CN115895055A - High-wear-resistance new-energy electric bus tire tread rubber, preparation method and application thereof, and tire - Google Patents
High-wear-resistance new-energy electric bus tire tread rubber, preparation method and application thereof, and tire Download PDFInfo
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- CN115895055A CN115895055A CN202211390853.1A CN202211390853A CN115895055A CN 115895055 A CN115895055 A CN 115895055A CN 202211390853 A CN202211390853 A CN 202211390853A CN 115895055 A CN115895055 A CN 115895055A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
Abstract
The invention relates to the technical field of new materials for manufacturing tires, in particular to a high-wear-resistance new-energy electric bus tire tread rubber, a preparation method, application and a tire. The tread composition comprises natural rubber in parts by mass30-40 percent of synthetic rubber, 10-30 percent of synthetic rubber, 28-38 percent of filler, 0.1-3.8 percent of filler dispersant, 1-4 percent of vulcanizing agent, 2:1-1:2 of sulfur/accelerator ratio, 2-15 percent of activator, 2-8 percent of anti-aging agent, 0.1-3 percent of modulus reinforcing agent and 0.1-4 percent of sulfur donor. After the tread composition is vulcanized under the conditions that the external temperature vulcanization temperature of the tire is 135-147 ℃, and the vulcanization time is 46-62 min, the total crosslinking density of the rubber is 14.5 multiplied by 10 ‑ 5 mol/cm 3 ～18.5×10 ‑5 mol/cm 3 The proportion of the monothio bond is 10-20%, the proportion of the disulfide bond is 15-30%, and the proportion of the polysulfide bond is 60-70%, and the prepared tire tread has super wear-resistant characteristic.
Description
Technical Field
The invention relates to the technical field of new materials for manufacturing tires, in particular to a high-wear-resistance new-energy electric bus tire tread rubber, a preparation method, application and a tire.
Background
In recent years, pure electric buses gradually replace traditional fuel buses. Data show that the new energy bus accounts for about 76% of the total amount of the new energy bus. According to calculation, the carbon emission amount reduced by one year of operation of every 30 pure electric buses is equivalent to the carbon emission amount absorbed by 12000 trees. Compared with the traditional fuel bus, the green new energy electric bus has the advantages of low noise, zero emission, zero pollution and the like.
According to introduction, the transmission mode of the electric vehicle is greatly different from that of a traditional vehicle, and the main characteristics are that (1) the dead weight of a new energy vehicle is quite large, the torque transmitted during instant starting is also larger, and the tire with stronger ground holding force needs to be adapted, and a common fuel vehicle tire is rarely reinforced aiming at the point, so that the new energy vehicle bus tire needs better ground holding force. (2) The new energy automobile has no engine noise, but the noise of the tire is more obvious, so that the new energy automobile needs to be matched with a mute tire. (3) Due to the high-torque power transmission of the new energy automobile, the pressure borne by the tire is higher when the automobile is accelerated and braked, the pressure of a common automobile tire possibly cannot meet the pressure under the limit condition, and the tire burst danger occurs, so the new energy automobile needs to be matched with the tire with higher strength and higher modulus. Meanwhile, higher requirements are provided for the abrasion performance of the tire, and the tire tread of the electric bus tire needs to be applied with a special tire tread compound rubber formula to effectively resist abnormal abrasion, so that the service life of the tire is prolonged, and the tire can be suitable for the driving state of urban bus sudden stop and sudden walking.
The high-speed development of electric vehicles puts higher demands on tires. However, in recent years, the frequent problem of the tire of the pure electric bus not only increases the challenge to the safe operation of the bus group, but also brings risks to the operation of the bus company. In the deep-ploughing public transport passenger market, various large tire factories actively respond to the actual conditions of public transport operation to research and develop adaptive tires. The development of a cross-linked network structure suitable for the high-wear-resistance new energy electric bus tread from a microstructure is a major topic of tire technology.
Disclosure of Invention
The invention aims to overcome the defects in the prior art from the microscopic view, and provides high-wear-resistance new-energy electric bus tire tread rubber.
In order to achieve the purpose, the invention adopts the following technical scheme:
the high-wear-resistance new-energy electric bus tire tread rubber comprises the following raw materials in percentage by weight:
the synthetic rubber is butadiene rubber and styrene-butadiene rubber, the combined use ratio of the butadiene rubber and the styrene-butadiene rubber is 4:1-1:1, the ratio of sulfur to an accelerator in a vulcanizing agent is 2:1-1:2, the accelerator comprises 0.1-1.0% of HMMM or HMT, the modulus reinforcing agent is resorcinol, and one, two or more than one of m-methyl resin and derivatives thereof are used in combination; the tread rubber composition is vulcanized under the conditions that the external temperature vulcanization temperature of the tire is 135-147 ℃ and the vulcanization time is 46-62 min, and the total cross-linking density of the vulcanized tread rubber is 14.5 multiplied by 10 -5 mol/cm 3 ～18.5×10 -5 mol/cm 3 The proportion of the monothio bond is 10-20%, the proportion of the disulfide bond is 15-30%, and the proportion of the polysulfide bond is 60-70%.
Preferably, the raw materials of the tread composition before vulcanization of the tread rubber comprise the following components in percentage by weight:
the total rubber crosslinking density of the tread rubber is 15.5 multiplied by 10 -5 mol/cm 3 ～17.5×10 -5 mol/cm 3 The proportion of the monothio bond is 12-18%, the proportion of the disulfide bond is 18-28%, and the proportion of the polysulfide bond is 62-68%.
Preferably, the synthetic rubber is neodymium butadiene rubber and solution-polymerized styrene-butadiene rubber, the cis 1,4 content of the neodymium butadiene rubber is not less than 98%, the styrene-butadiene rubber styrene content is 10-40%, and the glass transition temperature Tg is = -65 to-20 ℃.
Preferably, the filler is carbon black, the particle diameter of the carbon black is 10-20 nm, the iodine absorption value is 115-147 g/kg, and the oil absorption value is 120-132 multiplied by 10 -5 m 3 Kg, the coloring strength is 115-139%; preferably, the filler dispersant is: bis (gamma-triethoxysilylpropyl) tetrasulfide, bis- [3- (triethoxysilylpropyl) propyl]One or two or more of disulfide, zinc stearate, mercaptosilane, isophthaloyl hydrazide and the like.
Preferably, the modulus enhancer is present in a ratio of 3:1 to 1:1 to HMMM or HMT.
Preferably, the sulfur donor is: one, two or more of bis (gamma-triethoxysilylpropyl) tetrasulfide, bis- [3- (triethoxysilyl) propyl ] -disulfide, 4,4' -dithiodimorpholine, morpholine derivative, tetramethylthiuram disulfide, thiuram disulfide or polysulfide, and the like are used in combination.
Further, the invention also discloses a preparation method of the tread rubber, and the mixing method of the tread composition before vulcanization of the tread rubber comprises the following steps:
1) Plasticating: and (2) putting the natural rubber, the synthetic rubber, part of the filler and the filler dispersant into an internal mixer for mixing for 30-50 seconds, mixing at the rotating speed of 37-50 rpm, carrying out lump extraction and lump pressing once every 30-35 seconds, discharging rubber and flaking when the temperature of the rubber material reaches 142-162 ℃, and standing and cooling at room temperature for 8-12 hours to obtain the plasticated rubber.
2) First-stage mixing: and (2) putting the plasticated rubber, the residual filler, the anti-aging agent, the activator and the modulus enhancer into an internal mixer for mixing for 30-50 seconds, mixing at the rotating speed of 37-50 rpm, carrying out lump extraction and lump pressing once every 30-35 seconds, carrying out rubber discharge and piece dropping when the temperature of the rubber reaches 142-162 ℃, standing at room temperature for cooling for 8-12 hours to obtain a first-stage master batch, and then carrying out second-stage mixing.
3) And (3) second-stage mixing: putting the first-stage masterbatch obtained in the step 2) into an internal mixer, mixing at the rotating speed of 30-45 rpm, carrying out lump extraction and lump pressing once every 30-35 seconds, carrying out binder removal and piece dropping when the temperature of the rubber reaches 135-150 ℃, standing at room temperature and cooling for 8-12 hours to obtain second-stage masterbatch, and then carrying out final mixing;
4) And (3) final refining: and (3) putting the two-stage masterbatch obtained in the step 3), sulfur, an accelerator, HMMM or HMT into an internal mixer, mixing at the rotating speed of 20-30 rpm, sequentially carrying out lump extraction and lump pressing at intervals of 30-35 seconds and 25-30 seconds for 15-20 seconds, discharging rubber when the temperature of the rubber material reaches 100-120 ℃, and placing and cooling to obtain the tread rubber composition.
Preferably, the tread composition has an outer temperature vulcanization temperature of 135-147 ℃, a grinding sleeve vulcanization temperature of 135-147 ℃, a side plate vulcanization temperature of 142-147 ℃ and a vulcanization time of 46-62 minutes.
Further, the invention also discloses application of the tread rubber in preparation of the high-wear-resistance new energy electric bus tire tread rubber.
Further, the invention also discloses a high-wear-resistance new energy electric bus tire, and the tread rubber of the tire adopts the high-wear-resistance new energy electric bus tire tread rubber.
By adopting the technical scheme, the cross-linked network structure designed by the tread rubber composition and the distribution thereof have high wear resistance on the premise of ensuring low heat generation and low rolling resistance, which is shown in 1, a low-temperature vulcanization process is adopted, the proportion of double bonds in the cross-linked structure in the tread rubber composition is increased from the vulcanization temperature, the total cross-linked density is increased, and the wear resistance is further improved; 2. the modulus reinforcing agent is added to improve the definite elongation of the tread rubber, is a pre-condensed oligomer with a special structure, can further generate a crosslinking reaction in the rubber vulcanization process, and can improve the crosslinking density of vulcanized rubber so as to achieve the modulus of the vulcanized rubber under the dynamic use condition, is particularly suitable for application requiring high modulus, improves the modulus of rubber materials, and has an auxiliary effect on improving the adhesion between the rubber and framework materials; 3. the sulfur donor is added for vulcanization, the vulcanization effect does not occur at a lower temperature, and the vulcanization reaction is started only after the temperature is raised to the temperature that the sulfur donor is decomposed to release active sulfur. Therefore, the operation is generally safe. The scorching is avoided, the sulfur spraying phenomenon of the rubber material is greatly reduced compared with the sulfur vulcanization alone, and the distribution of the cross-linked network structure is adjusted through the sulfur donor so as to improve the wear resistance. The inventor verifies through the practical use of the tire that the total crosslinking density of the rubber is 14.5 multiplied by 10 -5 mol/cm 3 ～18.5×10 -5 mol/cm 3 The proportion of the monothio bond is 10-20%, the proportion of the disulfide bond is 15-30%, and the proportion of the polysulfide bond is 60-70%, and the prepared tire tread has high wear resistance.
Detailed Description
The technical solutions in the embodiments of the present invention will be examined and completely described below with reference to the embodiments of the present invention, so as to further explain the invention. It should be apparent that the described embodiments are only some embodiments of the present invention, and not all embodiments. Given the embodiments of the present invention, all other embodiments that can be obtained by a person of ordinary skill in the art without any inventive step are within the scope of the present invention.
The formulations of the comparative examples and examples of the present invention are shown in Table 1:
TABLE 1
Wherein:
natural rubber, available from RSS3#.
Neodymium cis-butadiene available from WELLOFF Co
Carbon black was purchased from Shanghai Kabot chemical Co., ltd
Zinc oxide is available from Univ-Ohwi Zinc products, inc. of Zhejiang
Stearic acid was purchased from Baily Co Ltd (horse)
Microcrystalline waxes were purchased from Bairema specialty Chemicals (Suzhou) Ltd
Anti-aging agents 4020 and RD obtained from Nanjing chemical industry, inc., petrochemical group of China
The modulus enhancer is resorcinol available from Hua Ji (China) Inc
HMMM/HMT was obtained from Yuan Tai Biochemical Co., ltd
Sulfur selected from Weifang Jiahong chemical industry limited company product
Accelerator NS was purchased from Shandong Turrieli New materials Co., ltd
Antiscorching agent CTP purchased from Shandong New Rake Material Co., ltd
1,6-bis (N, N-dibenzylthiocarbamoyldithio) hexane from Kyoto Kangsu
Bis (gamma-triethoxysilylpropyl) tetrasulfide from Dombedde New materials Co., ltd
The filler dispersant is mercaptosilane which is purchased from Jiangsu Qi Xiang high New materials Co.
The mixing method of the rubber composition comprises the following steps:
plasticating: and (2) putting natural rubber, synthetic rubber, 20% of filler and a filler dispersant into an internal mixer for mixing for 40 seconds, mixing at the rotating speed of 40rpm, carrying out lump lifting and lump pressing once every 30 seconds, carrying out rubber discharging and sheet dropping when the temperature of the rubber material reaches 152 ℃, and standing and cooling at room temperature for 10 hours to obtain the plasticated rubber.
First-stage mixing: and (2) putting the plasticated rubber, the rest of filler, the anti-aging agent, the activator and the modulus enhancer into an internal mixer for mixing for 40 seconds, mixing at the rotating speed of 43rpm, carrying out lump extraction and lump pressing once every 30 seconds, carrying out rubber discharge and piece dropping when the temperature of the rubber reaches 152 ℃, standing at room temperature and cooling for 10 hours to obtain a first-section master batch, and then carrying out second-section mixing on the first-section master batch.
And (3) second-stage mixing: putting the first-stage masterbatch obtained in the step (1) into an internal mixer, mixing at the rotating speed of 30rpm, carrying out lump extraction and lump pressing once every 30 seconds, carrying out binder removal and piece falling when the temperature of the rubber material reaches 140 ℃, standing at room temperature and cooling for 8-12 hours to obtain second-stage masterbatch, and then carrying out final mixing on the second-stage masterbatch;
and (3) final refining: and (3) putting the two-stage masterbatch obtained in the step (2), sulfur, an accelerator, HMMM or HMT into an internal mixer, mixing at the rotating speed of 25rpm, sequentially carrying out lump extraction and lump pressing at intervals of 30 seconds, 25 seconds and 1 second and 5 seconds, discharging rubber when the temperature of rubber reaches 110 ℃, and placing and cooling to obtain the tread rubber composition.
Vulcanization method 1 the tire vulcanization conditions were: the external temperature vulcanization temperature of the tire is 143 ℃, the vulcanization temperature of the grinding sleeve is 143 ℃, the vulcanization temperature of the side plate is 145 ℃, and the vulcanization time is 52min.
Vulcanization method 2 tire vulcanization conditions were: the external temperature vulcanization temperature of the tire is 151 ℃, wherein the vulcanization temperature of the grinding sleeve is 151 ℃, the vulcanization temperature of the side plate is 147 ℃, and the vulcanization time is 46min.
The crosslinked network structures and bond type distributions of the vulcanizates of examples and comparative examples were determined by the chemical swelling method as follows:
the physical property data are as follows:
from example 2, it can be seen that, by simultaneously using low-temperature vulcanization, adding a modulus enhancer, and adding a vulcanization donor, the crosslinking density is greatly improved compared with the comparative example, but the influence on the bond type distribution is obvious, particularly, the proportion of disulfide bonds is greatly improved, and accordingly, the Akron abrasion loss can be seen on macroscopic properties, compared with the comparative example, the Akron abrasion loss is reduced by 15-25%, and the abrasion index is improved by 25-40%.
By a combination mode, a low-temperature vulcanization process, a vulcanization system and a crude rubber system are simultaneously adopted, so that the total crosslinking density of the rubber is 14.5 multiplied by 10 -5 mol/cm 3 ～18.5×10 -5 mol/cm 3 The proportion of the monothio bond is 10-20%, the proportion of the disulfide bond is 15-30%, and the proportion of the polysulfide bond is 60-70%, and the prepared tire tread has high wear resistance.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention, including any reference to the above-mentioned embodiments. Various modifications to these embodiments will be readily apparent to those skilled in the art. The general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. The high-wear-resistance new-energy electric bus tire tread rubber is characterized in that the raw materials of a tire tread composition before vulcanization of the tire tread rubber comprise the following components in percentage by weight:
the synthetic rubber is butadiene rubber and styrene-butadiene rubber, the combined use ratio of the butadiene rubber and the styrene-butadiene rubber is 4:1-1:1, the ratio of sulfur to an accelerator in a vulcanizing agent is 2:1-1:2, the accelerator comprises 0.1-1.0% of HMMM or HMT, the modulus reinforcing agent is resorcinol, and one, two or more than one of m-methyl resin and derivatives thereof are used in combination; the tread rubber composition is vulcanized under the conditions that the external temperature vulcanization temperature of the tire is 135-147 ℃, the vulcanization time is 46-62 min, and the total cross-linking density of the vulcanized tread rubber is 14.5 multiplied by 10 -5 mol/cm 3 ～18.5×10 -5 mol/cm 3 The percentage of the monothio bond is 10-20%, the percentage of the disulfide bond is 15-30%, and the percentage of the polysulfide bond is 60-70%.
2. The high-wear-resistance new energy electric bus tire tread rubber as claimed in claim 1, wherein the raw materials of the tread composition before vulcanization of the tread rubber comprise the following components in percentage by weight:
the total rubber crosslinking density of the tread rubber is 15.5 multiplied by 10 -5 mol/cm 3 ～17.5×10 -5 mol/cm 3 The proportion of the monothio bond is 12-18%, the proportion of the disulfide bond is 18-28%, and the proportion of the polysulfide bond is 62-68%.
3. The tread rubber according to claim 1 or 2, wherein the synthetic rubber is neodymium-based butadiene rubber and solution-polymerized styrene-butadiene rubber, the content of cis 1,4 of the neodymium-based butadiene rubber is not less than 98%, the styrene content of the styrene-butadiene rubber is 10-40%, and the glass transition temperature Tg = -65-20 ℃.
4. The tread rubber according to claim 1 or 2, wherein the filler is carbon black having a particle diameter of 10 to 20nm, an iodine absorption of 115 to 147g/kg and an oil absorption of 120 to 132 x 10 -5 m 3 Kg, the coloring strength is 115-139%; preferably, the filler dispersant is: bis (gamma-triethoxysilylpropyl) tetrasulfide, bis- [3- (triethoxysilylpropyl) propyl]One or two or more of disulfide, zinc stearate, mercaptosilane, isophthaloyl hydrazide and the like.
5. The tread band of claim 1 or 2, wherein the modulus-enhancing agent to HMMM or HMT ratio is 3:1-1:1.
6. The tread rubber according to claim 1 or 2, wherein the sulfur donor is: one or two or more of bis (gamma-triethoxysilylpropyl) tetrasulfide, bis- [3- (triethoxysilylpropyl ] -disulfide, 4,4' -dithiodimorpholine, morpholine derivative, tetramethylthiuram disulfide, thiuram disulfide or polysulfide, and the like are used in combination.
7. The process for producing the tread rubber according to any one of claims 1 to 6, wherein the mixing of the tread composition before vulcanization of the tread rubber comprises the steps of:
1) Plasticating: and (2) putting the natural rubber, the synthetic rubber, part of the filler and the filler dispersant into an internal mixer for mixing for 30-50 seconds, mixing at the rotating speed of 37-50 rpm, carrying out lump extraction and lump pressing once every 30-35 seconds, discharging rubber and flaking when the temperature of the rubber material reaches 142-162 ℃, and standing and cooling at room temperature for 8-12 hours to obtain the plasticated rubber.
2) First-stage mixing: and (2) putting the plasticated rubber, the residual filler, the anti-aging agent, the activator and the modulus enhancer into an internal mixer for mixing for 30-50 seconds, mixing at the rotating speed of 37-50 rpm, carrying out lump extraction and lump pressing once every 30-35 seconds, carrying out rubber discharge and piece dropping when the temperature of the rubber reaches 142-162 ℃, standing at room temperature for cooling for 8-12 hours to obtain a first-stage master batch, and then carrying out second-stage mixing.
3) And (2) two-stage mixing: putting the first-stage masterbatch obtained in the step 2) into an internal mixer, mixing at the rotating speed of 30-45 rpm, carrying out lump extraction and lump pressing once every 30-35 seconds, carrying out binder removal and piece dropping when the temperature of the rubber reaches 135-150 ℃, standing at room temperature and cooling for 8-12 hours to obtain second-stage masterbatch, and then carrying out final mixing;
4) And (3) final refining: and (3) putting the two-stage masterbatch obtained in the step 3), sulfur, an accelerator, HMMM or HMT into an internal mixer, mixing at the rotating speed of 20-30 rpm, sequentially carrying out lump extraction and lump pressing at intervals of 30-35 seconds and 25-30 seconds for 15-20 seconds, discharging rubber when the temperature of the rubber material reaches 100-120 ℃, and placing and cooling to obtain the tread rubber composition.
8. The method for preparing the tread rubber according to claim 8, wherein the tread composition has an outer temperature vulcanization temperature of 135 ℃ to 147 ℃, a grinding sleeve vulcanization temperature of 135 ℃ to 147 ℃, a side plate vulcanization temperature of 142 ℃ to 147 ℃ and a vulcanization time of 46 minutes to 62 minutes.
9. The use of the tread rubber of any one of claims 1 to 6 in the preparation of high-wear-resistance new energy electric bus tire tread rubber.
10. A high-wear-resistance new energy electric bus tire is characterized in that the tread rubber of the tire adopts the tread rubber of the high-wear-resistance new energy electric bus tire in any one of claims 1 to 6.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211390853.1A CN115895055A (en) | 2022-11-07 | 2022-11-07 | High-wear-resistance new-energy electric bus tire tread rubber, preparation method and application thereof, and tire |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211390853.1A CN115895055A (en) | 2022-11-07 | 2022-11-07 | High-wear-resistance new-energy electric bus tire tread rubber, preparation method and application thereof, and tire |
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| CN115895055A true CN115895055A (en) | 2023-04-04 |
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| CN116218048A (en) * | 2023-04-19 | 2023-06-06 | 中策橡胶集团股份有限公司 | Base rubber with low rolling resistance, high control and excellent tear resistance, mixing method and tire |
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