CN112250922A - Low-rolling-resistance tread rubber composition and preparation method thereof - Google Patents
Low-rolling-resistance tread rubber composition and preparation method thereof Download PDFInfo
- Publication number
- CN112250922A CN112250922A CN202011233186.7A CN202011233186A CN112250922A CN 112250922 A CN112250922 A CN 112250922A CN 202011233186 A CN202011233186 A CN 202011233186A CN 112250922 A CN112250922 A CN 112250922A
- Authority
- CN
- China
- Prior art keywords
- parts
- rolling resistance
- low rolling
- rubber
- carbon black
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920001971 elastomer Polymers 0.000 title claims abstract description 62
- 239000005060 rubber Substances 0.000 title claims abstract description 62
- 239000000203 mixture Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000006229 carbon black Substances 0.000 claims abstract description 46
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000005096 rolling process Methods 0.000 claims abstract description 40
- 229920003048 styrene butadiene rubber Polymers 0.000 claims abstract description 34
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003607 modifier Substances 0.000 claims abstract description 17
- 229920006978 SSBR Polymers 0.000 claims abstract description 12
- 239000011787 zinc oxide Substances 0.000 claims abstract description 10
- 239000011159 matrix material Substances 0.000 claims abstract description 9
- 235000021355 Stearic acid Nutrition 0.000 claims abstract description 7
- 239000010692 aromatic oil Substances 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
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 7
- 239000008117 stearic acid Substances 0.000 claims abstract description 7
- 244000043261 Hevea brasiliensis Species 0.000 claims abstract description 6
- 235000019808 microcrystalline wax Nutrition 0.000 claims abstract description 6
- 239000004200 microcrystalline wax Substances 0.000 claims abstract description 6
- 229920003052 natural elastomer Polymers 0.000 claims abstract description 6
- 229920001194 natural rubber Polymers 0.000 claims abstract description 6
- 101100434170 Oryza sativa subsp. japonica ACR2.1 gene Proteins 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 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 abstract description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 19
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 10
- 238000007599 discharging Methods 0.000 claims description 10
- 239000011593 sulfur Substances 0.000 claims description 10
- 229910052717 sulfur Inorganic materials 0.000 claims description 10
- 230000003712 anti-aging effect Effects 0.000 claims description 9
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- 238000004073 vulcanization Methods 0.000 claims description 5
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 claims description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- 238000010521 absorption reaction Methods 0.000 claims description 4
- 239000012752 auxiliary agent Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000011065 in-situ storage Methods 0.000 claims description 4
- STSDHUBQQWBRBH-UHFFFAOYSA-N n-cyclohexyl-1,3-benzothiazole-2-sulfonamide Chemical compound N=1C2=CC=CC=C2SC=1S(=O)(=O)NC1CCCCC1 STSDHUBQQWBRBH-UHFFFAOYSA-N 0.000 claims description 4
- 238000007670 refining Methods 0.000 claims description 4
- -1 1, 3-dimethylbutyl Chemical group 0.000 claims description 3
- 230000003213 activating effect Effects 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 2
- 239000003292 glue Substances 0.000 claims description 2
- 229910001385 heavy metal Inorganic materials 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- 239000011630 iodine Substances 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 claims description 2
- 238000010074 rubber mixing Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 239000012190 activator Substances 0.000 claims 1
- 238000001556 precipitation Methods 0.000 claims 1
- 239000006185 dispersion Substances 0.000 abstract description 10
- 230000000694 effects Effects 0.000 description 13
- 238000012360 testing method Methods 0.000 description 13
- 239000000463 material Substances 0.000 description 11
- 239000000945 filler Substances 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 8
- 238000003860 storage Methods 0.000 description 6
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000003993 interaction Effects 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 2
- 241001441571 Hiodontidae Species 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000004134 energy conservation Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000002372 labelling Methods 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- ZZMVLMVFYMGSMY-UHFFFAOYSA-N 4-n-(4-methylpentan-2-yl)-1-n-phenylbenzene-1,4-diamine Chemical compound C1=CC(NC(C)CC(C)C)=CC=C1NC1=CC=CC=C1 ZZMVLMVFYMGSMY-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000006855 networking Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C1/0016—Compositions of the tread
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Tires In General (AREA)
Abstract
The invention relates to a tread rubber composition with low rolling resistance and a preparation method thereof. The rubber composition comprises the following raw materials in parts by weight: 10-20 parts of carbon black N234, 60-70 parts of precipitated white carbon black HD165MP 60, 20-30 parts of natural rubber TSR20/STR20, 70-80 parts of non-oil-extended solution-polymerized styrene-butadiene rubber SSBR, 9.6-11.2 parts of bis- [ gamma- (triethoxysilyl) propyl ] tetrasulfide Si69, 1-2 parts of microcrystalline wax Antilux111, 2-3 parts of zinc oxide ZnO, and SAD (stearic acid): 2-3 parts of environment-friendly aromatic oil V700, 10-20 parts of low rolling resistance modifier OCST, and 0.3-1.1 parts of low rolling resistance modifier OCST. The invention obtains good dispersion of the high-dispersion precipitated silica in the non-oil-extended solution-polymerized styrene-butadiene rubber SSBR (No. NS616) matrix by using the low rolling resistance modifier OCST.
Description
Technical Field
The invention relates to the technical field of tire preparation, in particular to a low-rolling-resistance tread rubber composition and a preparation method thereof.
Background
Along with the aggravation of the world energy crisis and environmental pollution, energy conservation and environmental protection are more and more emphasized in various countries. In order to reduce the consumption of fuel oil and the emission of greenhouse gases, the automobile industry is also developing towards energy conservation and environmental protection, the concept of green tires is more and more popular, and since the Michelin group pushes out energy-saving tires, precipitated silica (by partially or completely replacing carbon black) is proved to be a filler for manufacturing high-performance green car pneumatic tires. The main reason is that white carbon black can effectively balance the rolling resistance performance and the braking performance of the tire, and simultaneously, the white carbon black is a non-petroleum product and has environmental friendliness. In fact, when the vehicle is equipped with an anti-lock braking system, the tire performance is significantly improved due to the simultaneous improvement of rolling resistance, wet grip and braking distance, compared to carbon black. Due to the improvement of the performances, the white carbon black filled tread rubber material also becomes the best material for improving the performances of the tire.
The surface of the white carbon black is rich in silicon hydroxyl, and the surface property of the white carbon black is greatly different from that of Styrene Butadiene Rubber (SBR), so that the white carbon black is difficult to obtain good dispersion in a rubber matrix. To solve this problem, a great deal of work has been done by domestic and foreign scholars, and the most successful method among them is the use of a silane coupling agent. The interaction between the rubber and the filler can be effectively improved by using the silane coupling agent. However, with the release of the latest european labeling law, the requirement for tire rolling resistance is higher and higher, which requires tire manufacturers to further optimize and upgrade tire structures and formulations to meet the labeling law. These include weight reduction of tires, application of modified rubbers, development of novel coupling agents, development of novel additives, and the like.
Disclosure of Invention
In view of the above, the present invention provides a tread rubber composition with low rolling resistance and a preparation method thereof, so as to solve the above technical problems.
In order to achieve the above object, the present invention provides the following technical solutions:
a low rolling resistance tread rubber composition comprises the following raw materials in parts by weight: 100 parts of matrix rubber, 10-20 parts of carbon black N234, and 60-70 parts of precipitated white carbon black HD165MP 60, wherein the matrix rubber is natural rubber TSR20/STR20, 20-30 parts of non-oil-extended solution-polymerized styrene butadiene rubber SSBR, 70-80 parts of bis- [ gamma- (triethoxysilyl) propyl ] tetrasulfide Si69, 9.6-11.2 parts of microcrystalline wax Antilux111, 2-3 parts of zinc oxide ZnO, and stearic acid SAD: 2-3 parts of environment-friendly aromatic oil V700, 10-20 parts of low rolling resistance modifier OCST, and 0.3-1.1 parts of low rolling resistance modifier OCST.
As a further scheme of the invention: also comprises 1-2 parts of an anti-aging agent 4020[ N (1, 3-dimethylbutyl) -N/-phenyl p-phenylenediamine ]; 1-2 parts of accelerator DPG/diphenylguanidine; 1-2 parts of accelerator N-cyclohexyl-2-benzothiazole sulfonamide; 1-2 parts of vulcanizing agent sulfur S.
As a further scheme of the invention: the precipitated white carbon black HD165MP has a specific surface area (BET) of 165 square meters per gram, is relatively high, belongs to a high-dispersibility filler, and has improved dispersibility, which is beneficial to improving the comprehensive performance of the formula. Heating at 105 deg.C (2 hr) to reduce weight by 4% < R1 < 8%; ignition loss is less than 7 percent at 1000 ℃ (2 hours); water solubles < 2%.
As a further scheme of the invention: the environment-friendly aromatic oil V700 does not contain polycyclic aromatic hydrocarbon and heavy metal, is nontoxic aromatic oil, has environment-friendly property, conforms to the reach regulation of European Union, has the characteristics of good rubber compatibility, high temperature resistance, low volatilization and the like, can obviously improve the processability of rubber, and has good effect on the gripping property and the braking property of tires. Viscous liquid, heavy naphthenic oil, density 0.942g/cm3The flash point is more than 220 ℃, the aniline point is more than 75 ℃ and less than R290℃。
As a further scheme of the invention: the OCST is a rose-red powder material, and is used for modifying solution-polymerized styrene-butadiene rubber, the rolling resistance reducing effect is better when the addition amount of the OCST is larger, but the processing difficulty is increased, so that the optimal range of the OCST is 0.3-1.1 parts by weight.
As a further scheme of the invention: the anti-aging agent comprises 4020/6PPD, the accelerator comprises CBS and DPG, and the vulcanizing agent comprises sulfur.
As a further scheme of the invention: 20-30 parts of natural rubber TSR20/STR 20; 20# standard glue, ash content is less than 1.0%; chemical impurities are less than 0.16 percent; the volatile component is less than 0.8 percent.
As a further scheme of the invention: a non-oil-extended solution-polymerized styrene-butadiene rubber SSBR which contains 21 wt% of styrene and 63% of vinyl and is non-oil-extended and has a Mooney viscosity ML (1+4) at 100 ℃ of 62.
As a further scheme of the invention: 10-20 parts of carbon black N234, carbon black: black granular or powder, iodine absorption value is less than 125g/kg, DBP absorption value is less than 13010-5m3/kg, heating decrement at 125 ℃ is less than 2.0 percent; the 45-mesh screen residue is less than 1000 mg/kg.
A preparation method of a low rolling resistance tread rubber composition comprises the following steps: step 1: mixing non-oil-extended solution-polymerized styrene-butadiene rubber SSBR (No. NS616), a first part of carbon black N234 and a low rolling resistance modifier to obtain a modified solution-polymerized styrene-butadiene rubber polymer, mixing in an XM370 internal mixer, and discharging rubber when the rubber mixing temperature is raised to 165 ℃;
step 2: carrying out first-stage masterbatch on the modified solution polymerized styrene-butadiene rubber polymer, white carbon black, a silane coupling agent, an activating agent, an anti-aging agent and an auxiliary agent, and discharging the first-stage masterbatch;
and step 3: and (3) carrying out second-stage final refining on the first-stage master batch, the accelerator and the sulfur, discharging the final refined batch, extruding the final refined batch into a tire tread, and then carrying out molding and vulcanization to obtain the tire. The tire tread rubber is prepared by blending in-situ modified solution-polymerized styrene-butadiene rubber, firstly modifying the solution-polymerized styrene-butadiene rubber by using a low rolling resistance modifier, blending the low rolling resistance modifier, carbon black and the solution-polymerized styrene-butadiene rubber, carrying out in-situ modification on the solution-polymerized styrene-butadiene rubber at a certain temperature to obtain a modified solution-polymerized styrene-butadiene rubber premix, ensuring the full performance of the modification process by using sufficient mixing temperature and time and the existence of the carbon black, then mixing the modified solution-polymerized styrene-butadiene rubber premix, a second part of the carbon black, a silane coupling agent, silicon dioxide, an activating agent, an anti-aging agent, an accelerating agent, sulfur and an auxiliary agent together to obtain a final rubber compound, extruding the final rubber compound into a tire tread, forming and vulcanizing the tire together with other parts, and improving the dispersion of white carbon black in the solution-polymerized styrene-butadiene rubber due to the increased interaction between the modified solution-polymerized, the loss factor and the compression heat generation of the tread rubber material at the temperature of 50-70 ℃ are reduced, the resilience of the rubber material is improved, and the modified tread rubber material is applied to the tire to effectively reduce the rolling resistance of the tire
Compared with the prior art, the invention has the following advantages: the invention obtains good dispersion of the high-dispersion precipitated silica in the non-oil-extended solution-polymerized styrene-butadiene rubber SSBR (No. NS616) matrix by using the low rolling resistance modifier OCST.
Drawings
FIG. 1 vulcanizate storage modulus G'.
Figure 2 vulcanizate loss factor Tan delta.
FIG. 3 is a graph showing the influence of the amounts of OCST modified rubber and white carbon black on the vulcanization characteristics.
FIG. 4 is a graph showing the effect of the amount of OCST modified rubber and white carbon black on Payne effect.
FIG. 5 illustrates the amount of OCST modified rubber and white carbon black used versus tan & # 948; an influence graph.
Detailed Description
The present invention will be explained in more detail with reference to the following examples, but the present invention is not limited to these examples, and the present invention is not limited to these examples in any way.
A low rolling resistance tread rubber composition comprises the following raw materials in parts by weight: 100 parts of matrix rubber, 10-20 parts of carbon black N234, and 60-70 parts of precipitated white carbon black HD165MP 60, wherein the matrix rubber is natural rubber TSR20/STR20, 20-30 parts of non-oil-extended solution-polymerized styrene butadiene rubber SSBR, 70-80 parts of bis- [ gamma- (triethoxysilyl) propyl ] tetrasulfide Si69, 9.6-11.2 parts of microcrystalline wax Antilux111, 2-3 parts of zinc oxide ZnO, and stearic acid SAD: 2-3 parts of environment-friendly aromatic oil V700, 10-20 parts of low rolling resistance modifier OCST, and 0.3-1.1 parts of low rolling resistance modifier OCST.
Example 1
The tire is prepared by the following specific steps:
1. the preparation method of the modified solution polymerized styrene-butadiene rubber polymer comprises the following steps: the weight percentages are as follows: the SSBR (No. NS616) of the non-oil-extended solution-polymerized styrene-butadiene rubber is 256kg, the carbon black is 32kg, and the low rolling resistance modifier is 1.28 kg. And sequentially putting the composite materials into an XM370 type internal mixer for mixing, wherein the rotating speed of a rotor is 15-65r/min, the rubber discharge temperature is 165 ℃, and then discharging the mixture by an open mill to obtain the modified solution polymerized styrene-butadiene rubber polymer which is marked as MSSBR.
2. The preparation method of the tire comprises the following steps: the weight percentages are as follows: 135.6Kg of MSSBR, 30Kg of TSR20, 15Kg of carbon black, 97.5Kg of silicon dioxide HD165MP, 15.6Kg of silane coupling agent, 22.5Kg of oil, 3Kg of zinc oxide, 3Kg of stearic acid, 3Kg of p-phenylenediamine anti-aging agent 4020, 1.5Kg of microcrystalline wax Antilux111 and 1.5Kg of accelerator DPG/diphenylguanidine; 3kg of accelerator N-cyclohexyl-2-benzothiazole sulfonamide; the vulcanizing agent sulfur S is 2.25 kg. Processing the composition material by adopting a 3-stage mixing process, wherein 3-stage mixing is carried out in an F270 type internal mixer, and the rotating speed of a rotor is 10-65 r/min; 3, mixing and then discharging the sheets by an open mill; the feeding sequence is that 135.6Kg of MSSBR, 30Kg of TSR20, 15Kg of carbon black, 97.5Kg of silicon dioxide HD165MP, 15.6Kg of silane coupling agent, 22.5Kg of oil, 3Kg of zinc oxide, 3Kg of stearic acid, 3Kg of p-phenylenediamine antioxidant 4020, 1.5Kg of microcrystalline wax Antilux111 are added in the first-stage master batch, and the rubber discharging temperature of the first-stage master batch is 150 ℃, so that first-stage master batch is obtained; the first-stage masterbatch is subjected to a remill process of second-stage masterbatch to obtain second-stage masterbatch; and (3) carrying out third-stage final refining on the second-stage master batch, adding 1.5kg of accelerator DPG/diphenylguanidine, 3kg of accelerator N-cyclohexyl-2-benzothiazole sulfonamide, 2.25kg of vulcanizing agent sulfur S into the second-stage master batch, and controlling the rubber discharge temperature of the third-stage final refining to be 110 ℃. And after standing for 8 hours, discharging the final mixed rubber, extruding tire components, standing for 8-12 hours, forming a tire blank, and finally vulcanizing the tire blank to form the final tire.
Prior tread rubber compositions were compared to this case (test) by comparing NS616 with the OCST modification (test 1, test 2, test 3 for NS616/SIL60, NS616-M/SIL6, NS616-M/SIL70, respectively) as shown in Table 1 below:
testing and characterization
1 processability
The Mooney viscosity is tested according to ASTM D1646-2007, wherein the test temperature condition is 100 ℃, preheating is carried out for 1min, and testing is carried out for 4 min; the test temperature for mooney scorch was 130 ℃; the test of the vulcanization characteristic curve is carried out according to the national standard GB/T16584-96, the test temperature is 150 ℃, and the test time is 60 min.
TABLE 2 Effect of OCST modified rubber and white carbon Black on processability
As shown in Table 2, NS616 has better processability, has a Mooney viscosity value of about 66, and thus has better matching property with OCST having improved filler dispersion, and the addition of OCST causes increase of the Mooney viscosity, but the processability can still be maintained at a better level (generally, the Mooney viscosity is lower than 80, and the processability is better). In addition, the Mooney viscosity of the final rubber compound is increased along with the increase of the amount of the white carbon black. The scorch time change is very small after the OCST modified rubber is introduced into the ultra-low rolling resistance formula; the scorching time is shortened after the consumption of the white carbon black is increased.
As can be found from fig. 3, the use of the OCST modified rubber can reduce the torque at the initial stage of vulcanization, which indicates that the OCST can interact with the polar groups on the surface of the white carbon black while improving the efficiency of the coupling agent, the networking phenomenon of the white carbon black is weakened, and S' min is reduced; however, the S' min shows an increasing trend after the white carbon black dosage is increased.
2 static mechanical Properties
The prepared solution polymerized styrene-butadiene rubber composite material is subjected to tensile property test representation by adopting a tensile testing machine (Zwick Z010, Zwick company in Germany). The test procedure was carried out according to ASTM D412-2006, with a tensile rate of 500mm/min, a test temperature of (23. + -.2). degree.C., an active part of the specimen having a length of 25mm and a width of 4 mm. For each set of samples, three parallel experiments were performed and the results averaged.
TABLE 1 Effect of vulcanizate Properties
The use of an OCST-modified rubber improves the filler-rubber interaction and improves the filler dispersion, so that the hardness decreases and the MA300/MA100 ratio of the reinforcing properties increases, and the tear strength and elongation at break slightly decrease due to the increase in 300% tensile modulus.
3 DMA dynamic performance deformation scanning
The vulcanizate was subjected to strain scanning in planar shear mode using a Metravib DMA +1000 dynamic mechanical Analyzer. The strain range is 0.143% -99.115% from peak to peak, the frequency is 10Hz, and the temperature is 25 ℃.
TABLE 2 storage modulus G' Delta
The storage modulus G' of the cured compound as a function of strain is shown in FIG. 1 and Table 2. This non-linear behavior exhibited by the compound under continuously increasing strain is known as the Payne effect. The degree of the Payne effect, i.e., the degree of aggregation of the filler, is generally characterized by the values of G0 '-G ∞' and the values of G0 ', G ∞' and G0 '-G ∞' of the samples examined are shown in Table 2(G0 'is the storage modulus at 0.143% for small strains and G ∞' is the storage modulus at 97.115% for large strains). The rubber compound produced by the formula disclosed by the invention is low in Payne effect, namely the rubber compound is good in dispersion effect, and the rubber compound network is relatively difficult to damage.
For the chain end modified solution polymerized styrene butadiene rubber NS616, the storage modulus G' of the vulcanized rubber is obviously reduced after being modified again by 0.4phr of OCST, which shows that the interaction between the filler and the filler is weakened, and the dispersibility is improved; meanwhile, as can be seen from fig. 4, the Payne effect of adding 70phr of white carbon black in the OCST modified SSBR system is weaker than that of not adding OCST, which indicates that the effect of OCST in improving the dispersibility of white carbon black is very significant, especially at high filling amount. In the PCR field, tan. delta. is commonly used to characterize the rolling resistance of tires. As can be seen from FIG. 5, the tan. delta. decreased significantly with the addition of 0.4phr OCST, indicating that the decrease in rolling resistance is very significant.
The NS616 rubber material has low Mooney viscosity and long Mooney scorch time, which shows that the processing performance is excellent. The Payne effect of the sizing material prepared by using the NS616 formula is equivalent and lower, which shows that the dispersion effect of the filler in the sizing material is better, and the formula with better comprehensive performance can be considered.
The invention effectively improves the cutting resistance and tearing resistance of the tire tread formula. The physical properties of the tread formula are positively influenced, and the tear resistance of the rubber material is obviously improved due to the addition of the tear-resistant resin and the carbon nanotube material.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The tread rubber composition with low rolling resistance is characterized by comprising the following raw materials in parts by weight: 100 parts of matrix rubber, 10-20 parts of carbon black N234, and 60-70 parts of precipitated white carbon black HD165MP 60, wherein the matrix rubber is natural rubber TSR20/STR20, 20-30 parts of non-oil-extended solution-polymerized styrene butadiene rubber SSBR, 70-80 parts of bis- [ gamma- (triethoxysilyl) propyl ] tetrasulfide Si69, 9.6-11.2 parts of microcrystalline wax Antilux111, 2-3 parts of zinc oxide ZnO, and stearic acid SAD: 2-3 parts of environment-friendly aromatic oil V700, 10-20 parts of low rolling resistance modifier OCST, and 0.3-1.1 parts of low rolling resistance modifier OCST.
2. The low rolling resistance tread rubber composition according to claim 1, wherein: also comprises 1-2 parts of an anti-aging agent 4020[ N (1, 3-dimethylbutyl) -N/-phenyl p-phenylenediamine ]; 1-2 parts of accelerator DPG/diphenylguanidine; 1-2 parts of accelerator N-cyclohexyl-2-benzothiazole sulfonamide; 1-2 parts of vulcanizing agent sulfur S.
3. The low rolling resistance tread rubber composition according to claim 1, wherein: the precipitation method white carbon black HD165MP has a specific surface area (BET) of 165 square meters per gram and a heating loss of 4 percent at 105 ℃ which is more than R1 and less than 8 percent; ignition loss is less than 7 percent at 1000 ℃ (2 hours); water solubles < 2%.
4. The low rolling resistance tread rubber composition according to claim 1, wherein: the environment-friendly aromatic oil V700 does not contain polycyclic aromatic hydrocarbon and heavy metal and has the density of 0.942g/cm3The flash point is more than 220 ℃, the aniline point is more than 75 ℃ and less than R2 and less than 90 ℃.
5. A low rolling resistance tread rubber composition according to claim 2, wherein: the anti-aging agent comprises 4020/6PPD, the accelerator comprises CBS and DPG, and the vulcanizing agent comprises sulfur.
6. The low rolling resistance tread rubber composition according to claim 1, wherein: 20-30 parts of natural rubber TSR20/STR 20; 20# standard glue, ash content is less than 1.0%; chemical impurities are less than 0.16 percent; the volatile component is less than 0.8 percent.
7. The low rolling resistance tread rubber composition according to claim 1, wherein: a non-oil-extended solution-polymerized styrene-butadiene rubber SSBR which contains 21 wt% of styrene and 63% of vinyl and is non-oil-extended and has a Mooney viscosity ML (1+4) at 100 ℃ of 62.
8. The low rolling resistance tread rubber composition according to claim 1, wherein: 10-20 parts of carbon black N234, carbon black: black granular or powder, iodine absorption value is less than 125g/kg, DBP absorption value is less than 13010-5m3/kg, heating decrement at 125 ℃ is less than 2.0 percent; the 45-mesh screen residue is less than 1000 mg/kg.
9. A preparation method of a tread rubber composition with low rolling resistance is characterized by comprising the following steps:
step 1: mixing non-oil-extended solution-polymerized styrene-butadiene rubber SSBR, a first part of carbon black N234 and a low rolling resistance modifier to obtain a modified solution-polymerized styrene-butadiene rubber polymer, mixing in an XM370 internal mixer, and discharging rubber when the rubber mixing temperature is raised to 165 ℃;
step 2: carrying out first-stage masterbatch on the modified solution polymerized styrene-butadiene rubber polymer, white carbon black, a silane coupling agent, an activating agent, an anti-aging agent and an auxiliary agent, and discharging the first-stage masterbatch;
and step 3: and (3) carrying out second-stage final refining on the first-stage master batch, the accelerator and the sulfur, discharging the final refined batch, extruding the final refined batch into a tire tread, and then carrying out molding and vulcanization to obtain the tire.
10. The method for preparing a tread rubber composition with low rolling resistance as claimed in claim 9, wherein the tire tread rubber is prepared by blending in-situ modified solution-polymerized styrene-butadiene rubber, the solution-polymerized styrene-butadiene rubber is modified by the low rolling resistance modifier, the solution-polymerized styrene-butadiene rubber is modified in situ at a certain temperature by blending the low rolling resistance modifier, carbon black and the solution-polymerized styrene-butadiene rubber to obtain a modified solution-polymerized styrene-butadiene rubber pre-mixture, the modified solution-polymerized styrene-butadiene rubber pre-mixture is mixed with a second part of carbon black, silane coupling agent, silica, activator, anti-aging agent, accelerator, sulfur and auxiliary agent to obtain a final rubber, the final rubber is pressed into a tread, and the tread rubber is molded and vulcanized with other parts to obtain the tire.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011233186.7A CN112250922A (en) | 2020-11-06 | 2020-11-06 | Low-rolling-resistance tread rubber composition and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011233186.7A CN112250922A (en) | 2020-11-06 | 2020-11-06 | Low-rolling-resistance tread rubber composition and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112250922A true CN112250922A (en) | 2021-01-22 |
Family
ID=74266563
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011233186.7A Pending CN112250922A (en) | 2020-11-06 | 2020-11-06 | Low-rolling-resistance tread rubber composition and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112250922A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015109792A1 (en) * | 2014-01-23 | 2015-07-30 | 怡维怡橡胶研究院有限公司 | Method for improving elasticity and heat build-up performance of rubber product |
| CN109181039A (en) * | 2018-09-11 | 2019-01-11 | 万力轮胎股份有限公司 | A kind of tire in-situ modified rubber composition and tire and preparation method thereof |
| CN109369998A (en) * | 2018-09-30 | 2019-02-22 | 安徽佳通乘用子午线轮胎有限公司 | A kind of high humidity grabs the Tire tread rubber composition of performance and low rolling resistance |
-
2020
- 2020-11-06 CN CN202011233186.7A patent/CN112250922A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015109792A1 (en) * | 2014-01-23 | 2015-07-30 | 怡维怡橡胶研究院有限公司 | Method for improving elasticity and heat build-up performance of rubber product |
| CN109181039A (en) * | 2018-09-11 | 2019-01-11 | 万力轮胎股份有限公司 | A kind of tire in-situ modified rubber composition and tire and preparation method thereof |
| CN109824952A (en) * | 2018-09-11 | 2019-05-31 | 万力轮胎股份有限公司 | A kind of tire in-situ modified rubber composition and tire and preparation method thereof |
| CN109369998A (en) * | 2018-09-30 | 2019-02-22 | 安徽佳通乘用子午线轮胎有限公司 | A kind of high humidity grabs the Tire tread rubber composition of performance and low rolling resistance |
Non-Patent Citations (1)
| Title |
|---|
| 张殿荣: "《现代橡胶配方设计 第2版》", 31 October 2001, 化学工业出版社, pages: 73 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US11597820B2 (en) | Rubber composition and tire comprising sustainable resources and related methods | |
| JP5639121B2 (en) | Rubber composition for tire and pneumatic tire | |
| CN107108908B (en) | Method for producing rubber composition for tire, and tire | |
| JP6434585B1 (en) | Pneumatic tire | |
| WO2019198398A1 (en) | Rubber composition | |
| US20190241723A1 (en) | Method for producing tread rubber member and tire production method | |
| JP3992523B2 (en) | Rubber composition | |
| JP2019151743A (en) | Rubber composition for tire | |
| EP2754689B1 (en) | Composite and method for producing the same, rubber composition, and pneumatic tire | |
| CN111571844A (en) | Preparation method of low rolling resistance tread rubber | |
| CN109575372B (en) | Ultra-low rolling resistance all-steel radial tire tread rubber composition | |
| Zaeimoedin et al. | Improving the abrasion resistance of “green” tyre compounds | |
| JP2017218583A (en) | Production method of rubber composition, rubber composition and tire | |
| JP5540534B2 (en) | Pneumatic tire | |
| JP5038040B2 (en) | Rubber composition for tire tread and tire | |
| CN112250922A (en) | Low-rolling-resistance tread rubber composition and preparation method thereof | |
| JP2011026414A (en) | Rubber composition for tire and manufacturing method for the same | |
| CN112847870B (en) | White carbon black-containing rubber composition and mixing method thereof | |
| CN114835959A (en) | Ultralow rolling resistance rubber composition for four-season tire, mixing method thereof and tire | |
| CN109824952B (en) | In-situ modified rubber composition for tire, tire and preparation method of tire | |
| JP2005247985A (en) | Rubber composition for tire carcass and pneumatic tire produced by using the same | |
| JP4586468B2 (en) | Method for producing silica masterbatch and rubber composition containing the masterbatch | |
| KR100738675B1 (en) | Tire tread composition | |
| JP2017214535A (en) | Method for producing tire rubber composition, rubber composition and tire | |
| KR100534656B1 (en) | Tread Compound of Tire Having Improved Fuel expenses |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210122 |