CN118580580B - Tire tread composition with low rolling resistance and low VOCs emission, preparation method and tire - Google Patents
Tire tread composition with low rolling resistance and low VOCs emission, preparation method and tire Download PDFInfo
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- CN118580580B CN118580580B CN202411034482.2A CN202411034482A CN118580580B CN 118580580 B CN118580580 B CN 118580580B CN 202411034482 A CN202411034482 A CN 202411034482A CN 118580580 B CN118580580 B CN 118580580B
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- 239000012855 volatile organic compound Substances 0.000 title claims abstract description 30
- 238000005096 rolling process Methods 0.000 title claims abstract description 26
- 239000000203 mixture Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000006229 carbon black Substances 0.000 claims abstract description 29
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 20
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 14
- 230000003712 anti-aging effect Effects 0.000 claims abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- 239000007822 coupling agent Substances 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 12
- 244000043261 Hevea brasiliensis Species 0.000 claims abstract description 11
- 229920003052 natural elastomer Polymers 0.000 claims abstract description 11
- 229920001194 natural rubber Polymers 0.000 claims abstract description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 9
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 9
- 239000011593 sulfur Substances 0.000 claims abstract description 9
- -1 3-mercaptopropyl ethoxy Chemical group 0.000 claims abstract description 7
- 235000021355 Stearic acid Nutrition 0.000 claims abstract description 7
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims abstract description 7
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000008117 stearic acid Substances 0.000 claims abstract description 7
- 239000011787 zinc oxide Substances 0.000 claims abstract description 7
- 229920001971 elastomer Polymers 0.000 claims description 15
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 14
- 238000007670 refining Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- WITDFSFZHZYQHB-UHFFFAOYSA-N dibenzylcarbamothioylsulfanyl n,n-dibenzylcarbamodithioate Chemical compound C=1C=CC=CC=1CN(CC=1C=CC=CC=1)C(=S)SSC(=S)N(CC=1C=CC=CC=1)CC1=CC=CC=C1 WITDFSFZHZYQHB-UHFFFAOYSA-N 0.000 claims description 3
- UBUCNCOMADRQHX-UHFFFAOYSA-N N-Nitrosodiphenylamine Chemical compound C=1C=CC=CC=1N(N=O)C1=CC=CC=C1 UBUCNCOMADRQHX-UHFFFAOYSA-N 0.000 claims description 2
- 241000208125 Nicotiana Species 0.000 claims description 2
- 235000002637 Nicotiana tabacum Nutrition 0.000 claims description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N chloroform Substances ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 2
- UEZWYKZHXASYJN-UHFFFAOYSA-N cyclohexylthiophthalimide Chemical compound O=C1C2=CC=CC=C2C(=O)N1SC1CCCCC1 UEZWYKZHXASYJN-UHFFFAOYSA-N 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims description 2
- 239000003292 glue Substances 0.000 claims description 2
- 239000004816 latex Substances 0.000 claims description 2
- 229920000126 latex Polymers 0.000 claims description 2
- IUJLOAKJZQBENM-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)-2-methylpropan-2-amine Chemical compound C1=CC=C2SC(SNC(C)(C)C)=NC2=C1 IUJLOAKJZQBENM-UHFFFAOYSA-N 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000006087 Silane Coupling Agent Substances 0.000 abstract description 6
- 238000004513 sizing Methods 0.000 abstract description 3
- 235000019241 carbon black Nutrition 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 13
- 230000020169 heat generation Effects 0.000 description 7
- 230000000704 physical effect Effects 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 238000007906 compression Methods 0.000 description 5
- 230000006835 compression Effects 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000004073 vulcanization Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010074 rubber mixing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Abstract
The invention relates to a tire tread composition with low rolling resistance and low VOCs emission, a preparation method and a tire. The tire tread composition comprises the following components in parts by weight: 100 parts of natural rubber, 5-20 parts of carbon black, 20-50 parts of white carbon black, 2-5 parts of coupling agent, 3-5 parts of zinc oxide, 1-3 parts of stearic acid, 2-5 parts of anti-aging agent, 1-2 parts of sulfur, 1-4 parts of accelerator and 0.1-0.5 part of scorch retarder; the coupling agent comprises 3-mercaptopropyl ethoxy bis (propane-hexapropoxy) siloxane. Compared with the prior art, the invention uses the high-content white carbon black and simultaneously uses the novel silane coupling agent, so that the mechanical property of the sizing material meets the use requirement of the tire, the heat generating property is reduced, the emission of VOCs in workshops can be reduced by about 80%, and the use requirement of the low-rolling-resistance green tire can be met.
Description
Technical Field
The invention relates to the technical field of tire preparation, in particular to a tire tread composition with low rolling resistance and low VOCs emission, a preparation method and a tire.
Background
For the formal implementation of the pollutant emission standard of the rubber product industry, the emission limit of the waste emission concentration of rubber mixing and vulcanizing devices of tire and other product enterprises is required to be 10mg/m 3, the environmental protection pressure of the rubber industry is increased suddenly, and the environmental protection problem has become the bottleneck for the survival and development of various tire enterprises.
On the other hand, with the development of new energy automobiles, the requirements on low rolling resistance green tires are also higher and higher. The combined use of the white carbon black and the silane coupling agent is not possible to achieve in the aspect of solving the rolling resistance by other fillers at present. Therefore, the amount of the silica white silane coupling agent is gradually increased. The majority of silane coupling agents used in the current market are Si69, si69 is firstly hydrolyzed to remove ethanol gas, and then chemical bond combination is generated on the surface of white carbon black, so that the discharge of a large amount of ethanol gas in the production process leads to the exceeding of VOCs, the aim of finding a coupling agent with low gas emission is to become the key point of source control, meanwhile, the heat generation of sizing materials can be further reduced, the rolling resistance of tires is also a key technology for improving the product quality, and the market share and brand ability of products are improved.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a tire tread composition with low rolling resistance and low VOCs emission, a preparation method and a tire, and the invention provides a tire with low rolling resistance and low VOCs emission by using high-content white carbon black, meanwhile, the novel silane coupling agent is used, the mechanical property of the sizing material meets the use requirement of the tire, the heat generating property is reduced, the emission of VOCs in a workshop can be reduced by about 80%, and the use requirement of the low-rolling-resistance green tire can be met.
The aim of the invention can be achieved by the following technical scheme:
The invention provides a tire tread composition with low rolling resistance and low VOCs emission, which comprises the following components in parts by weight:
Natural rubber 100
Carbon black 5-20
20 To 50 percent of white carbon black
Coupling agent 2-5
Zinc oxide 3-5
Stearic acid 1-3
Anti-aging agent 2-5
1-2 Parts of sulfur
Accelerators 1-4
0.1 To 0.5 of scorch retarder;
the coupling agent comprises 3-mercaptopropyl ethoxy bis (propane-hexapropoxy) siloxane.
Further, the tire tread composition with low rolling resistance and low VOCs emission comprises the following components in parts by weight:
Natural rubber 100
Carbon black 5-20
20 To 50 percent of white carbon black
3-4.2 Coupling agent
Zinc oxide 4
Stearic acid 2
Anti-aging agent 4.5
1 To 1.2 percent of sulfur
Accelerator 2.4-2.8
0.3 Of scorch retarder;
further preferably, the carbon black is preferably 20 parts;
Further preferably, the coupling agent is preferably 3 parts by weight of 3-mercaptopropyl ethoxy bis (propane-hexapropoxy) siloxane, or 3 parts of 3-mercaptopropyl ethoxy bis (propane-hexapropoxy) siloxane+1.2 parts by weight of bis- (gamma-triethoxysilylpropyl) tetrasulfide.
Further, the natural rubber is full latex or tobacco flake rubber or standard natural rubber.
Further, the carbon black is selected from one or a mixture of two of the carbon blacks of model number N220 or N234.
Further, the white carbon black is precipitated white carbon black or high-dispersion white carbon black.
Further, the anti-aging agent is selected from one or more of anti-aging agent 4020, anti-aging agent RD and protective wax.
Further, the accelerator is selected from one or more of accelerator TBBS, accelerator DPG and accelerator TBzTD.
Further, after the use of the novel coupling agent, the vulcanization speed is lowered, and the use of an accelerator (2.4 to 2.8 parts) is required to increase the vulcanization speed.
Further, the scorch retarder is selected from one or more of N-chloroform thio-4-propylene-dicarboximide, zinc alkyl dithiophosphate, N-cyclohexyl thio phthalimide and N-nitrosodiphenylamine.
The second aspect of the invention provides a method for preparing a tire tread material with low rolling resistance and low VOCs emission, comprising the following steps:
S1: preparing a raw material according to the tire tread composition;
S2: masterbatch rubber: adding natural rubber, carbon black, white carbon black, a coupling agent, stearic acid, zinc oxide, an anti-aging agent and the like into an internal mixer for plasticating to obtain a section of masterbatch;
S3: and (3) remilling: adding the masterbatch obtained in the step S2 into an internal mixer for further refining to obtain a second-stage masterbatch;
S4: and (3) final refining: and (3) adding the masterbatch obtained in the step (S3), sulfur, an accelerator and a scorch retarder into an internal mixer for final refining to obtain the tire tread material with low rolling resistance and low VOCs emission.
Further, in S2, during masterbatch mixing, the preset filling coefficient is kept at 67% -75%, the mixing time is 2.5-3.5min, the pressure is 6kg/cm 2, and the masterbatch is discharged at 150-156 ℃;
S3, during remilling, keeping the filling coefficient to 67% -75%, wherein the mixing time is 1.5-2.5min, the pressure is 6kg/cm 2, and discharging glue at 140-145 ℃;
in S4, during final refining, the filling coefficient is kept at 67% -75%, the rubber refining time is 2.0-3.0min, the pressure is 6kg/cm 2, and rubber is discharged at 110-118 ℃.
In a third aspect, the present invention provides a low rolling resistance tire comprising a tire tread material obtained by the above-described preparation method.
Compared with the prior art, the invention has the following technical advantages:
According to the invention, the high-content white carbon black is used, and the novel silane coupling agent is used, so that the mechanical property of the rubber material meets the use requirement of the tire, the heat generating property is reduced, the emission of VOCs in workshops can be reduced by about 80%, and the use requirement of the low-rolling-resistance green tire can be met.
Detailed Description
The present invention will be described in detail with reference to specific examples. In the technical scheme, the characteristics of preparation means, materials, structures or composition ratios and the like which are not explicitly described are regarded as common technical characteristics disclosed in the prior art.
Comparative example 1
100 Parts by weight of natural rubber, 20 parts by weight of carbon black, 33 parts by weight of white carbon black, 3 parts by weight of bis- (gamma-triethoxysilylpropyl) tetrasulfide, 2 parts by weight of stearic acid, 4 parts by weight of zinc oxide, 4.5 parts by weight of an anti-aging agent, 1 part by weight of sulfur, 1.6 parts by weight of an accelerator and 0.3 part by weight of a scorch retarder are thoroughly mixed according to the above process, and the test performance is obtained by sample preparation, vulcanization and the results are shown in Table 2.
Example 1
The obtained samples were tested with the exception that 3-mercaptopropylethoxy-bis (propane-hexapropoxy) siloxane was used instead of bis- (gamma-triethoxysilylpropyl) tetrasulfide, the accelerator was added by 0.8 parts by weight, the remaining components and the process conditions were the same as those of the comparative example, the physical properties were shown in Table 2, the VOCs were reduced from 2834ppm to 578ppm, and the reduction of VOCs was 79.6%. Compared with comparative example 1, the 300% elongation of the rubber compound of example 1 is reduced by 1.3MPa, the elongation is improved by 9%, and the compression heat generation is reduced by 12%. The lower the heat generation is for a low rolling resistance tire, the better.
Example 2
The sulfur and accelerator were added in parts by weight of 0.1 and 0.1 respectively, and the rest of the components and the process were the same as those of example 1, and the obtained samples were tested and the physical properties are shown in Table 2. The tear properties of the compound of example 2 are improved by 16% and the heat generation under compression is reduced by 18% relative to comparative example 1. The decrease in VOCs was more than 70% compared to comparative example 1.
Example 3
The 3-mercaptopropylethoxy-bis (propane-hexapropoxy) siloxane was compounded with bis- (gamma-triethoxysilylpropyl) tetrasulfide (Si-69) and the remaining components and process were the same as in example 1, and the resulting samples were tested and the physical properties are shown in Table 2. The compound of example 3 had a slight increase in elongation and strength, a slight decrease in elongation and tear, and a 18% decrease in compression heat generation relative to the comparative example. The decrease in VOCs was more than 70% compared to comparative example 1.
Example 4
The sulfur and accelerator were added in parts by weight of 0.2 and 0.2, respectively, and the rest of the components and the process were the same as those of example 3, and the obtained samples were tested and the physical properties are shown in Table 2. Compared with comparative example 1, the mechanical property of the rubber compound of example 4 and the property of the comparative example are basically within 5%, and the compression heat generation is reduced by 14%. The decrease in VOCs was more than 70% compared to comparative example 1.
Example 5
The resulting samples were tested for physical properties as shown in Table 2 with a TBzTD weight increase of 0.2 parts and the remaining components and process being the same as in example 4. Example 5 showed a 20% decrease in tear and a 25% decrease in compression heat generation relative to comparative example 1. The decrease in VOCs was more than 70% compared to comparative example 1.
Table 1 summary of comparative examples and example formulations
The specific test data of the produced rubber is shown in Table 2 according to the rubber formula and the preparation process.
The physical and mechanical property test data according to the national standard are as follows:
table 2 physical Properties of the compounds
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present invention.
Claims (10)
1. A low rolling resistance low VOCs emitting tire tread composition comprising the following components in parts by weight:
Natural rubber 100
Carbon black 20
20 To 50 percent of white carbon black
3-5 Coupling agent
Zinc oxide 3-5
Stearic acid 1-3
Anti-aging agent 2-5
1-2 Parts of sulfur
Accelerators 1-4
0.1 To 0.5 of scorch retarder;
the coupling agent comprises 3-mercaptopropyl ethoxy bis (propane-hexapropoxy) siloxane;
3 parts by weight of 3-mercaptopropyl ethoxy bis (propane-hexapropoxy) siloxane, or 3 parts by weight of 3-mercaptopropyl ethoxy bis (propane-hexapropoxy) siloxane and 1.2 parts by weight of bis- (gamma-triethoxysilylpropyl) tetrasulfide in the coupling agent.
2. The low rolling resistance low VOCs emitting tire tread composition of claim 1 wherein said natural rubber is a full latex or a tobacco flake rubber or a standard natural rubber.
3. The low rolling resistance low VOCs emitting tire tread composition of claim 1 wherein said carbon black is selected from the group consisting of one or a mixture of two of model N220 or model N234.
4. The low rolling resistance low VOCs emitting tire tread composition of claim 1 wherein said white carbon black is a precipitated white carbon black or a highly dispersed white carbon black.
5. The low rolling resistance low VOCs emitting tire tread composition of claim 1 wherein said anti-aging agent is selected from one or more of the group consisting of anti-aging agent 4020, anti-aging agent RD, and protective wax.
6. The low rolling resistance low VOCs emitting tire tread composition of claim 1 wherein said accelerator is selected from the group consisting of accelerator TBBS, accelerator DPG, and a blend of one or more of accelerator TBzTD.
7. The low rolling resistance low VOCs emitting tire tread composition of claim 1 wherein said scorch retarder is selected from the group consisting of N-chloroform based thio-4-propylhexene-dicarboximide, zinc alkyl dithiophosphate, N-cyclohexyl thiophthalimide, N-nitrosodiphenylamine.
8. The preparation method of the tire tread material with low rolling resistance and low VOCs emission is characterized by comprising the following steps:
s1: preparing a raw material according to the tire tread composition as claimed in any one of claims 1 to 7;
s2: masterbatch rubber: adding natural rubber, carbon black, white carbon black, a coupling agent, stearic acid, zinc oxide and an anti-aging agent into an internal mixer for plasticating to obtain a section of master batch;
S3: and (3) remilling: adding the masterbatch obtained in the step S2 into an internal mixer for further refining to obtain a second-stage masterbatch;
S4: and (3) final refining: and (3) adding the masterbatch obtained in the step (S3), sulfur, an accelerator and a scorch retarder into an internal mixer for final refining to obtain the tire tread material with low rolling resistance and low VOCs emission.
9. The method for preparing the tire tread material with low rolling resistance and low VOCs emission according to claim 8, wherein in S2, the masterbatch is prepared by keeping a preset filling coefficient of 67-75%, the mixing time is 2.5-3.5min, the pressure is 6kg/cm 2, and the masterbatch is discharged at 150-156 ℃;
S3, during remilling, keeping the filling coefficient to 67% -75%, wherein the mixing time is 1.5-2.5min, the pressure is 6kg/cm 2, and discharging glue at 140-145 ℃;
in S4, during final refining, the filling coefficient is kept at 67% -75%, the rubber refining time is 2.0-3.0min, the pressure is 6kg/cm 2, and rubber is discharged at 110-118 ℃.
10. A low rolling resistance tire comprising the tire tread material obtained by the method of claim 8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202411034482.2A CN118580580B (en) | 2024-07-31 | Tire tread composition with low rolling resistance and low VOCs emission, preparation method and tire |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202411034482.2A CN118580580B (en) | 2024-07-31 | Tire tread composition with low rolling resistance and low VOCs emission, preparation method and tire |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN118580580A CN118580580A (en) | 2024-09-03 |
| CN118580580B true CN118580580B (en) | 2024-11-19 |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110305374A (en) * | 2019-07-22 | 2019-10-08 | 三角轮胎股份有限公司 | Low rolling hinders all-steel radial tyre tread rubber composition |
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110305374A (en) * | 2019-07-22 | 2019-10-08 | 三角轮胎股份有限公司 | Low rolling hinders all-steel radial tyre tread rubber composition |
Non-Patent Citations (1)
| Title |
|---|
| 不同类型硅烷偶联剂在半钢子午线轮胎胎面胶中的应用;姚翔等;轮胎工业;20230131;第43卷;30-33页 * |
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