mixture of natural rubber and isoprene rubber, where the mass ratio of natural rubber to isoprene rubber is 1:1): 100g

[0053] Composite coupling agent: 3g

[0054] First, according to the molar ratio of 3-aminopropyltrimethoxysilane to vinyltrimethoxysilane being 1:1.05, a certain amount of 3-aminopropyltrimethoxysilane and vinyltrimethoxysilane were weighed and dissolved in toluene, and the ratio of the added volume of toluene to the total volume of 3-aminopropyltrimethoxysilane and vinyltrimethoxysilane was 20:1. Then, potassium metal was added, and the amount of potassium metal added accounted for 2% w / w of the total weight of 3-aminopropyltrimethoxysilane and vinyltrimethoxysilane, and the composite coupling agent was prepared by reaction at room temperature.

[0055] Composite carbon black: 35g

[0056] Preparation method of modified carbon black:

[0057] S1: Dry carbon black N550 in a vacuum oven at 110 °C for 3 h to remove moisture and impurities;

[0058] S2: Add the dried carbon black to a 10%wt hydrogen peroxide solution (the mass ratio of carbon black to hydrogen peroxide is 1:3), stir and react at 60°C for 2h to introduce oxygen-containing functional groups on the surface of the carbon black;

[0059] S3: The oxidized carbon black is filtered and washed to neutrality, and then dispersed in a solution containing a silane coupling agent (the amount of the silane coupling agent is 5% w / w of the mass of the carbon black), and stirred at 70°C for 3 hours;

[0060] S4: The carbon black treated with the coupling agent is filtered and washed again, and then dried in a vacuum oven at 90° C. for 4 h to obtain modified carbon black.

[0061] Preparation method of composite carbon black:

[0062] Take 1 / 5 of the mass of modified carbon black with white carbon black HS-10, disperse the white carbon black and modified carbon black in ethanol, the amount of ethanol added is 2.5 times the total mass of white carbon black and modified carbon black, and ultrasonicate at 300W for 40min to obtain a mixed solution;

[0063] Continue to add titanate coupling agent to the mixed solution, the amount of titanate coupling agent added accounts for 3% w / w of the total mass of white carbon black and modified carbon black, heat to 65°C and stir to react for 3h;

[0064] Ethanol was distilled off at a temperature of 60°C and a pressure of <0.1MPa to obtain composite carbon black.

[0065] Graphene oxide: 10g

[0066] Hindered phenolic antioxidant: 3g

[0067] Dispersant: 1.5g (zinc stearate: 1.0g, polyethylene wax: 0.5g)

[0068] Resin additive in Example 1: 3.5 g

[0069] Vulcanizing agent: 2g (phenolic resin vulcanizing agent: 0.5g, sulfur: 1g, diisopropylbenzene peroxide vulcanizing agent: 0.5g). Example 5

[0070] Tire base material: 100g

[0071] Composite coupling agent: 5g

[0072] According to the molar ratio of 3-aminopropyltrimethoxysilane to vinyltrimethoxysilane being 1:1.08, two coupling agents were weighed and dissolved in toluene, and the ratio of the added volume of toluene to the total volume of 3-aminopropyltrimethoxysilane and vinyltrimethoxysilane was 10:1. Then, metallic potassium was added, and the amount of metallic potassium added accounted for 1% w / w of the total weight of 3-aminopropyltrimethoxysilane and vinyltrimethoxysilane, and the composite coupling agent was prepared by reaction at room temperature.

[0073] Composite carbon black: 45g

[0074] Preparation method of modified carbon black:

[0075] S1: Dry carbon black N550 in a vacuum oven at 100 °C for 4 h to remove moisture and impurities;

[0076] S2: Add the dried carbon black into a 15%wt potassium permanganate solution (the mass ratio of carbon black to potassium permanganate is 1:5), stir and react at 50°C for 3h to introduce oxygen-containing functional groups on the surface of the carbon black;

[0077] S3: The oxidized carbon black is filtered and washed to neutrality, and then dispersed in a solution containing a titanate coupling agent (the amount of the titanate coupling agent is 6% w / w of the mass of the carbon black), and stirred at 65°C for 3.5 hours;

[0078] S4: The carbon black treated with the coupling agent is filtered and washed again, and then dried in a vacuum oven at 80° C. for 5 h to obtain modified carbon black.

[0079] Preparation method of composite carbon black:

[0080] 3 / 4 of the mass of the modified carbon black was taken as white carbon black HS-10, and the white carbon black and the modified carbon black were dispersed in acetone. The amount of acetone added was twice the total mass of the white carbon black and the modified carbon black, and ultrasonicated at 100 W for 60 min to obtain a mixed solution;

[0081] Continue to add titanate coupling agent to the mixed solution, the amount of titanate coupling agent added accounts for 1% w / w of the total mass of white carbon black and modified carbon black, heat to 80°C and stir to react for 2h;

[0082] Acetone was distilled off at a temperature of 58°C and a pressure of <0.1 MPa to obtain composite carbon black.

[0083] Graphene oxide: 15g

[0084] Hindered phenol antioxidant: 1g

[0085] Dispersant: 3g (zinc stearate: 1.5g, polyethylene wax: 1.5g)

[0086] Resin additive in Example 2: 2 g

[0087] Vulcanizing agent: 1g (phenolic resin vulcanizing agent: 0.5g, sulfur: 0.5g, dicumyl peroxide vulcanizing agent: 0.5g). Example 6

[0088] Tire base material: 100g

[0089] Composite coupling agent: 2g

[0090] According to the molar ratio of 3-aminopropyltrimethoxysilane to vinyltrimethoxysilane being 1:1.1, two coupling agents were weighed and dissolved in toluene, and the ratio of the added volume of toluene to the total volume of 3-aminopropyltrimethoxysilane and vinyltrimethoxysilane was 30:1. Then, potassium metal was added, and the amount of potassium metal added accounted for 3% w / w of the total weight of 3-aminopropyltrimethoxysilane and vinyltrimethoxysilane, and the composite coupling agent was prepared by reaction at room temperature.

[0091] Composite carbon black: 25g

[0092] Preparation method of modified carbon black:

[0093] S1: Dry carbon black N550 in a vacuum oven at 120 °C for 2 h to remove moisture and impurities;

[0094] S2: Add the dried carbon black into a 5%wt hydrogen peroxide solution (the mass ratio of carbon black to hydrogen peroxide is 1:2), stir and react at 70°C for 1h to introduce oxygen-containing functional groups on the surface of the carbon black;

[0095] S3: The oxidized carbon black was filtered and washed to neutrality, and then dispersed in a solution containing a silane coupling agent (the amount of the silane coupling agent was 4% w / w of the mass of the carbon black), and stirred at 75°C for 2.5 hours;

[0096] S4: The carbon black treated with the coupling agent is filtered and washed again, and then dried in a vacuum oven at 100° C. for 3 h to obtain modified carbon black.

[0097] Preparation method of composite carbon black:

[0098] 1 / 6 of the mass of the modified carbon black was taken as white carbon black HS-10, and the white carbon black and the modified carbon black were dispersed in ethanol. The amount of ethanol added was 3 times the total mass of the white carbon black and the modified carbon black. Ultrasonic treatment was performed at 500 W for 20 min to obtain a mixed solution.

[0099] Continue to add titanate coupling agent to the mixed solution, the amount of titanate coupling agent added accounts for 5% w / w of the total mass of white carbon black and modified carbon black, heat to 50°C and stir to react for 4 hours;

[0100] Ethanol was distilled off at a temperature of 62°C and a pressure of <0.1 MPa to obtain composite carbon black.

[0101] Graphene oxide: 5g

[0102] Hindered phenolic antioxidant: 5g

[0103] Dispersant: 0.5g (zinc stearate: 0.25g, polyethylene wax: 0.25g)

[0104] Resin additive in Example 3: 5g

[0105] Vulcanizing agent: 3g (phenolic resin vulcanizing agent: 1g, sulfur: 1g, diisopropylbenzene peroxide vulcanizing agent: 1g). Example 7

[0106] The method for preparing the tire rubber material in Examples 4-6 comprises the following steps:

[0107] Put the tire base material into the internal mixer and start plasticating. Stir at 50-80℃ and 30-50rpm for 5-15min.

[0108] Add the composite coupling agent and graphene oxide to the internal mixer, raise the temperature of the internal mixer to 80-120°C, and continue mixing for 5-10 minutes to allow the composite coupling agent and graphene oxide to be evenly dispersed in the tire base material. The composite coupling agent can improve the interface bonding between the tire base material and the composite carbon black, while graphene oxide can enhance the mechanical properties and thermal conductivity of the rubber compound.

[0109] Next, add the composite carbon black into the internal mixer three times to avoid adding too much at one time, which will cause uneven mixing. Adjust the temperature of the internal mixer to 120-150℃ and mix for 10-20 minutes. During the mixing process, the uniform dispersion of carbon black is crucial to the performance of the rubber compound, which can significantly improve the strength, wear resistance and tear resistance of the tire.

[0110] Continue to add antioxidants and dispersants. Keep the mixing temperature at 120-150℃ and the mixing time at 3-8min to ensure that the antioxidants and dispersants are evenly dispersed. The function of antioxidants is to prevent the rubber from aging due to oxidation during subsequent processing and use, thereby extending the service life of the tire; dispersants help various additives to be better dispersed in the rubber compound.

[0111] Subsequently, the resin additive is added, and the mixing temperature and time are 120-150° C. and 3-8 min respectively, so that the resin additive is fully mixed with other components.

[0112] Finally, add the vulcanizer, control the mixing temperature at 120-150℃, and mix for about 3-8 minutes to ensure that the vulcanizer is evenly dispersed. The vulcanization process can form a cross-linked network in the rubber compound, giving the tire its final shape and performance.

[0113] When all the raw materials are fully and evenly mixed, the rubber compound is discharged from the internal mixer and pressed into a rubber sheet through an open mixer. The rubber sheet is then placed on a cooling rack to cool naturally or quickly cooled by air cooling, water cooling, etc. to obtain a tire rubber compound. Comparative Example 1

[0114] The resin auxiliary agent was replaced with terpene resin, and the rest was exactly the same as in Example 4. Comparative Example 2

[0115] The modified polyolefin resin in the resin additive is replaced by polypropylene, and the rest is exactly the same as in Example 4. Comparative Example 3

[0116] No polyester resin was added to the resin additive, and the rest was exactly the same as in Example 4. Comparative Example 4

[0117] The composite coupling agent was replaced with 3-aminopropyltrimethoxysilane, and the rest was exactly the same as in Example 4. Comparative Example 5

[0118] The composite coupling agent is replaced by an olefin-based silane coupling agent, and the rest is exactly the same as in Example 4. Comparative Example 6

[0119] The carbon black in the preparation process of the composite carbon black was not modified, and the rest was exactly the same as in Example 4. Comparative Example 7

[0120] The composite carbon black was replaced by carbon black N550, and the rest was exactly the same as in Example 4. Comparative Example 8

[0121] The composite carbon black was replaced by white carbon black HS-10, and the rest was exactly the same as in Example 4.

[0122] The tire rubber materials in Examples 4-6 and Comparative Examples 1-8 were tested for performance, and the results are shown in Table 1:

[0123] Table 1

[0124]

[0125] Through the above table, it can be seen from the data in Comparative Examples 1-3 that the resin additive has a significant effect on various indicators of tire rubber. The modified polyolefin resin in the resin additive is replaced by polypropylene, which has less constraint on the rubber molecular chain. The rubber molecular chain can stretch and move more freely when subjected to force, thereby improving the elongation at break. No polyester resin is added to the resin additive, and the activity of the rubber molecular chain is relatively enhanced, and the elongation at break is also increased. It can be seen from Comparative Examples 4-5 that a single coupling agent has a greater effect on the porosity of the tire rubber. It can be seen from Comparative Examples 6-8 that carbon black modification can greatly improve the various properties of the tire rubber. However, when unmodified carbon black or white carbon black is used alone, its surface properties are relatively inert, and its compatibility with rubber is relatively poor. It is easy to agglomerate during the mixing process, resulting in an increase in the difficulty of dispersing carbon black in the rubber. In order to achieve a good dispersion effect, a longer mixing time and a higher shear force are required, which will increase the bonding strength of the rubber.

[0126] It should be understood that these embodiments are only used to illustrate the present invention and are not used to limit the scope of the present invention. In addition, it should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope limited by the appended claims of the application.

Claims

1. A tire rubber material, characterized in that: The tire rubber material is composed of a tire base material, a composite coupling agent, composite carbon black, graphene oxide, an antioxidant, a dispersant, a resin additive and a vulcanizing agent in a weight ratio of 100: (1-5): (25-45): (5-15): (1-5): (0.5-3): (2-5): (1-3); The resin additive is composed of a modified polyolefin resin, a xylene resin, a polyester resin, an organic solvent, a modified tackifying resin and a blocked isocyanate curing agent in a weight ratio of 100: (5-20): (30-70): (200-400): (5-15): (1-2), wherein the deblocking temperature of the blocked isocyanate curing agent is 110-130° C.; The preparation method of the modified tackifying resin is as follows: tackifying resin, diethylenetriamine and p-toluenesulfonic acid are added to toluene, and reacted at 60-80° C. for 2-4 hours to obtain the modified tackifying resin, wherein the molar ratio of the amine group in the diethylenetriamine to the active functional group of the tackifying resin is 0.5-2, the amount of toluene added accounts for 100-150% of the total volume of the tackifying resin and the diethylenetriamine, and the amount of p-toluenesulfonic acid added accounts for 0.5-2% of the mass of the tackifying resin; The preparation method of the modified polyolefin resin comprises: adding polyolefin, methylcyclohexane, acid anhydride and diacyl peroxide in a weight ratio of 100: (300-500): (10-20): (2-5) into an autoclave, heating while stirring, reacting at 140-160° C. for 1-3 hours to obtain a reaction liquid, cooling the reaction liquid to 40° C. to obtain the modified polyolefin resin; The preparation method of the resin additive is as follows: adding modified polyolefin resin, xylene resin, polyester resin and modified tackifying resin into an organic solvent, heating to 30-50° C., stirring at 150-200 rpm for 30-50 min, continuously adding a blocked isocyanate curing agent, stirring at 120-140 rpm for 40-60 min, cooling to room temperature, filtering through a 200-800 mesh filter to obtain the resin additive; The composite coupling agent is prepared by dissolving 3-aminopropyltrimethoxysilane and an olefin-based silane coupling agent in toluene, then adding metallic potassium and reacting at room temperature; The molar ratio of the 3-aminopropyltrimethoxysilane to the olefin-based silane coupling agent is 1:1.05-1.1, the amount of potassium metal added accounts for 1-3% w / w of the total weight of the 3-aminopropyltrimethoxysilane and the olefin-based silane coupling agent, and the ratio of the added volume of toluene to the total volume of the 3-aminopropyltrimethoxysilane and the olefin-based silane coupling agent is 10-30:1; The mass ratio of white carbon black to modified carbon black in the composite carbon black is 1-3:4-6, wherein the preparation method of the modified carbon black comprises the following steps: S1. Preprocessing Dry the carbon black in a vacuum oven at 100-120°C for 2-4 hours to remove moisture and impurities; S2. Oxidation treatment Add the dried carbon black to the oxidizing solution, and stir the reaction at 50-70°C for 1-3 hours, wherein the oxidizing solution is one of hydrogen peroxide or potassium permanganate solution, the concentration of the oxidizing solution is 5%-15%wt, and the mass ratio of carbon black to hydrogen peroxide or potassium permanganate is 1:2-1:5; S3. Coupling agent treatment The oxidized carbon black is filtered and washed to neutrality, and then dispersed in a solution containing a coupling agent, and stirred at 60-80°C for 2-4 hours, wherein the coupling agent is one of a silane coupling agent or a titanate coupling agent, and the amount of the coupling agent is 2-8% w / w of the mass of the carbon black; S4. Post-processing The carbon black treated with the coupling agent is filtered and washed again, and then dried in a vacuum oven at 80-100° C. for 3-5 hours to obtain modified carbon black; The preparation method of the composite carbon black comprises the following steps: S5, dispersing white carbon black and modified carbon black in ethanol or acetone, and ultrasonicating at 100-500W for 20-60min to obtain a mixed solution; S6. Continue to add titanate coupling agent to the mixed solution, raise the temperature to 50-80°C and stir to react for 2-4h; S7. Distill off ethanol or acetone at a temperature of 55-65°C and a pressure of less than 0.1 MPa to obtain composite carbon black.

2. A tire rubber material according to claim 1, characterized in that: The preparation method of the polyester resin is as follows: under the catalysis of tetraisopropyl titanate, an aromatic dibasic acid, a diol and a polyamine are mixed, and the mixture is first reacted at a temperature of 180 to 200° C. and a stirring speed of 120 to 180 r / min for 2 to 3 hours, and then hydroquinone is added to react at a temperature of 230 to 250° C. and a stirring speed of 150 to 200 r / min for 1 to 2 hours, and then the temperature is lowered to 150 to 170° C., antimony trioxide is added, and the mixture is reacted at a vacuum degree of -0.08 to -0.1 MPa for 3 to 5 hours to obtain the polyester resin, wherein the amount of tetraisopropyl titanate used accounts for 0.055 to 0.075% w / w of the total weight of the aromatic dibasic acid, the diol and the polyamine, and the amount of hydroquinone added accounts for 0.1 to 1.0% of the total weight of the aromatic dibasic acid, the diol and the polyamine. w / w, the amount of antimony trioxide added is 0.025-0.055% w / w of the total weight of the aromatic dibasic acid, diol and polyamine; The organic solvent is any one of ethyl acetate, acetone, butanone, cyclohexanone, methyl isobutyl ketone, and cyclohexane, or a mixed solution of two or more thereof.

3. A tire rubber material according to claim 1, characterized in that: The amount of the titanate coupling agent added is 1-5% w / w of the total mass of the white carbon black and the modified carbon black, and the amount of the ethanol or acetone added is 2-3 times the total mass of the white carbon black and the modified carbon black.

4. A tire, characterized in that: A tire rubber material comprising the tire rubber material according to any one of claims 1 to 3.

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