High-performance tire tread material as well as preparation method and application thereof

Abstract

The invention provides a high-performance tire tread material as well as a preparation method and application thereof. The high-performance tire tread material is prepared from the following raw materials: functionalized solution polymerized styrene-butadiene rubber, epoxidized rubber, filler, an activating agent, an anti-aging agent, a plasticizer, an accelerant and a vulcanizing agent. The composition comprises the following components in parts by weight: 50-95 parts of functionalized solution polymerized styrene-butadiene rubber based on the total weight of the functionalized solution polymerized styrene-butadiene rubber and the epoxidized rubber being 100 parts; 5-50 parts by weight of epoxidized rubber; the functional group of the functionalized solution polymerized styrene-butadiene rubber is at least one of siloxane group, amido, carboxyl, ester group, hydroxyl, acylamino, sulfur-containing group and perfluoroalkyl. The prepared high-performance tire tread material can be used for preparing green tire treads, has lower rolling resistance and heat generation and higher elongation at break, and improves wet skid resistance and wear resistance.

Description

Technical Field

[0001] The present invention relates to the technical field of composite materials. Further, it relates to a high-performance tire tread material, its preparation method and application. Background Art

[0002] With the successive implementation of the EU REACH regulation and the tire labeling regulation, tire products must focus on solving three important problems: safety, environmental protection and energy conservation. Such tires are called "green tires", and their main characteristics are high wet grip, high wear resistance and low rolling resistance.

[0003] The surface of the filler contains a large number of hydroxyl groups, which are easily agglomerated with each other through hydrogen bonds, and it is very difficult to be uniformly dispersed in the non-polar rubber matrix. Moreover, it is easy to form stress concentration points in the matrix, seriously affecting the comprehensive performance of rubber products. The prior art usually adopts the method of surface modification of the filler with a silane coupling agent or functionalization modification of the non-polar rubber to solve the above problems. According to the position of the functional group in the rubber chain, it can be divided into chain-end functionalization and in-chain functionalization. Among them, the in-chain functional group can effectively improve the compatibility between the reinforcing filler and the rubber through polar interaction or chemical connection. More importantly, the modification of the reinforcing filler by the in-chain functionalized rubber not only inhibits the filler-filler network, but also enhances the filler-rubber network during the mixing process, effectively inhibiting the transformation of the filler-filler network during storage and the initial stage of vulcanization, and thus being beneficial to the improvement of the comprehensive performance of the rubber, so that it can be better applied to high-performance tires.

[0004] In the tire industry, generally two or more rubbers are used as the matrix for mixing to meet the requirements of high-performance tire treads. Chinese invention patent CN111218038A discloses an environmentally friendly radial tire with low rolling resistance prepared from solution styrene-butadiene rubber, smoked sheet rubber, cis-1,4-polybutadiene rubber, silica and carbon black; Chinese invention patent CN116903945A discloses a tread rubber with high wet grip prepared from natural rubber, styrene-butadiene rubber, cis-1,4-polybutadiene rubber, environmentally friendly recycled rubber and silica; Zhang Tiezhu et al. (China Rubber Industry, 2020, 67(04): 439-442.) proposed a tire tread rubber formulation with better wet grip performance based on styrene-butadiene rubber and cis-1,4-polybutadiene rubber as the main body.

[0005] In the blend composite filler system of functionalized solution styrene-butadiene rubber and other non-polar rubbers, the functionalized solution styrene-butadiene rubber enhances the interaction between the rubber and the filler through functional groups. There is less filler distribution in the non-polar rubber, resulting in poor dispersibility and affecting the performance of the tread rubber. Therefore, it is necessary to increase the polarity of the blend rubber to improve the performance of the tread rubber. After epoxidation modification of other rubbers, the epoxy group can react with the hydroxyl groups on the surface of the filler, thereby improving the dispersion of the filler in the rubber matrix and obtaining a tread rubber with excellent performance. Summary of the Invention

[0006] In order to solve the technical problems existing in the prior art, the present invention provides a high-performance tire tread material, a preparation method thereof and an application thereof.

[0007] The present invention uses the prepared functionalized solution-polymerized styrene-butadiene rubber and epoxidized rubber for blending modification to prepare a blended rubber composite material with excellent properties, which can be used for preparing the tread of green tires. The green tire tread is mainly composed of functionalized solution-polymerized styrene-butadiene rubber, and epoxidized rubber is used as the rubber matrix. When applied to the tire tread, it has lower rolling resistance, higher wet skid resistance and wear resistance. The raw materials used in the present invention are widely sourced and the process is simple, which can meet the requirements of the existing tire industrial production.

[0008] One of the purposes of the present invention is to provide a high-performance tire tread material.

[0009] The high-performance tire tread material is prepared from raw materials including functionalized solution-polymerized styrene-butadiene rubber, epoxidized rubber, filler, activator, antioxidant, plasticizer, accelerator and vulcanizing agent;

[0010] Based on the total amount of functionalized solution-polymerized styrene-butadiene rubber and epoxidized rubber being 100 parts by weight,

[0011]

[0012]

[0013] Among them, it includes 50-95 parts by weight of functionalized solution-polymerized styrene-butadiene rubber; preferably 60-90 parts by weight; 5-50 parts by weight of epoxidized rubber; preferably 10-40 parts by weight;

[0014] The functional group of the functionalized solution-polymerized styrene-butadiene rubber is at least one of siloxanyl group, amino group, carboxyl group, ester group, hydroxyl group, amide group, sulfur-containing group, perfluorinated alkyl group.

[0015] In a preferred embodiment of the present invention,

[0016] The functionalized solution-polymerized styrene-butadiene rubber is chain-end functionalized solution-polymerized styrene-butadiene rubber or chain-middle functionalized solution-polymerized styrene-butadiene rubber; preferably,

[0017] The chain-end functionalized solution-polymerized styrene-butadiene rubber is obtained by copolymerization of functionalized monomers. The chain-end functionalized solution-polymerized styrene-butadiene rubber is mostly commercially available, such as solution-polymerized styrene-butadiene rubber 5251H, solution-polymerized styrene-butadiene rubber 5360H, solution-polymerized styrene-butadiene rubber 5260H, solution-polymerized styrene-butadiene rubber 5271H, solution-polymerized styrene-butadiene rubber 6440H of Kumho in South Korea, solution-polymerized styrene-butadiene rubber 4602 of Trinseo in the United States, and solution-polymerized styrene-butadiene rubber 2466 of Taian in Taiwan;

[0018] The functionalized solution-polymerized styrene-butadiene rubber in the chain is obtained by functionalization modification, more preferably by thiol-ene click chemical reaction.

[0019] In a preferred embodiment of the present invention,

[0020] The functionalized solution-polymerized styrene-butadiene rubber in the chain is prepared by uniformly mixing raw materials including solution-polymerized styrene-butadiene rubber and polyfunctional thiol reagents by heat treatment; preferably, the molar ratio of the polyfunctional thiol reagent to the rubber double bond is (0.01-0.9):1, more preferably (0.03-0.55):1.

[0021] In a preferred embodiment of the present invention,

[0022] The polyfunctional thiol reagent has at least one of siloxanyl, amino, carboxyl, ester group, hydroxyl functional groups and a thiol functional group; preferably at least one of 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, ethyl mercaptoacetate, methyl mercaptoacetate, mercaptoethanol, 3-mercaptopropanol, 3-mercaptopropionic acid, mercaptoundecanoic acid, cysteine, mercaptosuccinic acid, mercaptoethylamine;

[0023] The heat treatment temperature is 40°C to 160°C; preferably 80°C to 140°C; generally speaking, increasing the reaction temperature can accelerate the reaction rate and shorten the reaction time, but if the temperature is too high, side reactions are likely to occur, so the reaction temperature should be controlled within an appropriate range;

[0024] The heat treatment time is 5 min to 30 min; preferably 5 min to 20 min; extending the reaction time can increase the click rate, but will reduce the click efficiency, so the reaction time should be appropriately controlled to be more conducive to achieving the implementation effect of the present invention;

[0025] The mixing method is by processing methods, such as mixing with an open mill, a Banbury mixer or mixing with a single-screw, twin-screw extruder, planetary screw extruder, kneader, and the mixing is carried out under shear force, not limited to the above mixing methods.

[0026] In a preferred embodiment of the present invention,

[0027] The preparation method of the functionalized solution-polymerized styrene-butadiene rubber in the chain includes: uniformly mixing the solution-polymerized styrene-butadiene rubber and the polyfunctional thiol reagent according to the dosage ratio, and after heat treatment, obtaining the functionalized solution-polymerized styrene-butadiene rubber in the chain; preferably,

[0028] The heat treatment temperature is 40°C to 160°C; preferably 80°C to 140°C;

[0029] The heat treatment time is 5 min to 30 min; preferably 5 min to 20 min

[0030] The mixing method is mixing by an open mill, a Banbury mixer, or by a single-screw, twin-screw extruder, planetary screw extruder, or kneader.

[0031] The epoxidized rubber is at least one of epoxidized natural rubber, epoxidized cis-butadiene rubber, epoxidized solution-polymerized styrene-butadiene rubber, epoxidized isoprene rubber, epoxidized eucommia rubber, epoxidized emulsion-polymerized styrene-butadiene rubber, epoxidized nitrile rubber, epoxidized chloroprene rubber, epoxidized ethylene-propylene-diene monomer rubber, epoxidized butyl rubber, epoxidized silicone rubber; the epoxidized rubber can be an epoxidized rubber of the prior art;

[0032] Preferably,

[0033] The epoxidized rubber is the epoxidized rubber prepared by Chinese invention patent CN116135887A (publication date: May 19, 2023, invention title: "A preparation method, epoxidized rubber and application of epoxidized rubber"), or the epoxidized solution-polymerized styrene-butadiene rubber of Chinese invention patent CN116162205A (publication date: May 26, 2023, invention title: "An epoxidized solution-polymerized styrene-butadiene rubber and its preparation method and application").

[0034] More preferably, the epoxy degree of the epoxidized rubber is 1% to 20%; more preferably 3% to 15%.

[0035] In a preferred embodiment of the present invention,

[0036] The filler is a filler with hydroxyl groups on the surface; preferably at least one of silica and carbon black;

[0037] The activator is at least one of metal oxides, fatty acids, zinc fatty acids, and amines; preferably at least one of zinc oxide, stearic acid, zinc stearate, and ammonium stearate;

[0038] The antioxidant is at least one of amines, phenols, and organic sulfides; preferably at least one of antioxidant 4010NA, antioxidant 264, and antioxidant MB;

[0039] The plasticizer is at least one of petroleum-based plasticizers, coal tar-based plasticizers, pine oil-based plasticizers, fatty oil-based plasticizers, and synthetic plasticizers; preferably at least one of paraffin, coumarone resin, rosin, stearic acid, and dioctyl phthalate;

[0040] The accelerator is at least one of thiazole, thiuram, sulfenamide, guanidine, dithiocarbamate, thiourea, aldehyde-amine, and xanthate; preferably at least one of dibenzothiazole disulfide (accelerator DM), tetramethylthiuram disulfide (accelerator TMTD), N-cyclohexyl-2-benzothiazole sulfenamide (accelerator CZ), diphenylguanidine (accelerator D), zinc dimethyldithiocarbamate (accelerator ZDMC), tetramethylthiourea (accelerator TMTU), hexamethylenetetramine (accelerator H), and zinc isopropylxanthate;

[0041] The vulcanizing agent is at least one of sulfur and non-sulfur vulcanizing agents; the non-sulfur vulcanizing agent is preferably dicumyl peroxide (DCP).

[0042] The second object of the present invention is to provide a method for preparing a high-performance tire tread material, comprising the following steps:

[0043] (1) Mix components including functionalized solution styrene-butadiene rubber, epoxidized rubber, filler, activator, antioxidant, and plasticizer, and then obtain a mixed material after heat treatment;

[0044] (2) Add the vulcanizing agent and accelerator to the mixed material obtained in step (1), mix evenly, and vulcanize to obtain the high-performance tire tread material.

[0045] In a preferred embodiment of the present invention,

[0046] Step (1),

[0047] The mixing time is 10 min to 15 min;

[0048] The heat treatment temperature is 60 °C to 180 °C; preferably 100 °C to 160 °C;

[0049] The heat treatment time is 2 min to 10 min; preferably 3 min to 6 min;

[0050] Mixing is carried out at room temperature on commonly used mixing equipment in the art, such as a mixer, kneader, or open mill. After mixing evenly, transfer it to a heatable mixing equipment for heat treatment, such as a mixer, kneader, and a heatable open mill;

[0051] Step (2),

[0052] After heat treatment, when the temperature of the rubber compound is reduced to room temperature, add the vulcanizing agent and accelerator for mixing, and the mixing time is 3 min to 5 min;

[0053] The vulcanization temperature is 130 °C to 180 °C; preferably 140 °C to 160 °C;

[0054] The vulcanization pressure is 10 MPa to 20 MPa; preferably 10 MPa to 15 MPa;

[0055] The vulcanization time is carried out according to the optimum vulcanization time.

[0056] The third object of the present invention is to provide an application of the above-mentioned high-performance tire tread material in a tire.

[0057] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0058] (1) The present invention provides a more efficient and simple preparation method of functionalized rubber, which is simple in operation, low in cost and does not require post-treatment, solving the disadvantages of high cost, heavy pollution and complex process existing in the functionalization modification of rubber in solution. By directly adding a multi-functional mercapto reagent during processing, the use of solvents and post-treatment problems are effectively avoided, the limitation of the solvent boiling point is overcome, the reaction temperature is high, the reaction time is shortened, and the reaction efficiency is higher.

[0059] (2) The present invention uses functionalized solution styrene-butadiene rubber and epoxidized rubber as the rubber matrix, improving the compatibility and dispersion of fillers in the rubber matrix.

[0060] (3) A high-performance tire tread material is prepared, which can improve the mechanical properties, wet skid resistance and wear resistance of the tread material, reduce its rolling resistance, and can be used to prepare green tire treads;

[0061] (4) The raw materials of the rubber composite material of the present invention are widely sourced, low in cost and simple in process, and can meet the requirements of the existing tire industrial production. Specific embodiments

[0062] The present invention will be specifically described below in conjunction with specific embodiments. It is necessary to point out here that the following embodiments are only for further illustration of the present invention and should not be construed as limiting the protection scope of the present invention. Some non-essential improvements and adjustments made by those skilled in the art to the present invention based on the content of the present invention still fall within the protection scope of the present invention.

[0063] The phase transfer catalyst CPC-PW in the embodiment 4 O 16 and epoxidized natural rubber and epoxidized cis-butadiene rubber are all self-made;

[0064] Preparation of the phase transfer catalyst:

[0065] [π-C 5 H 5 NC 16 H 33 3 [PW 4 O 16 , namely CPC-PW​4 O 16 Preparation of

[0066] Dissolve tungstic acid in hydrogen peroxide H 2 O 2 , heat and stir until colorless, filter, and after cooling the filtrate to room temperature, add H 3 PO 4 , stir for 0.5 h, then dropwise add a solution of cetylpyridinium chloride dissolved in CH 2 Cl 2 solution to this solution, stir for another 0.5 h, separate the organic layer, and dry it with anhydrous Na 2 SO 4 , evaporate the solvent to dryness to obtain CPC-PW 4 O 16 .

[0067] Preparation of 1% epoxidized cis-butadiene rubber:

[0068] Dissolve 40 g of cis-butadiene rubber (containing 0.6 mol of carbon-carbon double bonds) in 320 ml of cyclohexane solvent, add 0.92 g of formic acid and 8 drops of Tween 80. After 10 minutes, dropwise add 3.31 g of hydrogen peroxide at a rate of 5 ml / min. After the addition is complete, react for 4 hours to obtain an epoxidized cis-butadiene rubber latex. Add an aqueous sodium carbonate solution with a concentration of 5 g / 100 mL (2.1 g of sodium carbonate, with a molar ratio of sodium carbonate to formic acid of 1:1), stir at 25 °C for 1 hour, add 800 mL of ethanol to precipitate the rubber, and place the precipitated rubber in a 60 °C forced-air oven for drying to obtain 1% epoxidized cis-butadiene rubber.

[0069] Preparation of 3% epoxidized cis-butadiene rubber:

[0070] Dissolve 40 g of cis-butadiene rubber (containing 0.6 mol of carbon-carbon double bonds) in 320 ml of cyclohexane solvent, add 1.38 g of formic acid and 8 drops of Tween 80. After 10 minutes, dropwise add 4.96 g of hydrogen peroxide at a rate of 5 ml / min. After the addition is complete, react for 4 hours to obtain an epoxidized cis-butadiene rubber latex. Add an aqueous sodium carbonate solution with a concentration of 5 g / 100 mL (3 g of sodium carbonate, with a molar ratio of sodium carbonate to formic acid of 1:1), stir at 25 °C for 1 hour, add 800 mL of ethanol to precipitate the rubber, and place the precipitated rubber in a 60 °C forced-air oven for drying to obtain 3% epoxidized cis-butadiene rubber.

[0071] Preparation of 20% epoxidized natural rubber:

[0072] Dissolve 68 g of natural rubber (containing 1 mol of carbon-carbon double bonds) in 500 ml of dichloroethane solvent, and add 0.004 mol of CPC-PW 4 O 16(5.2 g) was dissolved in 0.24 mol of hydrogen peroxide. While controlling the temperature at 40 °C, it was added dropwise into the natural rubber solution at a rate of 5 ml / min. After reacting for 2 hours, centrifugation was carried out to recover the catalyst, and the residual hydrogen peroxide was removed. After separating the aqueous phase, the rubber was dried to a constant weight to obtain 20% epoxidized natural rubber.

[0073] Other raw materials in the examples and comparative examples were all conventional commercially available raw materials;

[0074] Functionalized solution-polymerized styrene-butadiene rubber 5360H (Kumho 5360H, South Korea), functionalized solution-polymerized styrene-butadiene rubber 4602 (Trinseo, USA), solution-polymerized styrene-butadiene rubber 2557S (Dushanzi Petrochemical), natural rubber (Xishuangbanna Jingyang Rubber Co., Ltd.), cis-1,4-polybutadiene rubber BR9000 (Zhejiang Transfar), formic acid (Shanghai Macklin Biochemical Co., Ltd.), hydrogen peroxide (Beijing Chemical Plant), Tween 80 (Shanghai Aladdin Biochemical Technology Co., Ltd.), Si75 (Evonik, Germany), 3-mercaptopropyltriethoxysilane (Anhui Zesheng Technology Co., Ltd.).

[0075] Testing methods:

[0076] NMR testing: Using CDCl 3 As a solvent, about 5 mg of rubber was dissolved, and nuclear magnetic resonance hydrogen spectrum testing was carried out on a Bruker AV400 spectrometer (600 MHz). The epoxy degree could be calculated according to the spectrum and formula;

[0077] Tensile testing: Dumbbell-shaped specimens with a thickness of 2 mm and a width of 6 mm were prepared and tested on a SANS-CMT-4104 machine at a speed of 500 mm / min at room temperature according to ASTM D412 standard to obtain the elongation at break and the stress at a specified elongation;

[0078] RPA: It was carried out on an RPA2000 rubber processing analyzer at 60 °C. The vulcanizate was tested in the strain range of 0.28 - 42% at 10 Hz;

[0079] DMA: Rectangular splines were tested on a dynamic thermomechanical analyzer (DMTA, VA3000, 01dB-Metravib Co., Ltd., France) in tensile mode at a frequency of 10 Hz, a strain of 0.1%, and a heating rate of 3 °C / min in the temperature range of -80 °C to 80 °C.

[0080] Heat build-up in compression: The test standard was GB / T 1687.3, and cylindrical specimens with a size of were tested on an RH-2000N heat build-up in compression testing machine;

[0081] Ackermann abrasion: The test standard is GB / T1689-201451, and the wear performance of the nanocomposite is measured on an Akron wear tester (MZ-4061, Jiangsu Mingzhu Test Machinery Co., Ltd.).

[0082] The parts in the examples and comparative examples all refer to parts by weight.

[0083] Example 1

[0084] According to the formula, 70 parts of commercially available functionalized solution-polymerized styrene-butadiene rubber (5360H), 30 parts of the prepared 3% epoxidized cis-1,4-polybutadiene rubber, 3 parts of zinc oxide, 2 parts of stearic acid, 80 parts of white carbon black VN3, 6.4 parts of Si75, 2 parts of antioxidant 4010NA, and 1.5 parts of paraffin wax were kneaded on an open mill at room temperature for 15 min, then heat-treated on an open mill at 150 °C for 5 min. After cooling to room temperature, 2 parts of accelerator CZ, 2 parts of accelerator D, and 1.5 parts of sulfur were added, and the mixture was continuously kneaded on an open mill at room temperature for 3 min. After vulcanization at 150 °C and 15 MPa according to the optimum vulcanization time, a high-performance tire tread material was obtained and its performance was tested.

[0085] Example 2

[0086] According to the formula, 90 parts of commercially available functionalized solution-polymerized styrene-butadiene rubber (5360H), 10 parts of the prepared 1% epoxidized cis-1,4-polybutadiene rubber, 2 parts of zinc oxide, 1 part of stearic acid, 100 parts of white carbon black VN3, 6.4 parts of Si75, 1 part of antioxidant 4010NA, and 1.5 parts of paraffin wax were kneaded on an open mill at room temperature for 10 min, then heat-treated on an open mill at 100 °C for 3 min. After cooling to room temperature, 3 parts of accelerator CZ, 4 parts of accelerator D, and 3 parts of sulfur were added, and the mixture was continuously kneaded on an open mill at room temperature for 3 min. After vulcanization at 150 °C and 15 MPa according to the optimum vulcanization time, a high-performance tire tread material was obtained and its performance was tested.

[0087] Example 3

[0088] According to the formula, 60 parts of commercially available functionalized solution-polymerized styrene-butadiene rubber (4602), 40 parts of the prepared 20% epoxidized natural rubber, 3 parts of zinc oxide, 2 parts of stearic acid, 80 parts of white carbon black VN3, 6.4 parts of Si75, 2 parts of antioxidant 4010NA, and 1.5 parts of paraffin wax were kneaded on an open mill at room temperature for 15 min, then heat-treated on an open mill at 150 °C for 5 min. After cooling to room temperature, 2 parts of accelerator CZ, 2 parts of accelerator D, and 1.5 parts of sulfur were added, and the mixture was continuously kneaded on an open mill at room temperature for 3 min. After vulcanization at 150 °C and 15 MPa according to the optimum vulcanization time, a high-performance tire tread material was obtained and its performance was tested.

[0089] Example 4

[0090] 137.5 g of solution-polymerized styrene-butadiene rubber 2557S (containing 1.39 mol of carbon-carbon double bonds) and 5.01 g of ethyl mercaptoacetate (the molar ratio of ethyl mercaptoacetate to the double bonds in the solution-polymerized styrene-butadiene rubber is 0.03:1) were mixed on an open mill at a roll temperature of 80 °C and heat-treated for 5 min. After mixing evenly, a functionalized solution-polymerized styrene-butadiene rubber (functional group is an ester group) was obtained.

[0091] According to the formula, 70 parts of the above-prepared functionalized solution-polymerized styrene-butadiene rubber, 30 parts of the prepared 3% epoxidized cis-1,4-polybutadiene rubber, 3 parts of zinc oxide, 2 parts of stearic acid, 80 parts of white carbon black VN3, 2 parts of antioxidant 4010NA, and 1.5 parts of paraffin were kneaded on an open mill at room temperature for 15 min, and then heat-treated on an open mill at 150 °C for 5 min. After cooling, 2 parts of accelerator CZ, 2 parts of accelerator D, and 1.5 parts of sulfur were added, and the mixture was continuously kneaded on an open mill at room temperature for 3 min to obtain a kneaded rubber. The kneaded rubber was vulcanized at 150 °C and 15 MPa according to the optimum vulcanization time, and then its properties were tested.

[0092] Example 5

[0093] 137.5 g of solution-polymerized styrene-butadiene rubber 2557S (containing 1.39 mol of carbon-carbon double bonds) and 49.71 g of 3-mercaptopropyltriethoxysilane (the molar ratio of 3-mercaptopropyltriethoxysilane to the double bonds in the solution-polymerized styrene-butadiene rubber is 0.15:1) were mixed on an open mill at a roll temperature of 80 °C and heat-treated for 5 min. After mixing evenly, a functionalized solution-polymerized styrene-butadiene rubber (functional group is a siloxanyl group) was obtained.

[0094] According to the formula, 60 parts of the above-prepared functionalized solution-polymerized styrene-butadiene rubber, 40 parts of the prepared 20% epoxidized natural rubber, 3 parts of zinc oxide, 2 parts of stearic acid, 80 parts of white carbon black VN3, 2 parts of antioxidant 4010NA, and 1.5 parts of paraffin were kneaded on an open mill at room temperature for 15 min, and then heat-treated on an open mill at 150 °C for 5 min. After cooling, 2 parts of accelerator CZ, 2 parts of accelerator D, and 1.5 parts of sulfur were added, and the mixture was continuously kneaded on an open mill at room temperature for 3 min to obtain a kneaded rubber. The kneaded rubber was vulcanized at 150 °C and 15 MPa according to the optimum vulcanization time, and then its properties were tested.

[0095] Example 6

[0096] 137.5 g of solution-polymerized styrene-butadiene rubber 2557S (containing 1.39 mol of carbon-carbon double bonds) and 182.3 g of 3-mercaptopropyltriethoxysilane (the molar ratio of 3-mercaptopropyltriethoxysilane to the double bonds in the solution-polymerized styrene-butadiene rubber is 0.55:1) were mixed in a Banbury mixer at a temperature of 140 °C and heat-treated for 20 min. After mixing evenly, a functionalized solution-polymerized styrene-butadiene rubber (functional group is a siloxanyl group) was obtained.

[0097] According to the formula, 60 parts of the functionalized solution-polymerized styrene-butadiene rubber prepared above, 40 parts of the prepared 20% epoxidized natural rubber, 3 parts of zinc oxide, 2 parts of stearic acid, 80 parts of white carbon black VN3, 2 parts of antioxidant 4010NA, and 3 parts of paraffin were kneaded on an open mill at room temperature for 15 min, then heat-treated on an open mill at 150 °C for 5 min. After cooling, 3 parts of accelerator TMTD, 3 parts of accelerator DM, and 2 parts of sulfur were added, and the mixture was continuously kneaded on an open mill at room temperature for 3 min to obtain a kneaded rubber. The kneaded rubber was vulcanized at 150 °C and 15 MPa according to the optimum vulcanization time, and then its properties were tested.

[0098] Comparative Example 1

[0099] The difference from Example 1 is that: 6.4 parts of Si75 were added to the formula; 3% of epoxidized cis-1,4-polybutadiene was replaced with cis-1,4-polybutadiene in equal mass;

[0100] Except for the above differences, other conditions of Comparative Example 1 were the same as those of Example 1. A kneaded rubber was obtained, and the kneaded rubber was vulcanized at 150 °C and 15 MPa according to the optimum vulcanization time, and then its properties were tested.

[0101] Comparative Example 2

[0102] The difference from Example 3 is that: the commercially available functionalized solution-polymerized styrene-butadiene rubber (4602) was replaced with solution-polymerized styrene-butadiene rubber 2557S in equal mass; 20% of epoxidized natural rubber was replaced with natural rubber in equal mass; 6.4 parts of Si75 were added to the formula;

[0103] Except for the above differences, other conditions of Comparative Example 2 were the same as those of Example 3. A kneaded rubber was obtained, and the kneaded rubber was vulcanized at 150 °C and 15 MPa according to the optimum vulcanization time, and then its properties were tested.

[0104] Comparative Example 3

[0105] The difference from Example 4 is that: the functionalized solution-polymerized styrene-butadiene rubber in the formula was replaced with solution-polymerized styrene-butadiene rubber 2557S in equal mass;

[0106] Except for the above differences, other conditions of Comparative Example 3 were the same as those of Example 4. A kneaded rubber was obtained, and the kneaded rubber was vulcanized at 150 °C and 15 MPa according to the optimum vulcanization time, and then its properties were tested.

[0107] Comparative Example 4

[0108] The difference from Example 4 is that: 3% of epoxidized cis-1,4-polybutadiene in the formula was replaced with cis-1,4-polybutadiene in equal mass;

[0109] Except for the above differences, other conditions of Comparative Example 4 were the same as those of Example 4. A kneaded rubber was obtained, and the kneaded rubber was vulcanized at 150 °C and 15 MPa according to the optimum vulcanization time, and then its properties were tested.

[0110] Comparative Example 5

[0111] The differences from Example 4 are as follows: The functionalized solution-polymerized styrene-butadiene rubber in the formulation is replaced with solution-polymerized styrene-butadiene rubber 2557S in equal mass; 3% epoxidized cis-1,4-polybutadiene rubber in the formulation is replaced with cis-1,4-polybutadiene rubber in equal mass.

[0112] Except for the above differences, other conditions of Comparative Example 5 are the same as those of Example 4. A mixed rubber was obtained, and the properties were tested after curing the mixed rubber at 150 °C and 15 MPa for the optimum cure time.

[0113] Table 1 Performance test results of Examples 1-6 and Comparative Examples 1-5

[0114]

[0115] RPA-tanδ(7%) refers to the tangent of the loss angle at a strain of 7%, which is usually used to describe the magnitude of the rolling resistance. The smaller the value, the smaller the rolling resistance; DMA-tanδ(0 °C) is usually used to describe the wet skid resistance of the material. The larger the value, the better the wet skid resistance.

[0116] Comparing Example 1 with Comparative Example 1:

[0117] The DMA-tanδ(0 °C) of Example 1 is 0.34, and the DMA-tanδ(0 °C) of Comparative Example 1 is 0.30. Compared with Comparative Example 1, Example 1 has better wet skid resistance;

[0118] The RPA-tanδ(7%) of Example 1 is 0.110, and the RPA-tanδ(7%) of Comparative Example 1 is 0.129. Compared with Comparative Example 1, Example 1 has lower rolling resistance;

[0119] The compression fatigue temperature rise of Example 1 is 28.0 °C, and the compression fatigue of Comparative Example 1 is 31.7 °C. Compared with Comparative Example 1, Example 1 generates less heat and has a lower compression fatigue temperature rise;

[0120] The abrasion of Example 1 is 0.115 cm 3 , and the abrasion of Comparative Example 1 is 0.119 cm 3 , Compared with Comparative Example 1, Example 1 has better abrasion resistance.

[0121] Comparing Example 3 with Comparative Example 2:

[0122] The DMA-tanδ(0 °C) of Example 3 is 0.4, and the DMA-tanδ(0 °C) of Comparative Example 2 is 0.28. Example 3 has better wet skid resistance;

[0123] The RPA-tanδ (7%) of Example 3 is 0.118, and the RPA-tanδ (7%) of Comparative Example 2 is 0.125. Example 3 has lower rolling resistance;

[0124] The compression fatigue temperature rise of Example 3 is 29.3 °C, and the compression fatigue temperature rise of Comparative Example 2 is 31.3 °C. Example 3 has lower compression fatigue temperature rise;

[0125] The abrasion of Example 3 is 0.118 cm 3 , and the abrasion of Comparative Example 2 is 0.128 cm 3 , and Example 3 has better wear resistance.

[0126] When comparing Example 4 with Comparative Examples 3-5:

[0127] The DMA-tanδ (0 °C) of Example 4 is 0.43, and the DMA-tanδ (0 °C) of Comparative Examples 3-5 are 0.31, 0.36, and 0.25 respectively. Example 4 has better wet skid resistance;

[0128] The RPA-tanδ (7%) of Example 4 is 0.109, and the RPA-tanδ (7%) of Comparative Examples 3-5 are 0.124, 0.121, and 0.129 respectively. Example 4 has lower rolling resistance;

[0129] The compression fatigue temperature rise of Example 4 is 28.5 °C, and the compression fatigue temperature rises of Comparative Examples 3-5 are 30.8 °C, 30.1 °C, and 31.6 °C respectively. Example 4 has lower compression fatigue temperature rise;

[0130] The abrasion of Example 4 is 0.113 cm 3 , and the abrasions of Comparative Examples 3-5 are 0.124 cm 3 , 0.119 cm 3 , 0.118 cm 3 , and Example 4 has better wear resistance.

[0131] The DMA-tanδ (0 °C) of Examples 1-6 is 0.31-0.56, indicating that the high-performance tire tread material prepared by the present invention has good wet skid resistance; the RPA-tanδ (7%) is 0.109-0.118, indicating that the high-performance tire tread material prepared by the present invention has lower rolling resistance; the compression fatigue temperature rise is 27.2-29.6 °C, indicating that the high-performance tire tread material prepared by the present invention has lower heat generation and lower compression fatigue temperature rise; the abrasion is 0.112-0.119 cm 3 , indicating that the high-performance tire tread material prepared by the present invention has very good wear resistance.

[0132] The above test data prove that the high-performance functionalized solution styrene-butadiene rubber and epoxidized rubber nanocomposites prepared in Examples 1 to 6 have low heat build-up, good abrasion resistance, good wet skid resistance, and low rolling resistance, and are a rubber composite material for tread rubber with excellent performance.

Claims

1. A high-performance tire tread material, characterized in that: The high-performance tire tread material is prepared from raw materials including functionalized solution-polymerized styrene-butadiene rubber, epoxidized rubber, filler, activator, antioxidant, plasticizer, accelerator and vulcanizer; Taking the total amount of functionalized solution-polymerized styrene-butadiene rubber and epoxidized rubber as 100 parts by weight, The invention comprises 50 to 95 parts by weight of functionalized solution-polymerized styrene-butadiene rubber and 5 to 50 parts by weight of epoxidized rubber. The functional group of the functionalized solution-polymerized styrene-butadiene rubber is at least one of a siloxane group, an amine group, a carboxyl group, an ester group, a hydroxyl group, an amide group, a sulfur-containing group, and a perfluoroalkyl group.

2. The high performance tire tread material according to claim 1, characterized in that: Taking the total amount of functionalized solution-polymerized styrene-butadiene rubber and epoxidized rubber as 100 parts by weight, The invention comprises 60 to 90 parts by weight of functionalized solution-polymerized styrene-butadiene rubber and 10 to 40 parts by weight of epoxidized rubber.

3. The high performance tire tread material according to claim 1 or 2, characterized in that: The functionalized solution polymerized styrene butadiene rubber is a chain-end functionalized solution polymerized styrene butadiene rubber or a chain-mid functionalized solution polymerized styrene butadiene rubber; preferably, The chain-end functionalized solution-polymerized styrene-butadiene rubber is obtained by copolymerization of functionalized monomers; and / or, The in-chain functionalized solution-polymerized styrene-butadiene rubber is obtained by functionalization modification, more preferably by mercapto-ene click chemistry reaction.

4. The high performance tire tread material according to claim 3, characterized in that: The in-chain functionalized solution polymerized styrene butadiene rubber is prepared by uniformly mixing raw materials including solution polymerized styrene butadiene rubber and a multifunctional thiol reagent by heat treatment; preferably, the molar ratio of the multifunctional thiol reagent to the rubber double bond is (0.01-0.9):1, more preferably (0.03-0.55):

1.

5. The high performance tire tread material according to claim 4, characterized in that: The multifunctional thiol reagent has at least one of a siloxane group, an amine group, a carboxyl group, an ester group, and a hydroxyl functional group and a thiol functional group; the multifunctional thiol reagent is preferably at least one of 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, ethyl mercaptoacetate, methyl mercaptoacetate, mercaptoethanol, 3-mercaptopropanol, 3-mercaptopropionic acid, mercaptoundecanoic acid, cysteine, mercaptosuccinic acid, and mercaptoethylamine; and / or, The heat treatment temperature is 40°C to 160°C; preferably 80°C to 140°C; and / or, The heat treatment time is 5 min to 30 min; preferably 5 min to 20 min; and / or, The mixing method is mixing in an open mixer, mixing in an internal mixer, or mixing through a single-screw or twin-screw extruder, a planetary screw extruder, or a kneader.

6. The high performance tire tread material according to claim 4, characterized in that: The method for preparing the chain-functionalized solution-polymerized styrene-butadiene rubber comprises: uniformly mixing the solution-polymerized styrene-butadiene rubber and the multifunctional thiol reagent according to the dosage ratio, and obtaining the chain-functionalized solution-polymerized styrene-butadiene rubber after heat treatment; preferably, The heat treatment temperature is 40°C to 160°C; preferably 80°C to 140°C; and / or, The heat treatment time is 5 min to 30 min; preferably 5 min to 20 min; and / or, The mixing method is mixing in an open mixer, mixing in an internal mixer, or mixing through a single-screw or twin-screw extruder, a planetary screw extruder, or a kneader.

7. The high performance tire tread material according to claim 1, characterized in that: The epoxidized rubber is at least one of epoxidized natural rubber, epoxidized butadiene rubber, epoxidized solution-polymerized styrene-butadiene rubber, epoxidized isoprene rubber, epoxidized eucommia rubber, epoxidized emulsion-polymerized styrene-butadiene rubber, epoxidized nitrile rubber, epoxidized chloroprene rubber, epoxidized ethylene-propylene-diene rubber, epoxidized butyl rubber, and epoxidized silicone rubber; preferably, the epoxidized degree of the epoxidized rubber is 1% to 20%, more preferably 3% to 15%; and / or, The filler is a filler containing hydroxyl groups on the surface; preferably at least one of white carbon black and carbon black; and / or, The activator is at least one of metal oxides, fatty acids, fatty acid zinc, and amines; preferably at least one of zinc oxide, stearic acid, zinc stearate, and ammonium stearate; and / or, The antioxidant is at least one of amines, phenols and organic sulfides; and / or, The plasticizer is at least one of petroleum plasticizer, coal tar plasticizer, pine oil plasticizer, fatty oil plasticizer, and synthetic plasticizer; preferably at least one of paraffin, coumarone resin, rosin, stearic acid, and dioctyl phthalate; and / or, The accelerator is at least one of thiazoles, thiurams, sulfenamides, guanidines, dithiocarbamates, thioureas, aldehyde amines, and xanthates; preferably at least one of benzothiazole disulfide, tetramethylthiuram disulfide, N-cyclohexyl-2-benzothiazole sulfenamide, diphenylguanidine, zinc dimethyldithiocarbamate, tetramethylthiourea, hexamethylenetetramine, and zinc isopropyl xanthate; and / or, The vulcanizing agent is at least one of sulfur and non-sulfur sulfide; the non-sulfur sulfide is preferably dicumyl peroxide.

8. A method for preparing a high-performance tire tread material according to any one of claims 1 to 7, the method comprising the following steps: (1) mixing components including functionalized solution-polymerized styrene-butadiene rubber, epoxidized rubber, filler, activator, antioxidant, and plasticizer uniformly, and then heat-treating to obtain a mixed material; (2) adding a vulcanizing agent and an accelerator to the mixture obtained in step (1), kneading the mixture evenly, and vulcanizing the mixture to obtain the high-performance tire tread material.

9. The method for preparing a high performance tire tread material according to claim 8, characterized in that: Step (1), The mixing time is 10 to 15 minutes; and / or, The heat treatment temperature is 60°C to 180°C; preferably 100°C to 160°C; and / or, The heat treatment time is 2 min to 10 min; preferably 3 min to 6 min; and / or, Step (2), The mixing time is 3 to 5 minutes; and / or, The vulcanization temperature is 130°C to 180°C; preferably 140°C to 160°C; and / or, The vulcanization pressure is 10 MPa to 20 MPa, preferably 10 MPa to 15 MPa.

10. Use of the high-performance tire tread material according to any one of claims 1 to 7 or the high-performance tire tread material obtained by the preparation method according to claim 8 or 9 in a tire.

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