Method for preparing wet-skid-resistant tread rubber and application of wet-skid-resistant tread rubber

Abstract

The invention provides a method for preparing wet-skid-resistant tread rubber and application of the wet-skid-resistant tread rubber, and relates to the technical field of tire manufacturing. According to the invention, the tread rubber is prepared by compounding the rare earth butadiene rubber and the hydrogenated butadiene-acrylonitrile rubber, and the tread rubber with wet skid resistance and wear resistance can be prepared by taking methacryloyloxypropyltrimethoxysilane as a coupling agent, so that a new tread rubber material is provided for tires for new energy automobiles. In order to further improve the anti-aging performance of the tread rubber, the cellulose acetate butyrate is added into a tread rubber formula for the first time, and the dispersity of the cellulose acetate butyrate in the tread rubber is improved by adding the cationic active agent, namely the chlorinated diphenyl sulphonate, so that the tread rubber with high yield and good physical properties is obtained; and the production cost of the tread rubber is saved.

Description

Technical Field

[0001] The present application relates to the technical field of tire manufacturing, and in particular to a method for preparing anti-wet skid resistant tread rubber and its application. Background Art

[0002] Tires are important components of automobiles and important products of the rubber industry. They support loads and transmit braking, driving and steering forces to the ground. At present, new energy vehicles are gradually entering the public eye due to their green and environmentally friendly characteristics. New energy vehicles use a large number of battery packs instead of internal combustion engines, and they are concentrated in the chassis. The body weight is about 30% larger than that of ordinary internal combustion engine vehicles, and the tires wear faster, which requires high wear resistance of tires. In addition, new energy vehicles use electric motor direct drive, eliminating mechanical transmission methods such as gearboxes and drive shafts. The instantaneous torque of the wheels is large when starting, the power response is more direct, and the vehicle starts and accelerates very quickly, which requires the tires to have better grip performance and no slipping when starting. However, there are currently few tires launched for new energy vehicles, and there is an urgent need to fill this market gap. Summary of the invention

[0003] The purpose of the present invention is to provide a tire for new energy vehicles that has both anti-skid performance and wear resistance.

[0004] In one aspect, the present application provides a method for preparing an anti-skid tread rubber, the method comprising:

[0005] Step 1, rare earth cis-1,4-butadiene rubber and hydrogenated nitrile rubber are mixed, and plasticized for 30-120 seconds, and then fillers and coupling agents are added for the first mixing for 30-120 seconds, and then cellulose acetate butyrate and surfactant are added, and the second mixing is carried out for 30-120 seconds, and the rubber is discharged to obtain a mixed rubber;

[0006] Step 2: Roll the mixed rubber described in step 1, add a vulcanizing agent and an accelerator, roll the mixed rubber, and vulcanize the mixed rubber to obtain a tread rubber.

[0007] Preferably, the mastication is 50-70s, the first mixing is 110-130s, and the second mixing is 50-70s.

[0008] Furthermore, the mass ratio of the rare earth butadiene rubber to the hydrogenated nitrile rubber is 20-30:20-30; more preferably, 25:30.

[0009] Further, the coupling agent is a silane coupling agent; preferably, the coupling agent is methacryloxypropyltrimethoxysilane; and / or,

[0010] The surfactant is a cationic surfactant; preferably, the surfactant is diphenyl sulfonyl chloride; and / or,

[0011] The filler is white carbon black and / or carbon black; preferably, white carbon black; and / or,

[0012] The vulcanizing agent is sulfur; and / or,

[0013] The accelerator is zinc dithiocarbamate.

[0014] Furthermore, the tread rubber comprises, by mass, 20-30 parts of rare earth butadiene rubber, 20-30 parts of hydrogenated nitrile rubber, 1-5 parts of methacryloyloxypropyl trimethoxysilane, 20-30 parts of white carbon black, 1-5 parts of zinc dithiocarbamate, 1-5 parts of sulfur, 1-5 parts of cellulose acetate butyrate, and 1-5 parts of diphenyl chloride sulfonate; preferably, 25 parts of rare earth butadiene rubber, 30 parts of hydrogenated nitrile rubber, 5 parts of methacryloyloxypropyl trimethoxysilane, 30 parts of white carbon black, 2 parts of zinc dithiocarbamate, 1 part of sulfur, 5 parts of cellulose acetate butyrate, and 2 parts of diphenyl chloride sulfonate.

[0015] Furthermore, the conditions for the mastication, the first mixing and the second mixing are a temperature of 80° C.-100° C. and a rotation speed of 60-80 rpm.

[0016] Preferably, the temperature is 90° C. and the rotation speed is 70 rpm.

[0017] Further, the debinding temperature is 140°C-160°C; preferably, 150°C; and / or,

[0018] The mixing rubber bag roll conditions include: temperature of 50-70°C, front roll speed of 10-30r / min, rear roll speed of 10-30r / min; preferably, temperature of 60°C, front roll speed of 20r / min, rear roll speed of 22r / min; and / or,

[0019] The vulcanization conditions include: temperature 150-170° C., pressure 10-20 MPa; preferably, temperature 160° C., pressure 15 MPa.

[0020] In a preferred embodiment, a method for preparing an anti-skid tread rubber comprises the following steps:

[0021] Step 1, putting rare earth butadiene rubber and hydrogenated nitrile rubber into an internal mixer, plasticizing for 50-70s at a temperature of 80°C-100°C and a rotation speed of 60-80rpm, then adding white carbon black and methacryloyloxypropyl trimethoxysilane and mixing for 110-130s, then adding cellulose acetate butyrate and diphenyl sulfonyl chloride, mixing for 50-70s, and finally draining at 140°C-160°C to obtain a mixed rubber;

[0022] Step 2: Roll the mixed rubber described in step 1 at a temperature of 50-70°C, a front roller speed of 10-30r / min, a rear roller speed of 10-30r / min, mix the rubber evenly, add sulfur and zinc dithiocarbamate, adjust the distance to an appropriate distance and then put the sheet down, finally vulcanize at a vulcanizer temperature of 150-170°C and a pressure of 10-20MPa to obtain tread rubber.

[0023] More preferably,

[0024] Step 1, rare earth cis-1,4-butadiene rubber and hydrogenated nitrile rubber are put into an internal mixer, and plasticized for 60 seconds at a temperature of 90°C and a rotation speed of 70 rpm, followed by adding white carbon black and methacryloyloxypropyltrimethoxysilane and mixing for 120 seconds, and then adding cellulose acetate butyrate and diphenyl sulfonyl chloride, mixing for 60 seconds, and finally draining the rubber (150°C) to obtain a mixed rubber;

[0025] Step 2: Roll the mixed rubber described in step 1 at a temperature of 60°C, a front roller speed of 20r / min, and a rear roller speed of 22r / min, and add sulfur and zinc dithiocarbamate after mixing evenly. After adjusting the distance to an appropriate distance, roll the mixed rubber and vulcanize it in a vulcanizer at a temperature of 160°C and a pressure of 15MPa to obtain a tread rubber.

[0026] On the other hand, the present application also provides a tread rubber prepared by the method.

[0027] On the other hand, the present application also provides the use of the method or the tread rubber in improving the anti-skid, anti-aging and / or wear resistance of a tire.

[0028] On the other hand, the present application also provides a tire with the tread rubber.

[0029] Furthermore, the tire is a tire for new energy vehicles.

[0030] The present invention has the following beneficial effects:

[0031] 1. In this application, rare earth cis-1,4-butadiene rubber and hydrogenated nitrile rubber are compounded to prepare tread rubber, and methacryloyloxypropyltrimethoxysilane is used as a coupling agent to prepare tread rubber with both anti-skid and wear resistance, providing a new tread rubber material for tires for new energy vehicles.

[0032] 2. In order to further improve the anti-aging performance of the tread rubber, cellulose acetate butyrate is added to the tread rubber formula for the first time in this application, and the dispersibility of cellulose acetate butyrate in the tread rubber is improved by adding the cationic active agent diphenyl sulfonate chloride, so that a tread rubber with high yield and good physical properties is obtained, saving the production cost of the tread rubber.

[0033] 3. In this application, the production conditions of the above-mentioned tread rubber are optimized to obtain the best production method. DETAILED DESCRIPTION

[0034] In order to more clearly illustrate the overall concept of the application, the following is described in detail by way of embodiment. In the following description, a large amount of specific details are provided to provide a more thorough understanding of the present invention. However, it is obvious to those skilled in the art that the present invention can be implemented without one or more of these details. In other examples, in order to avoid confusion with the present invention, some technical features well known in the art are not described.

[0035] If no specific conditions are specified in the examples, the experiments were carried out according to conventional conditions or conditions recommended by the manufacturer.

[0036] Among them, rare earth butadiene rubber (BRNd40) was purchased from Shenzhen Longlifeng Materials Co., Ltd., hydrogenated nitrile rubber (HNBR) was purchased from Nanjing Manco New Materials Co., Ltd., and the Akron abrasion machine CSI-A00 was purchased from Shanghai Chengsi Intelligent Technology Co., Ltd.

[0037] Unless otherwise specified, in the following embodiments, the reagents or instruments used without indicating the manufacturer are all conventional products that can be purchased commercially.

[0038] Example 1 Screening of anti-slip and wear-resistant tread rubber

[0039] In this embodiment, the components of the tread rubber are screened in order to obtain a tread rubber having excellent anti-skid and wear-resistant properties.

[0040] The tread rubber formula in this embodiment is as follows: rubber, coupling agent, white carbon black, 2 parts of zinc dithiocarbamate, 1 part of sulfur, a total of 100 parts. If there is a change in the ingredients during the test, white carbon black is used to make up 100 parts.

[0041] The tread rubber preparation method comprises:

[0042] Step 1: Put the rubber into an internal mixer, and plasticize it for 60 seconds at a temperature of 90°C and a speed of 70 rpm, then add white carbon black and a coupling agent and mix them for 120 seconds, and finally discharge the rubber (150°C) to obtain a mixed rubber;

[0043] Step 2: Roll the mixed rubber described in step 1 at a temperature of 60°C, a front roller speed of 20r / min, and a rear roller speed of 22r / min, and add sulfur and zinc dithiocarbamate after mixing evenly. After adjusting the distance to an appropriate distance, roll the mixed rubber and vulcanize it in a vulcanizer at a temperature of 160°C and a pressure of 15MPa to obtain a tread rubber.

[0044] Anti-skid performance test of tread rubber: Test according to the "Test Method for Relative Grip Performance of Passenger Car Tires on Wet Road Surfaces (GB / T21910-2008)" and obtain the tire wet road surface grip performance index.

[0045] Wear resistance test of tread rubber: Use Akron abrasion machine to characterize the wear resistance of rubber according to GB / T 1689-1998. For each sample, a total of 3 measurements are performed and the final test results are averaged.

[0046] The control group was a tread rubber of a commercially available tire RU06 205 / 40ZR17.

[0047] The specific parameters and test results are shown in Table 1.

[0048] Table 1

[0049]

[0050]

[0051] As can be seen from the results in Table 1, the tread rubber prepared by compounding rare earth cis-butadiene rubber and hydrogenated nitrile rubber in this application, when the ratio of the parts is 25:30, can be prepared by using methacryloyloxypropyl trimethoxysilane (5 parts) as a coupling agent to produce a tread rubber with both anti-slip and wear resistance, providing a new tread rubber material for high-performance special scene tires. Specifically, its Akron wear can reach 0.13cm 3 / 1.61km, and its tire wet road grip performance index can reach 72.35%, and the rolling resistance reduction rate of tires compared with commercially available products is 18%, proving that the composite tread rubber has excellent anti-wet grip performance.

[0052] Example 2 Improvement of aging resistance

[0053] During use, it was found that the aging resistance of the tread rubber prepared by compounding rare earth butadiene rubber and hydrogenated nitrile rubber was affected to a certain extent, and was slightly lower than that of commercially available tires.

[0054] In this embodiment, the optimized formula obtained in Example 1 is further improved to solve the problem of poor aging resistance. Specifically, in this embodiment, cellulose acetate butyrate is added to the tread rubber formula for the first time to further improve the tread rubber performance.

[0055] In this embodiment, the tread rubber formula is: 25 parts of rare earth cis-butadiene rubber, 30 parts of hydrogenated nitrile rubber, 5 parts of methacryloyloxypropyl trimethoxysilane, white carbon black, 2 parts of zinc dithiocarbamate, 1 part of sulfur, and cellulose acetate butyrate, a total of 100 parts. If there is a change in the composition during the test, white carbon black is used to make up 100 parts.

[0056] The tread rubber preparation method comprises:

[0057] Step 1, putting rare earth cis-1,1-butadiene rubber and hydrogenated nitrile rubber into an internal mixer, and plasticizing for 60 seconds at a temperature of 90°C and a rotation speed of 70 rpm, then adding white carbon black and methacryloyloxypropyltrimethoxysilane and mixing for 60 seconds, then adding cellulose acetate butyrate and diphenyl sulfonyl chloride, mixing for 60 seconds, and finally draining the rubber (150°C) to obtain a mixed rubber;

[0058] Step 2: Roll the mixed rubber described in step 1 at a temperature of 60°C, a front roller speed of 20r / min, and a rear roller speed of 22r / min, and add sulfur and zinc dithiocarbamate after mixing evenly. After adjusting the distance to an appropriate distance, roll the mixed rubber and vulcanize it in a vulcanizer at a temperature of 160°C and a pressure of 15MPa to obtain a tread rubber.

[0059] Tread rubber aging resistance test: The durability of the tire is tested according to GB / T 4502-2023, with an inflation pressure of 220kPa and a test speed of 120km·h -1 Before testing, the tires should be parked at (38±3)℃ for more than 3h.

[0060] Calculate the yield rate of tread rubber. Yield rate = number of tread rubbers without irregular particles or cracks / total number of tread rubbers * 100%.

[0061] The specific parameters and results are shown in Table 2.

[0062] Table 2

[0063]

[0064] In this embodiment, cellulose acetate butyrate is used as an auxiliary agent for the first time to improve the poor aging resistance of rare earth butadiene rubber and hydrogenated nitrile rubber tread rubber. In this embodiment, it is also found that after the addition of cellulose acetate butyrate, there is an uneven dispersion in some tread rubbers, resulting in a decrease in the yield. Then, by adding a surfactant component (especially a cationic active agent diphenyl chlorinated sulfonate), the dispersibility of cellulose acetate butyrate in the tread rubber composition is increased, thereby improving the yield and reducing the production cost of the tread rubber.

[0065] After testing, the cumulative running time of the tire is 79.99h, which is far higher than the national standard requirements.

[0066] Example 3 Optimization of tread rubber preparation conditions

[0067] Based on the optimization results of Example 2, this example further optimizes the specific conditions of the tread rubber preparation method. The method includes the following steps:

[0068] Step 1, 25 parts of rare earth cis-1,4-butadiene rubber and 30 parts of hydrogenated nitrile rubber are put into an internal mixer at a temperature of 90°C and a speed of 70 rpm for plasticization, and then 30 parts of white carbon black and 5 parts of methacryloyloxypropyltrimethoxysilane are added for the first mixing, and then 5 parts of cellulose acetate butyrate and 2 parts of diphenyl sulfonyl chloride are added for the second mixing, and finally the rubber is discharged (150°C) to obtain a mixed rubber;

[0069] Step 2: Roll the mixed rubber described in step 1 at a temperature of 60°C, a front roller speed of 20r / min, and a rear roller speed of 22r / min. After mixing evenly, add 1 part of sulfur and 2 parts of zinc dithiocarbamate, adjust the distance to an appropriate distance and then put the sheet down. Finally, vulcanize at a vulcanizer temperature of 160°C and a pressure of 15MPa to obtain a tread rubber.

[0070] The detection methods of anti-slip performance, wear resistance and aging resistance are the same as those of Example 1 and Example 2.

[0071] The specific parameters and results are shown in Table 3.

[0072] Table 3

[0073]

[0074]

[0075] From the results in Table 3, it can be seen that the tread rubber performance is better when the plasticating time is 60s, the first mixing time is 120s, and the second mixing time is 60s, which is suitable for new energy off-road vehicles.

[0076] The above is only the embodiment of the present application and is not intended to limit the present application. For those skilled in the art, the present application may have various changes and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the scope of the claims of the present application.

Claims

1. A method for preparing an anti-skid tread rubber, characterized in that: The method comprises: Step 1, rare earth cis-1,4-butadiene rubber and hydrogenated nitrile rubber are mixed, and plasticized for 30-120 seconds, and then fillers and coupling agents are added for the first mixing for 30-120 seconds, and then cellulose acetate butyrate and surfactant are added, and the second mixing is carried out for 30-120 seconds, and the rubber is discharged to obtain a mixed rubber; Step 2: Roll the mixed rubber described in step 1, add a vulcanizing agent and an accelerator, roll the mixed rubber, and vulcanize the mixed rubber to obtain a tread rubber.

2. The method according to claim 1, characterized in that The mass ratio of the rare earth butadiene rubber to the hydrogenated nitrile rubber is 20-30:20-30; more preferably, 25:

30.

3. The method according to claim 1, characterized in that The coupling agent is a silane coupling agent; preferably, the coupling agent is methacryloxypropyltrimethoxysilane; and / or, The surfactant is a cationic surfactant; preferably, the surfactant is diphenyl sulfonyl chloride; and / or, The filler is white carbon black and / or carbon black; preferably, white carbon black; and / or, The vulcanizing agent is sulfur; and / or, The accelerator is zinc dithiocarbamate.

4. The method according to claim 3, characterized in that In parts by mass, the tread rubber includes: 20-30 parts of rare earth butadiene rubber, 20-30 parts of hydrogenated nitrile rubber, 1-5 parts of methacryloyloxypropyl trimethoxysilane, 20-30 parts of white carbon black, 1-5 parts of zinc dithiocarbamate, 1-5 parts of sulfur, 1-5 parts of cellulose acetate butyrate, and 1-5 parts of diphenyl chloride sulfonate; preferably, 25 parts of rare earth butadiene rubber, 30 parts of hydrogenated nitrile rubber, 5 parts of methacryloyloxypropyl trimethoxysilane, 30 parts of white carbon black, 2 parts of zinc dithiocarbamate, 1 part of sulfur, 5 parts of cellulose acetate butyrate, and 2 parts of diphenyl chloride sulfonate.

5. The method according to claim 1, characterized in that The conditions for the plasticating, the first mixing and the second mixing are a temperature of 80° C.-100° C. and a rotation speed of 60-80 rpm.

6. The method according to claim 1, characterized in that The debinding temperature is 140°C-160°C; and / or, The mixing rubber roll conditions include: temperature of 50-70°C, front roll speed of 10-30r / min, rear roll speed of 10-30r / min; and / or, The vulcanization conditions include: temperature 150-170° C., pressure 10-20 MPa.

7. A tread rubber prepared by the method according to any one of claims 1 to 6.

8. Use of the method according to any one of claims 1 to 6 or the tread rubber according to claim 7 in improving the anti-skid, anti-aging and / or wear resistance of a tire.

9. A tire comprising the tread rubber according to claim 7.

10. The tire according to claim 9, characterized in that The tire is a tire for new energy vehicles.

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