CN117903505B - Aramid tire tread rubber and preparation method thereof - Google Patents
Aramid tire tread rubber and preparation method thereof Download PDFInfo
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- CN117903505B CN117903505B CN202410073799.0A CN202410073799A CN117903505B CN 117903505 B CN117903505 B CN 117903505B CN 202410073799 A CN202410073799 A CN 202410073799A CN 117903505 B CN117903505 B CN 117903505B
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- 239000004760 aramid Substances 0.000 title claims abstract description 186
- 229920003235 aromatic polyamide Polymers 0.000 title claims abstract description 179
- 229920001971 elastomer Polymers 0.000 title claims abstract description 111
- 239000005060 rubber Substances 0.000 title claims abstract description 111
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000835 fiber Substances 0.000 claims abstract description 100
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 78
- 238000002156 mixing Methods 0.000 claims abstract description 65
- 239000007788 liquid Substances 0.000 claims abstract description 43
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 claims abstract description 42
- 239000011787 zinc oxide Substances 0.000 claims abstract description 39
- 230000004048 modification Effects 0.000 claims abstract description 32
- 238000012986 modification Methods 0.000 claims abstract description 32
- 239000002131 composite material Substances 0.000 claims abstract description 31
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 30
- 230000003712 anti-aging effect Effects 0.000 claims abstract description 23
- 239000006229 carbon black Substances 0.000 claims abstract description 17
- 244000043261 Hevea brasiliensis Species 0.000 claims abstract description 15
- 229920005557 bromobutyl Polymers 0.000 claims abstract description 15
- 229920003052 natural elastomer Polymers 0.000 claims abstract description 15
- 229920001194 natural rubber Polymers 0.000 claims abstract description 15
- 229920001195 polyisoprene Polymers 0.000 claims abstract description 15
- 238000004073 vulcanization Methods 0.000 claims abstract description 15
- 239000005062 Polybutadiene Substances 0.000 claims abstract description 13
- 229920002857 polybutadiene Polymers 0.000 claims abstract description 13
- 229920003048 styrene butadiene rubber Polymers 0.000 claims abstract description 13
- 235000021355 Stearic acid Nutrition 0.000 claims abstract description 11
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims abstract description 11
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000008117 stearic acid Substances 0.000 claims abstract description 11
- 239000004014 plasticizer Substances 0.000 claims abstract description 7
- 229960000892 attapulgite Drugs 0.000 claims description 87
- 229910052625 palygorskite Inorganic materials 0.000 claims description 87
- 238000009987 spinning Methods 0.000 claims description 58
- 229920006231 aramid fiber Polymers 0.000 claims description 52
- 239000000243 solution Substances 0.000 claims description 46
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 41
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 32
- 238000001035 drying Methods 0.000 claims description 32
- 238000001914 filtration Methods 0.000 claims description 26
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 26
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 22
- 239000011246 composite particle Substances 0.000 claims description 22
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 20
- 239000002253 acid Substances 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 15
- 239000007795 chemical reaction product Substances 0.000 claims description 14
- 125000002883 imidazolyl group Chemical group 0.000 claims description 14
- 238000005520 cutting process Methods 0.000 claims description 13
- 239000011592 zinc chloride Substances 0.000 claims description 13
- 235000005074 zinc chloride Nutrition 0.000 claims description 13
- 239000006185 dispersion Substances 0.000 claims description 12
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 12
- 159000000000 sodium salts Chemical class 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 10
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 10
- 239000002002 slurry Substances 0.000 claims description 10
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 claims description 10
- 239000004246 zinc acetate Substances 0.000 claims description 10
- XAFOTXWPFVZQAZ-UHFFFAOYSA-N 2-(4-aminophenyl)-3h-benzimidazol-5-amine Chemical compound C1=CC(N)=CC=C1C1=NC2=CC=C(N)C=C2N1 XAFOTXWPFVZQAZ-UHFFFAOYSA-N 0.000 claims description 8
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 8
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 8
- 239000001099 ammonium carbonate Substances 0.000 claims description 8
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 8
- 239000001110 calcium chloride Substances 0.000 claims description 8
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 230000001112 coagulating effect Effects 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 239000011593 sulfur Substances 0.000 claims description 8
- 229910052717 sulfur Inorganic materials 0.000 claims description 8
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims description 7
- 239000000853 adhesive Substances 0.000 claims description 7
- 230000001070 adhesive effect Effects 0.000 claims description 7
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims description 7
- 238000010528 free radical solution polymerization reaction Methods 0.000 claims description 7
- 238000000678 plasma activation Methods 0.000 claims description 7
- 238000007598 dipping method Methods 0.000 claims description 6
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 6
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 230000015271 coagulation Effects 0.000 claims description 2
- 238000005345 coagulation Methods 0.000 claims description 2
- 238000002347 injection Methods 0.000 claims description 2
- 239000007924 injection Substances 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 239000011297 pine tar Substances 0.000 claims description 2
- 229940068124 pine tar Drugs 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 abstract description 7
- 239000000945 filler Substances 0.000 abstract description 4
- 230000002776 aggregation Effects 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000005054 agglomeration Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 15
- 230000008569 process Effects 0.000 description 10
- 238000005470 impregnation Methods 0.000 description 9
- 239000011159 matrix material Substances 0.000 description 7
- 239000011148 porous material Substances 0.000 description 6
- 238000005096 rolling process Methods 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000007873 sieving Methods 0.000 description 4
- 238000005299 abrasion Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000005411 Van der Waals force Methods 0.000 description 2
- 239000012792 core layer Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000013040 rubber vulcanization Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000002166 wet spinning Methods 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 1
- 239000010692 aromatic oil Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
-
- 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
-
- 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)
Abstract
The invention relates to the technical field of tire production, in particular to an aramid tire tread rubber and a preparation method thereof. The preparation method comprises the following steps: carrying out surface modification on the aramid staple fiber containing benzimidazole groups by adopting hydroxyl-terminated liquid polyisoprene rubber to obtain modified aramid staple fiber; uniformly mixing the modified aramid short fibers and the brominated butyl rubber to obtain an aramid composite rubber; mixing natural rubber, butadiene rubber, styrene-butadiene rubber, aramid composite rubber, zinc oxide, stearic acid, an anti-aging agent, carbon black and a plasticizer for one-stage mixing, and then adding an accelerator and a vulcanizing agent for two-stage mixing to obtain a mixed rubber; and (3) placing the mixed rubber into a mold for vulcanization to obtain the aramid tire tread rubber. The invention avoids the problem of Yi Fei scattered agglomeration when the aramid staple fiber is used as the filler for mixing, greatly improves the dispersibility of the aramid staple fiber in the rubber compound, and finally obtains the tire tread rubber with excellent comprehensive performance.
Description
Technical Field
The invention relates to the technical field of tire production, in particular to an aramid tire tread rubber and a preparation method thereof.
Background
The tread, namely the running surface, of the tire is an outer tire crown part, namely an outer tire rubber layer on a belt layer or a buffer layer, is a main stress part of the radial tire, and along with the economic development of China, the requirements on the performance of the tire are higher and higher, and the high-performance tread rubber can enable the tire to have lower rolling resistance, good wear resistance and longer service life.
The aramid fiber is a high-molecular synthetic fiber, has excellent physical and chemical properties, has the advantages of good heat resistance, corrosion resistance, wear resistance and the like, can be used as a filler for manufacturing tires, can improve the elasticity, wear resistance, tensile strength and tear strength of the tires, ensures that the tires have longer service life, can reduce rolling resistance and improve the wet skid resistance of the tires, thereby improving the steering performance and safety of vehicles. However, the aramid short fiber has light weight, is easy to scatter when being mixed with the rubber matrix as filler, and has poor dispersibility in the rubber matrix and extremely easy aggregation because the aramid short fiber can not realize chemical bonding with the rubber matrix, thereby reducing the performance of the tread rubber.
The patent with the application number of CN202210183380.1 discloses a high-wear-resistance rubber-based composite material and a preparation method thereof, wherein ionic liquid with double bonds on side chains in a cationic structure is used for treating aramid fibers, so that the compatibility of the aramid fibers and a rubber matrix and the chemical bonding capability of the aramid fibers and the rubber are improved, and the mechanical property and the wear resistance of the rubber-based composite material are improved. However, the method still does not deviate from the category of the traditional surface impregnation modification of the para-aramid staple fibers, the dispersibility of the para-aramid staple fibers in the rubber matrix is limited, and the modified para-aramid staple fibers, the rubber matrix and other auxiliary agents are simultaneously fed during mixing, so that the problem that the para-aramid staple fibers are easy to scatter and difficult to mix still exists.
In view of the foregoing, there is a need for a new method for preparing an aramid tire tread rubber, which avoids the scattering of the aramid staple fibers during mixing and improves the dispersibility of the aramid staple fibers in the rubber matrix, thereby improving the tire performance.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method of an aramid tire tread rubber, which comprises the following steps:
Step S100, preparing a modified aramid staple fiber: dipping the aramid staple fiber containing benzimidazole groups in aluminum chloride solution at room temperature, filtering to obtain dipped aramid, uniformly mixing the dipped aramid and hydroxyl-terminated liquid polyisoprene rubber in toluene, dipping at room temperature, filtering, washing and drying to obtain modified aramid staple fiber;
Step S200, preparing an aramid composite adhesive: uniformly mixing the modified aramid short fibers and the brominated butyl rubber to obtain an aramid composite rubber;
Step S300, mixing: mixing natural rubber, butadiene rubber, styrene-butadiene rubber, aramid composite rubber, zinc oxide, stearic acid, an anti-aging agent, carbon black and a plasticizer for one-stage mixing, and then adding an accelerator and a vulcanizing agent for two-stage mixing to obtain a mixed rubber;
Step S400, vulcanization: and (3) placing the mixed rubber into a mold for vulcanization to obtain the aramid tire tread rubber.
In the technical scheme, the aramid staple fiber containing the benzimidazole group is prepared by carrying out low-temperature solution polymerization on terephthaloyl chloride, p-phenylenediamine and a monomer containing the benzimidazole group in a solvent, and then spinning and cutting the aramid staple fiber, and can be prepared by adopting any suitable polymerization and spinning route in the prior art. Compared with the traditional aramid fiber polymerized by terephthaloyl chloride and p-phenylenediamine, the molecular chain structure of the aramid fiber contains benzimidazole groups. The surface modification is carried out on the aramid staple fiber containing the benzimidazole group by adopting the hydroxyl-terminated liquid polyisoprene rubber, and then the modified aramid staple fiber is mixed with the brominated butyl rubber to prepare the aramid composite rubber. When the tire tread rubber is prepared, the aramid composite rubber is directly mixed with the natural rubber, the butadiene rubber and the styrene butadiene rubber, so that the problem of scattered and agglomerated aramid staple fibers generated by directly adding the aramid staple fibers in the mixing process in the traditional process is solved, and meanwhile, the dispersibility of the aramid staple fibers in the mixed rubber can be greatly improved due to good compatibility of the modified aramid staple fibers, the brominated butyl rubber and the natural rubber.
In one embodiment of the present invention, in one embodiment,
In the step S100, the mass ratio of the aramid staple fiber containing the benzimidazole group to the hydroxyl-terminated liquid polyisoprene rubber is 100 (10-50);
In the step S200, the mass ratio of the modified aramid short fiber to the brominated butyl rubber is 10:20;
In the step S300, the mass ratio of the natural rubber, the butadiene rubber, the styrene-butadiene rubber, the aramid composite rubber, the zinc oxide, the stearic acid, the anti-aging agent, the carbon black, the plasticizer, the accelerator and the vulcanizing agent is (66-84): (8-10): (5-6): (3-18): (1.5-6): (1-3): (1-2): (40-60): (1-20): (0.5-2): (0.5-2).
In one embodiment of the present invention, in one embodiment,
In the step S100, the concentration of the aluminum chloride solution is 3-4wt%; the component force of the hydroxyl-terminated liquid polyisoprene rubber is 45000-55000;
in the step S300, the anti-aging agent is a mixture of an anti-aging agent 4020 and an anti-aging agent D according to a mass ratio of 1.5:1; the carbon black is at least one of N330 and N550; the plasticizer is at least one of dioctyl phthalate, pine tar and aromatic hydrocarbon oil; the accelerator is at least one of N-cyclohexyl-2-benzothiazole sulfenamide, N-dicyclohexyl-2-benzothiazole sulfenamide and hexamethylenetetramine; the vulcanizing agent is sulfur.
In one embodiment of the present invention, in one embodiment,
In the step S100, the aramid staple fiber containing benzimidazole group is immersed in aluminum chloride solution for 20 to 30 minutes by ultrasonic; dipping aramid fiber and hydroxyl-terminated liquid polyisoprene rubber in toluene for 20-30 min, filtering, drying the toluene at 140-150 ℃, washing with water and drying;
In the step S200, the mixing temperature is 60-120 ℃, and the mixing time is 10-15 min;
In the step S300, the first-stage mixing temperature is 60-120 ℃, the mixing time is 5-10 min, the second-stage mixing temperature is 20-40 ℃, and the mixing time is 5-15 min;
in the step S400, the vulcanization temperature is 140-170 ℃ and the vulcanization time is 10-20 min.
In a specific embodiment, in step S100, the aramid staple fiber containing an imidazole group is a porous aramid fiber having a sheath-core structure, and the preparation thereof includes the steps of:
Step S110, preparing attapulgite/zinc oxide composite particles: dispersing nano attapulgite in water to obtain nano attapulgite dispersion liquid, simultaneously dripping zinc chloride solution and ammonium carbonate solution into the nano attapulgite dispersion liquid in a stirring state at 30-100 ℃, keeping the pH value of a reaction system at 6-8, continuing stirring and reacting for 1-3 hours after dripping, obtaining a reaction product, and obtaining attapulgite/zinc oxide composite particles after filtering, washing, drying, roasting and crushing the reaction product;
Step S120, preparing aramid fiber slurry: uniformly dispersing terephthaloyl chloride, p-phenylenediamine and 2- (4-aminophenyl) -5-aminobenzimidazole in N-methylpyrrolidone containing calcium chloride, and polymerizing at a low temperature to obtain aramid pulp containing benzimidazole groups;
step S130, preparing spinning sheath liquid: uniformly mixing and stirring aramid fiber slurry containing benzimidazole groups, zinc acetate and N' N-dimethylacetamide to obtain spinning dope;
step S140, preparing spinning core liquid: uniformly mixing and stirring aramid fiber slurry containing benzimidazole groups, attapulgite/zinc oxide composite particles and N' N-dimethylacetamide to obtain spinning core solution;
step S150, coaxial spinning: respectively adding spinning core liquid and spinning sheath liquid into an injector, connecting the injector to a coaxial needle, and injecting the coaxial needle into a coagulating bath for coaxial spinning to obtain primary fibers with a sheath-core structure;
Step S160, solvent replacement: sequentially replacing the nascent fiber with water, a mixed solution of water and acetone and a gradient solvent in acetone, and then drying to obtain the porous aramid fiber with a sheath-core structure;
step S170, cutting: cutting the porous aramid fiber to obtain the aramid short fiber containing imidazole groups, wherein the length of the aramid short fiber is 3-6 mm.
According to the technical scheme, the aramid short fiber containing the imidazole group is a porous aramid fiber with a sheath-core structure, zinc acetate in spinning sheath liquid and zinc oxide in spinning core liquid can form a metal coordination bond crosslinked aramid system with benzimidazole groups on an aramid main chain, and the metal coordination bond crosslinked aramid system can quickly and uniformly undergo sol-gel transformation in a wet spinning process, so that a uniform three-dimensional crosslinked structure is formed, and after a solvent is removed, the porous aramid fiber with uniform pores can be formed. The core layer of the porous aramid fiber contains attapulgite as a supporting framework, so that the shrinkage deformation of the aramid porous fiber can be avoided, meanwhile, the attapulgite has a porous structure, an interpenetrating network structure can be formed with the aramid body, and the combination of the attapulgite and the aramid body is improved. In addition, zinc oxide loaded on the attapulgite is also beneficial to the subsequent rubber vulcanization process.
In one embodiment of the present invention, in one embodiment,
In the step S110, the mass ratio of the nano attapulgite to the zinc chloride is 100 (15-20);
In the step S120, the mass ratio of terephthaloyl chloride, p-phenylenediamine, 2- (4-aminophenyl) -5-aminobenzimidazole, calcium chloride and N-methylpyrrolidone is 100:27:55:55:2000;
in the step S130, the mass ratio of the aramid pulp containing the benzimidazole group to the zinc acetate to the N' N-dimethylacetamide is 2237:20:1800;
in the step S140, the mass ratio of the aramid pulp containing the benzimidazole group, the attapulgite/zinc oxide composite particles and the N' N-dimethylacetamide is 2237:88:1800.
In one embodiment of the present invention, in one embodiment,
In the step S110, the concentration of the zinc chloride solution is 0.1 to 0.5 weight percent; the concentration of the ammonium carbonate is 0.1 to 0.2 weight percent;
In the step S150, the coagulating bath is a mixed solvent of N' N-dimethylacetamide and water in a volume ratio of 1:1;
In step S160, the volume ratio of water to acetone in the mixed solution of water and acetone is 1:1.
In one embodiment of the present invention, in one embodiment,
In the step S110, the reaction product is filtered and then washed by deionized water, then dried for 1-2 hours at the temperature of below 100 ℃, baked for 1-10 hours at the temperature of 300-600 ℃, crushed and ground by a ball mill after baking, and sieved to obtain the attapulgite/zinc oxide composite particles with the particle size of 400-600 nm;
In the step S120, the solution polymerization temperature is-5-0 ℃ and the polymerization reaction time is 30-40 min;
In the step S150, the type of the coaxial needle is 22G/17G, and the injection speed is 0.03mm/S; the coagulation bath temperature was 80 ℃.
In a specific embodiment, the nano attapulgite in the step S100 is modified by plasma, acid and sodium salt in sequence, and specifically includes the following steps:
Step S111, plasma modification: putting the nano attapulgite into an arc plasma generator, performing plasma activation for 5-10 min under the direct current voltage of 30-50 kV, then cleaning with deionized water, and finally filtering and drying to obtain the plasma modified attapulgite;
Step S112, acid modification: adding the plasma modified attapulgite into a dilute hydrochloric acid solution with the concentration of 0.5-1 wt%, and performing ultrasonic dispersion for 1-1.5 hours at the temperature of 60-80 ℃ to obtain acid modified attapulgite;
Step S113, sodium salt modification: and (3) dropwise adding a sodium hydroxide solution into the acid modified attapulgite at 65-75 ℃, regulating the pH value to 4-5, continuing ultrasonic dispersion for 1-2 hours, and washing, filtering and drying to obtain the modified nano attapulgite.
The invention provides an aramid tire tread rubber, which is prepared by adopting the preparation method of the aramid tire tread rubber.
According to the technical scheme, the nano attapulgite with a large pore structure can be obtained through plasma activation, acid modification and sodium salt modification, and the loading capacity of the nano attapulgite on zinc oxide is improved. The arc plasma activation can break Van der Waals force among attapulgite molecules and bonding force of other ionic bonds, so that the structure of the attapulgite is loosened, and then the attapulgite is washed by deionized water to primarily remove soluble impurities and inorganic salts; the acid modification can improve the specific surface area and pore volume of the attapulgite, and obviously increase the adsorption capacity of the attapulgite; sodium hydroxide solution reacts with dilute hydrochloric acid to produce sodium chloride and water during sodium salt modification, so that the pH value in the modification process can be effectively controlled, the modification environment is kept to be weak acid, and the generated sodium salt can be utilized to further modify the attapulgite.
Compared with the prior art, the invention has the following beneficial technical effects:
1. The surface modification is carried out on the aramid staple fiber containing the benzimidazole group by adopting the hydroxyl-terminated liquid polyisoprene rubber, and then the modified aramid staple fiber is mixed with the brominated butyl rubber to prepare the aramid composite rubber. When the tire tread rubber is prepared, the aramid composite rubber is directly mixed with the natural rubber, the butadiene rubber and the styrene butadiene rubber, so that the problem of scattered and agglomerated aramid staple fibers generated by directly adding the aramid staple fibers in the mixing process in the traditional process is solved, and meanwhile, the dispersibility of the aramid staple fibers in the mixed rubber can be greatly improved due to good compatibility of the modified aramid staple fibers, the brominated butyl rubber and the natural rubber.
2. The aramid short fiber containing imidazole groups is a porous aramid fiber with a sheath-core structure, zinc acetate in spinning sheath liquid and zinc oxide in spinning core liquid can form a metal coordination bond crosslinked aramid fiber system with benzimidazole groups on an aramid main chain, and the metal coordination bond crosslinked aramid fiber system can quickly and uniformly generate sol-gel transition in the wet spinning process, so that a uniform three-dimensional crosslinked structure is formed, and after a solvent is removed, the porous aramid fiber with uniform pores can be formed. Because the core layer of the porous aramid fiber contains the attapulgite as a supporting framework, the shrinkage deformation of the aramid porous fiber can be avoided, and meanwhile, because the attapulgite has a porous structure, an interpenetrating network structure can be formed with the aramid body, and the combination of the attapulgite and the aramid body is improved. In addition, zinc oxide loaded on the attapulgite is also beneficial to the subsequent rubber vulcanization process.
3. The nano attapulgite with a large pore structure can be obtained through plasma activation, acid modification and sodium salt modification, and the loading capacity of the nano attapulgite on zinc oxide is improved. The arc plasma activation can break Van der Waals force among attapulgite molecules and bonding force of other ionic bonds, so that the structure of the attapulgite is loosened, and then the attapulgite is washed by deionized water to primarily remove soluble impurities and inorganic salts; the acid modification can improve the specific surface area and pore volume of the attapulgite, and obviously increase the adsorption capacity of the attapulgite; sodium hydroxide solution reacts with dilute hydrochloric acid to produce sodium chloride and water during sodium salt modification, so that the pH value in the modification process can be effectively controlled, the modification environment is kept to be weak acid, and the generated sodium salt can be utilized to further modify the attapulgite.
In conclusion, the method solves the problem of Yi Fei scattered agglomeration when the aramid staple fibers are used as the filler for mixing, greatly improves the dispersibility of the aramid staple fibers in the mixed rubber, and finally obtains the tire tread rubber with excellent comprehensive performance.
Detailed Description
In order that the above-recited objects, features and advantages of the application will be more clearly understood, a more particular description of the application will be rendered by reference to specific embodiments thereof. It should be noted that, without conflict, the embodiments of the present application and features in the embodiments may be combined with each other.
Example 1
The embodiment prepares the aramid tire tread rubber, which comprises the following steps:
Step S100, preparing a modified aramid staple fiber: carrying out ultrasonic impregnation on 100 parts by mass of aramid staple fibers containing benzimidazole groups in 3-4wt% of aluminum chloride solution at room temperature for 20-30min, filtering to obtain impregnated aramid fibers, uniformly mixing the impregnated aramid fibers and 10 parts by mass of hydroxyl-terminated liquid polyisoprene rubber in toluene, carrying out ultrasonic impregnation on the mixture at room temperature for 20-30min, filtering, drying the toluene at 140-150 ℃ firstly, washing and drying to obtain modified aramid staple fibers;
The aramid short fiber containing imidazole groups is a porous aramid fiber with a sheath-core structure, and the preparation method comprises the following steps:
Step S110, preparing attapulgite/zinc oxide composite particles: dispersing 100 parts by mass of nano attapulgite in water to obtain nano attapulgite dispersion, simultaneously dripping a zinc chloride solution with the concentration of 0.1-0.5 wt% and an ammonium carbonate solution with the concentration of 0.1-0.2 wt% into the nano attapulgite dispersion in a stirring state at the temperature of 30-100 ℃, keeping the pH value of a reaction system at 6-8 by the total addition amount of zinc chloride, continuously stirring for reaction for 1-3 hours after dripping, obtaining a reaction product, washing the reaction product with deionized water after filtering, drying for 1-2 hours at the temperature of below 100 ℃, roasting for 1-10 hours at the temperature of 300-600 ℃, grinding by a ball mill after roasting, and sieving to obtain attapulgite/zinc oxide composite particles with the particle size of 400-600 nm;
Step S120, preparing aramid fiber slurry: uniformly dispersing 100 parts by mass of terephthaloyl chloride, 27 parts by mass of p-phenylenediamine, 55 parts by mass of 2- (4-aminophenyl) -5-aminobenzimidazole and 55 parts by mass of calcium chloride in 2000 parts by mass of N-methylpyrrolidone, and carrying out low-temperature solution polymerization for 30-40 min at-5-0 ℃ to obtain aramid pulp containing benzimidazole groups;
Step S130, preparing spinning sheath liquid: 2237 parts by mass of aramid pulp containing benzimidazole groups, 20 parts by mass of zinc acetate and 1800 parts by mass of N' N-dimethylacetamide are mixed and stirred uniformly to obtain spinning sheath liquid;
Step S140, preparing spinning core liquid: 2237 parts by mass of aramid pulp containing benzimidazole groups, 88 parts by mass of attapulgite/zinc oxide composite particles and 1800 parts by mass of N' N-dimethylacetamide are mixed and stirred uniformly to obtain spinning core solution;
Step S150, coaxial spinning: respectively adding spinning core solution and spinning sheath solution into an injector, connecting the injector to a coaxial needle with the model of 22G/17G, injecting the coaxial needle into a coagulating bath with the volume ratio of 1:1 of N' N-dimethylacetamide and water at the speed of 0.03mm/s for coaxial spinning, and obtaining the primary fiber with a sheath-core structure after coaxial spinning;
Step S160, solvent replacement: sequentially replacing the nascent fiber with a mixed solution of water and acetone in a volume ratio of 1:1 and a gradient solvent in acetone, and drying to obtain the porous aramid fiber with a sheath-core structure;
step S170, cutting: cutting the porous aramid fiber to obtain the aramid short fiber containing imidazole groups, wherein the length of the aramid short fiber is 3-6 mm.
Step S200, preparing an aramid composite adhesive: mixing 10 parts by mass of modified aramid short fibers and 20 parts by mass of brominated butyl rubber at 60-120 ℃ for 10-15 min to obtain aramid composite rubber;
Step S300, mixing: 66 parts by mass of natural rubber, 10 parts by mass of butadiene rubber, 6 parts by mass of styrene-butadiene rubber, 18 parts by mass of aramid composite rubber, 1.5 parts by mass of zinc oxide, 3 parts by mass of stearic acid, 0.6 part by mass of an anti-aging agent 4020, 0.4 part by mass of an anti-aging agent D, 40 parts by mass of carbon black N330 and 1 part by mass of aromatic oil are subjected to one-stage mixing at 60-120 ℃ for 5-10 min, then 0.5 part by mass of N-cyclohexyl-2-benzothiazole sulfenamide and 0.5 part by mass of sulfur are added, and two-stage mixing is performed at 20-40 ℃ for 5-15 min to obtain a rubber compound;
Step S400, vulcanization: and (3) placing the mixed rubber into a mould, and vulcanizing for 10-20 min at 140-170 ℃ to obtain the aramid tire tread rubber.
Example 2
The embodiment prepares the aramid tire tread rubber, which comprises the following steps:
Step S100, preparing a modified aramid staple fiber: carrying out ultrasonic impregnation on 100 parts by mass of aramid staple fibers containing benzimidazole groups in 3-4wt% of aluminum chloride solution at room temperature for 20-30min, filtering to obtain impregnated aramid fibers, uniformly mixing the impregnated aramid fibers and 30 parts by mass of hydroxyl-terminated liquid polyisoprene rubber in toluene, carrying out ultrasonic impregnation on the mixture at room temperature for 20-30min, filtering, drying the toluene at 140-150 ℃ firstly, washing with water and drying to obtain modified aramid staple fibers;
The aramid short fiber containing imidazole groups is a porous aramid fiber with a sheath-core structure, and the preparation method comprises the following steps:
Step S110, preparing attapulgite/zinc oxide composite particles: dispersing 100 parts by mass of nano attapulgite in water to obtain nano attapulgite dispersion, simultaneously dripping a zinc chloride solution with the concentration of 0.1-0.5 wt% and an ammonium carbonate solution with the concentration of 0.1-0.2 wt% into the nano attapulgite dispersion in a stirring state at the temperature of 30-100 ℃, keeping the pH value of a reaction system at 6-8 by the total addition amount of the zinc chloride, continuously stirring for reacting for 1-3 hours after dripping, obtaining a reaction product, washing the reaction product with deionized water after filtering, drying for 1-2 hours at the temperature of below 100 ℃, roasting for 1-10 hours at the temperature of 300-600 ℃, crushing and grinding by a ball mill after roasting, and sieving to obtain attapulgite/zinc oxide composite particles with the particle size of 400-600 nm;
Step S120, preparing aramid fiber slurry: uniformly dispersing 100 parts by mass of terephthaloyl chloride, 27 parts by mass of p-phenylenediamine, 55 parts by mass of 2- (4-aminophenyl) -5-aminobenzimidazole and 55 parts by mass of calcium chloride in 2000 parts by mass of N-methylpyrrolidone, and carrying out low-temperature solution polymerization for 30-40 min at-5-0 ℃ to obtain aramid pulp containing benzimidazole groups;
Step S130, preparing spinning sheath liquid: 2237 parts by mass of aramid pulp containing benzimidazole groups, 20 parts by mass of zinc acetate and 1800 parts by mass of N' N-dimethylacetamide are mixed and stirred uniformly to obtain spinning sheath liquid;
Step S140, preparing spinning core liquid: 2237 parts by mass of aramid pulp containing benzimidazole groups, 88 parts by mass of attapulgite/zinc oxide composite particles and 1800 parts by mass of N' N-dimethylacetamide are mixed and stirred uniformly to obtain spinning core solution;
Step S150, coaxial spinning: respectively adding spinning core solution and spinning sheath solution into an injector, connecting the injector to a coaxial needle with the model of 22G/17G, injecting the coaxial needle into a coagulating bath with the volume ratio of 1:1 of N' N-dimethylacetamide and water at the speed of 0.03mm/s for coaxial spinning, and obtaining the primary fiber with a sheath-core structure after coaxial spinning;
Step S160, solvent replacement: sequentially replacing the nascent fiber with a mixed solution of water and acetone in a volume ratio of 1:1 and a gradient solvent in acetone, and drying to obtain the porous aramid fiber with a sheath-core structure;
step S170, cutting: cutting the porous aramid fiber to obtain the aramid short fiber containing imidazole groups, wherein the length of the aramid short fiber is 3-6 mm.
Step S200, preparing an aramid composite adhesive: mixing 10 parts by mass of modified aramid short fibers and 20 parts by mass of brominated butyl rubber at 60-120 ℃ for 10-15 min to obtain aramid composite rubber;
step S300, mixing: 73 parts by mass of natural rubber, 9 parts by mass of butadiene rubber, 5 parts by mass of styrene-butadiene rubber, 13 parts by mass of aramid composite rubber, 3 parts by mass of zinc oxide, 2 parts by mass of stearic acid, 1.2 parts by mass of an anti-aging agent 4020, 0.8 part by mass of an anti-aging agent D, 30 parts by mass of carbon black N330, 25 parts by mass of carbon black N550 and 10 parts by mass of dioctyl phthalate are subjected to one-stage mixing at 60-120 ℃ for 5-10 min, then 1 part by mass of hexamethylenetetramine and 1 part by mass of sulfur are added, and two-stage mixing is performed at 20-40 ℃ for 5-15 min to obtain a rubber compound;
Step S400, vulcanization: and (3) placing the mixed rubber into a mould, and vulcanizing for 10-20 min at 140-170 ℃ to obtain the aramid tire tread rubber.
Example 3
The embodiment prepares the aramid tire tread rubber, which comprises the following steps:
Step S100, preparing a modified aramid staple fiber: carrying out ultrasonic impregnation on 100 parts by mass of aramid staple fibers containing benzimidazole groups in 3-4wt% of aluminum chloride solution at room temperature for 20-30min, filtering to obtain impregnated aramid fibers, uniformly mixing the impregnated aramid fibers and 50 parts by mass of hydroxyl-terminated liquid polyisoprene rubber in toluene, carrying out ultrasonic impregnation on the mixture at room temperature for 20-30min, filtering, drying the toluene at 140-150 ℃ firstly, washing and drying to obtain modified aramid staple fibers;
The aramid short fiber containing imidazole groups is a porous aramid fiber with a sheath-core structure, and the preparation method comprises the following steps:
Step S110, preparing attapulgite/zinc oxide composite particles: dispersing 100 parts by mass of nano attapulgite in water to obtain nano attapulgite dispersion, simultaneously dripping a zinc chloride solution with the concentration of 0.1-0.5 wt% and an ammonium carbonate solution with the concentration of 0.1-0.2 wt% into the nano attapulgite dispersion in a stirring state at the temperature of 30-100 ℃, keeping the pH value of a reaction system at 6-8 by the total addition amount of 20 parts by mass, continuously stirring for reaction for 1-3 hours after dripping, obtaining a reaction product, washing the reaction product with deionized water after filtering, drying for 1-2 hours at the temperature of below 100 ℃, roasting for 1-10 hours at the temperature of 300-600 ℃, grinding by a ball mill after roasting, and sieving to obtain attapulgite/zinc oxide composite particles with the particle size of 400-600 nm;
Step S120, preparing aramid fiber slurry: uniformly dispersing 100 parts by mass of terephthaloyl chloride, 27 parts by mass of p-phenylenediamine, 55 parts by mass of 2- (4-aminophenyl) -5-aminobenzimidazole and 55 parts by mass of calcium chloride in 2000 parts by mass of N-methylpyrrolidone, and carrying out low-temperature solution polymerization for 30-40 min at-5-0 ℃ to obtain aramid pulp containing benzimidazole groups;
Step S130, preparing spinning sheath liquid: 2237 parts by mass of aramid pulp containing benzimidazole groups, 20 parts by mass of zinc acetate and 1800 parts by mass of N' N-dimethylacetamide are mixed and stirred uniformly to obtain spinning sheath liquid;
Step S140, preparing spinning core liquid: 2237 parts by mass of aramid pulp containing benzimidazole groups, 88 parts by mass of attapulgite/zinc oxide composite particles and 1800 parts by mass of N' N-dimethylacetamide are mixed and stirred uniformly to obtain spinning core solution;
Step S150, coaxial spinning: respectively adding spinning core solution and spinning sheath solution into an injector, connecting the injector to a coaxial needle with the model of 22G/17G, injecting the coaxial needle into a coagulating bath with the volume ratio of 1:1 of N' N-dimethylacetamide and water at the speed of 0.03mm/s for coaxial spinning, and obtaining the primary fiber with a sheath-core structure after coaxial spinning;
Step S160, solvent replacement: sequentially replacing the nascent fiber with a mixed solution of water and acetone in a volume ratio of 1:1 and a gradient solvent in acetone, and drying to obtain the porous aramid fiber with a sheath-core structure;
step S170, cutting: cutting the porous aramid fiber to obtain the aramid short fiber containing imidazole groups, wherein the length of the aramid short fiber is 3-6 mm.
Step S200, preparing an aramid composite adhesive: mixing 10 parts by mass of modified aramid short fibers and 20 parts by mass of brominated butyl rubber at 60-120 ℃ for 10-15 min to obtain aramid composite rubber;
Step S300, mixing: 84 parts by mass of natural rubber, 8 parts by mass of butadiene rubber, 5 parts by mass of styrene-butadiene rubber, 3 parts by mass of aramid composite rubber, 6 parts by mass of zinc oxide, 1 part by mass of stearic acid, 1.2 parts by mass of an anti-aging agent 4020, 0.8 part by mass of an anti-aging agent D, 60 parts by mass of carbon black N330 and 20 parts by mass of dioctyl phthalate are subjected to one-stage mixing at 60-120 ℃ for 5-10 min, then 2 parts by mass of hexamethylenetetramine and 2 parts by mass of sulfur are added, and two-stage mixing is performed at 20-40 ℃ for 5-15 min to obtain a rubber compound;
Step S400, vulcanization: and (3) placing the mixed rubber into a mould, and vulcanizing for 10-20 min at 140-170 ℃ to obtain the aramid tire tread rubber.
Example 4
The embodiment prepares the aramid tire tread rubber, which comprises the following steps:
Step S100, preparing a modified aramid staple fiber: carrying out ultrasonic impregnation on 100 parts by mass of aramid staple fibers containing benzimidazole groups in 3-4wt% of aluminum chloride solution at room temperature for 20-30min, filtering to obtain impregnated aramid fibers, uniformly mixing the impregnated aramid fibers and 30 parts by mass of hydroxyl-terminated liquid polyisoprene rubber in toluene, carrying out ultrasonic impregnation on the mixture at room temperature for 20-30min, filtering, drying the toluene at 140-150 ℃ firstly, washing with water and drying to obtain modified aramid staple fibers;
The aramid short fiber containing imidazole groups is a porous aramid fiber with a sheath-core structure, and the preparation method comprises the following steps:
Step S110, preparing attapulgite/zinc oxide composite particles: dispersing 100 parts by mass of nano attapulgite in water to obtain nano attapulgite dispersion, simultaneously dripping a zinc chloride solution with the concentration of 0.1-0.5 wt% and an ammonium carbonate solution with the concentration of 0.1-0.2 wt% into the nano attapulgite dispersion in a stirring state at the temperature of 30-100 ℃, keeping the pH value of a reaction system at 6-8 by the total addition amount of the zinc chloride, continuously stirring for reacting for 1-3 hours after dripping, obtaining a reaction product, washing the reaction product with deionized water after filtering, drying for 1-2 hours at the temperature of below 100 ℃, roasting for 1-10 hours at the temperature of 300-600 ℃, crushing and grinding by a ball mill after roasting, and sieving to obtain attapulgite/zinc oxide composite particles with the particle size of 400-600 nm;
The nano attapulgite is subjected to plasma modification, acid modification and sodium salt modification in sequence, and specifically comprises the following steps:
Step S111, plasma modification: putting the nano attapulgite into an arc plasma generator, performing plasma activation for 5-10 min under the direct current voltage of 30-50 kV, then cleaning with deionized water, and finally filtering and drying to obtain the plasma modified attapulgite;
Step S112, acid modification: adding the plasma modified attapulgite into a dilute hydrochloric acid solution with the concentration of 0.5-1 wt%, and performing ultrasonic dispersion for 1-1.5 hours at the temperature of 60-80 ℃ to obtain acid modified attapulgite;
Step S113, sodium salt modification: and (3) dropwise adding a sodium hydroxide solution into the acid modified attapulgite at 65-75 ℃, regulating the pH value to 4-5, continuing ultrasonic dispersion for 1-2 hours, and washing, filtering and drying to obtain the modified nano attapulgite.
Step S120, preparing aramid fiber slurry: uniformly dispersing 100 parts by mass of terephthaloyl chloride, 27 parts by mass of p-phenylenediamine, 55 parts by mass of 2- (4-aminophenyl) -5-aminobenzimidazole and 55 parts by mass of calcium chloride in 2000 parts by mass of N-methylpyrrolidone, and carrying out low-temperature solution polymerization for 30-40 min at-5-0 ℃ to obtain aramid pulp containing benzimidazole groups;
Step S130, preparing spinning sheath liquid: 2237 parts by mass of aramid pulp containing benzimidazole groups, 20 parts by mass of zinc acetate and 1800 parts by mass of N' N-dimethylacetamide are mixed and stirred uniformly to obtain spinning sheath liquid;
Step S140, preparing spinning core liquid: 2237 parts by mass of aramid pulp containing benzimidazole groups, 88 parts by mass of attapulgite/zinc oxide composite particles and 1800 parts by mass of N' N-dimethylacetamide are mixed and stirred uniformly to obtain spinning core solution;
Step S150, coaxial spinning: respectively adding spinning core solution and spinning sheath solution into an injector, connecting the injector to a coaxial needle with the model of 22G/17G, injecting the coaxial needle into a coagulating bath with the volume ratio of 1:1 of N' N-dimethylacetamide and water at the speed of 0.03mm/s for coaxial spinning, and obtaining the primary fiber with a sheath-core structure after coaxial spinning;
Step S160, solvent replacement: sequentially replacing the nascent fiber with a mixed solution of water and acetone in a volume ratio of 1:1 and a gradient solvent in acetone, and drying to obtain the porous aramid fiber with a sheath-core structure;
step S170, cutting: cutting the porous aramid fiber to obtain the aramid short fiber containing imidazole groups, wherein the length of the aramid short fiber is 3-6 mm.
Step S200, preparing an aramid composite adhesive: mixing 10 parts by mass of modified aramid short fibers and 20 parts by mass of brominated butyl rubber at 60-120 ℃ for 10-15 min to obtain aramid composite rubber;
Step S300, mixing: 73 parts by mass of natural rubber, 9 parts by mass of butadiene rubber, 5 parts by mass of styrene-butadiene rubber, 13 parts by mass of aramid composite rubber, 3 parts by mass of zinc oxide, 2 parts by mass of stearic acid, 1.2 parts by mass of an anti-aging agent 4020, 0.8 part by mass of an anti-aging agent D, 30 parts by mass of carbon black N330, 25 parts by mass of carbon black N550 and 10 parts by mass of dioctyl phthalate are subjected to one-stage mixing at 60-120 ℃ for 5-10 min, then 1 part by mass of N-cyclohexyl-2-benzothiazole sulfenamide and 1 part by mass of sulfur are added, and two-stage mixing is performed at 20-40 ℃ for 5-15 min to obtain a rubber compound;
Step S400, vulcanization: and (3) placing the mixed rubber into a mould, and vulcanizing for 10-20 min at 140-170 ℃ to obtain the aramid tire tread rubber.
Comparative example 1
The comparative example prepared a tire tread rubber without aramid staple fibers, comprising the steps of:
step S100, mixing: 78 parts by mass of natural rubber, 9 parts by mass of butadiene rubber, 5 parts by mass of styrene-butadiene rubber, 8 parts by mass of brominated butyl rubber, 3 parts by mass of zinc oxide, 2 parts by mass of stearic acid, 1.2 parts by mass of an anti-aging agent 4020, 0.8 part by mass of an anti-aging agent D, 30 parts by mass of carbon black N330, 25 parts by mass of carbon black N550 and 10 parts by mass of dioctyl phthalate are subjected to one-stage mixing at 60-120 ℃ for 5-10 min, then 1 part by mass of hexamethylenetetramine and 1 part by mass of sulfur are added, and two-stage mixing is performed at 20-40 ℃ for 5-15 min to obtain a rubber compound;
step S200, vulcanization: and (3) placing the mixed rubber into a mould, and vulcanizing for 10-20 min at 140-170 ℃ to obtain the aramid tire tread rubber.
Comparative example 2
The comparative example adopts conventional aramid staple fibers to replace the aramid staple fibers containing benzimidazole groups to prepare the aramid tire tread rubber, and the method comprises the following steps:
step S100, preparing an aramid composite adhesive: mixing 10 parts by mass of aramid short fibers and 20 parts by mass of brominated butyl rubber at 60-120 ℃ for 10-15 min to obtain aramid composite rubber;
Step S200, mixing: 73 parts by mass of natural rubber, 9 parts by mass of butadiene rubber, 5 parts by mass of styrene-butadiene rubber, 13 parts by mass of aramid composite rubber, 3 parts by mass of zinc oxide, 2 parts by mass of stearic acid, 1.2 parts by mass of an anti-aging agent 4020, 0.8 part by mass of an anti-aging agent D, 30 parts by mass of carbon black N330, 25 parts by mass of carbon black N550 and 10 parts by mass of dioctyl phthalate are subjected to one-stage mixing at 60-120 ℃ for 5-10 min, then 1 part by mass of hexamethylenetetramine and 1 part by mass of sulfur are added, and two-stage mixing is performed at 20-40 ℃ for 5-15 min to obtain a rubber compound;
step S300, vulcanization: and (3) placing the mixed rubber into a mould, and vulcanizing for 10-20 min at 140-170 ℃ to obtain the aramid tire tread rubber.
Performance detection
1. Tensile strength: the tread bands prepared in examples 1-4 and comparative examples 1-2 were tested for tensile strength according to GB/T528 standard;
2. shore hardness: the tread bands prepared in examples 1-4 and comparative examples 1-2 were tested for hardness using GB/T6031-1998 standard;
3. Tear strength: the tread bands prepared in examples 1-4 and comparative examples 1-2 were tested for tear strength using GB/T529 standards;
4. Elongation at break: the tread bands prepared in examples 1-4 and comparative examples 1-2 were tested for elongation at break using GB/T528 standard;
5. abrasion resistance test: the acle abrasion of the tread bands prepared in examples 1-4 and comparative examples 1-2 was measured using the GB/T1689-2014 standard;
6. Rolling resistance: the rolling resistance coefficients of the tread bands prepared in examples 1 to 4 and comparative examples 1 to 2 were determined using GB/T18861-2002 standard.
The results of the performance test are shown in Table 1:
TABLE 1 results of Performance test for examples 1-4 and comparative examples 1-2
| Example 1 | Example 2 | Example 3 | Example 4 | Comparative example 1 | Comparative example 2 | |
| Tensile Strength (Mpa) | 40 | 41 | 40 | 42 | 20 | 33 |
| Shore hardness (degree) | 71 | 73 | 72 | 74 | 62 | 68 |
| Tear Strength (kN/m) | 172 | 174 | 172 | 176 | 123 | 165 |
| Elongation at break (%) | 650 | 671 | 663 | 679 | 519 | 605 |
| Acle abrasion (cm) | 0.171 | 0.169 | 0.170 | 0.167 | 0.331 | 0.201 |
| Rolling resistance coefficient (N/kN) | 3.2 | 3.1 | 3.3 | 3.1 | 4.9 | 3.9 |
As can be seen from Table 1, the various performance indexes of the tread rubber prepared by using the aramid staple fibers containing benzimidazole groups in examples 1 to 4 are significantly higher than those of the tread rubber prepared by using the conventional aramid staple fibers in comparative example 2 without the aramid staple fibers in comparative example 1.
The embodiments of the present invention are not limited to the above-described embodiments, but any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principles of the present invention should be made in the scope of the present invention.
Claims (9)
1. The preparation method of the aramid tire tread rubber is characterized by comprising the following steps of:
Step S100, preparing a modified aramid staple fiber: dipping the aramid staple fiber containing benzimidazole groups in aluminum chloride solution at room temperature, filtering to obtain dipped aramid, uniformly mixing the dipped aramid and hydroxyl-terminated liquid polyisoprene rubber in toluene, dipping at room temperature, filtering, washing and drying to obtain modified aramid staple fiber; the aramid short fiber containing imidazole groups is a porous aramid fiber with a sheath-core structure, and the preparation method comprises the following steps:
Step S110, preparing attapulgite/zinc oxide composite particles: dispersing nano attapulgite in water to obtain nano attapulgite dispersion liquid, simultaneously dripping zinc chloride solution and ammonium carbonate solution into the nano attapulgite dispersion liquid in a stirring state at 30-100 ℃, keeping the pH value of a reaction system at 6-8, continuing stirring and reacting for 1-3 hours after dripping, obtaining a reaction product, and obtaining attapulgite/zinc oxide composite particles after filtering, washing, drying, roasting and crushing the reaction product;
Step S120, preparing aramid fiber slurry: uniformly dispersing terephthaloyl chloride, p-phenylenediamine and 2- (4-aminophenyl) -5-aminobenzimidazole in N-methylpyrrolidone containing calcium chloride, and polymerizing at a low temperature to obtain aramid pulp containing benzimidazole groups;
step S130, preparing spinning sheath liquid: uniformly mixing and stirring aramid fiber slurry containing benzimidazole groups, zinc acetate and N' N-dimethylacetamide to obtain spinning dope;
step S140, preparing spinning core liquid: uniformly mixing and stirring aramid fiber slurry containing benzimidazole groups, attapulgite/zinc oxide composite particles and N' N-dimethylacetamide to obtain spinning core solution;
step S150, coaxial spinning: respectively adding spinning core liquid and spinning sheath liquid into an injector, connecting the injector to a coaxial needle, and injecting the coaxial needle into a coagulating bath for coaxial spinning to obtain primary fibers with a sheath-core structure;
Step S160, solvent replacement: sequentially replacing the nascent fiber with water, a mixed solution of water and acetone and a gradient solvent in acetone, and then drying to obtain the porous aramid fiber with a sheath-core structure;
Step S170, cutting: cutting the porous aramid fiber to obtain an aramid short fiber containing imidazole groups, wherein the length of the aramid short fiber is 3-6 mm;
Step S200, preparing an aramid composite adhesive: uniformly mixing the modified aramid short fibers and the brominated butyl rubber to obtain an aramid composite rubber;
Step S300, mixing: mixing natural rubber, butadiene rubber, styrene-butadiene rubber, aramid composite rubber, zinc oxide, stearic acid, an anti-aging agent, carbon black and a plasticizer for one-stage mixing, and then adding an accelerator and a vulcanizing agent for two-stage mixing to obtain a mixed rubber;
Step S400, vulcanization: and (3) placing the mixed rubber into a mold for vulcanization to obtain the aramid tire tread rubber.
2. The method for preparing the aramid tire tread rubber according to claim 1, wherein,
In the step S100, the mass ratio of the aramid staple fiber containing the benzimidazole group to the hydroxyl-terminated liquid polyisoprene rubber is 100 (10-50);
In the step S200, the mass ratio of the modified aramid short fiber to the brominated butyl rubber is 10:20;
In the step S300, the mass ratio of the natural rubber, the butadiene rubber, the styrene-butadiene rubber, the aramid composite rubber, the zinc oxide, the stearic acid, the anti-aging agent, the carbon black, the plasticizer, the accelerator and the vulcanizing agent is (66-84): (8-10): (5-6): (3-18): (1.5-6): (1-3): (1-2): (40-60): (1-20): (0.5-2): (0.5-2).
3. The method for preparing the aramid tire tread rubber according to claim 1, wherein,
In the step S100, the concentration of the aluminum chloride solution is 3-4wt%; the component force of the hydroxyl-terminated liquid polyisoprene rubber is 45000-55000;
in the step S300, the anti-aging agent is a mixture of an anti-aging agent 4020 and an anti-aging agent D according to a mass ratio of 1.5:1; the carbon black is at least one of N330 and N550; the plasticizer is at least one of dioctyl phthalate, pine tar and aromatic hydrocarbon oil; the accelerator is at least one of N-cyclohexyl-2-benzothiazole sulfenamide, N-dicyclohexyl-2-benzothiazole sulfenamide and hexamethylenetetramine; the vulcanizing agent is sulfur.
4. The method for preparing the aramid tire tread rubber according to claim 1, wherein,
In the step S100, the aramid staple fiber containing benzimidazole group is immersed in aluminum chloride solution for 20 to 30 minutes by ultrasonic; dipping aramid fiber and hydroxyl-terminated liquid polyisoprene rubber in toluene for 20-30 min, filtering, drying the toluene at 140-150 ℃, washing with water and drying;
In the step S200, the mixing temperature is 60-120 ℃, and the mixing time is 10-15 min;
In the step S300, the first-stage mixing temperature is 60-120 ℃, the mixing time is 5-10 min, the second-stage mixing temperature is 20-40 ℃, and the mixing time is 5-15 min;
in the step S400, the vulcanization temperature is 140-170 ℃ and the vulcanization time is 10-20 min.
5. The method for preparing the aramid tire tread rubber according to claim 1, wherein,
In the step S110, the mass ratio of the nano attapulgite to the zinc chloride is 100 (15-20);
In the step S120, the mass ratio of terephthaloyl chloride, p-phenylenediamine, 2- (4-aminophenyl) -5-aminobenzimidazole, calcium chloride and N-methylpyrrolidone is 100:27:55:55:2000;
in the step S130, the mass ratio of the aramid pulp containing the benzimidazole group to the zinc acetate to the N' N-dimethylacetamide is 2237:20:1800;
in the step S140, the mass ratio of the aramid pulp containing the benzimidazole group, the attapulgite/zinc oxide composite particles and the N' N-dimethylacetamide is 2237:88:1800.
6. The method for preparing the aramid tire tread rubber according to claim 1, wherein,
In the step S110, the concentration of the zinc chloride solution is 0.1 to 0.5 weight percent; the concentration of the ammonium carbonate is 0.1 to 0.2 weight percent;
In the step S150, the coagulating bath is a mixed solvent of N' N-dimethylacetamide and water in a volume ratio of 1:1;
In step S160, the volume ratio of water to acetone in the mixed solution of water and acetone is 1:1.
7. The method for preparing the aramid tire tread rubber according to claim 1, wherein,
In the step S110, the reaction product is filtered and then washed by deionized water, then dried for 1-2 hours at the temperature of below 100 ℃, baked for 1-10 hours at the temperature of 300-600 ℃, crushed and ground by a ball mill after baking, and sieved to obtain the attapulgite/zinc oxide composite particles with the particle size of 400-600 nm;
In the step S120, the solution polymerization temperature is-5-0 ℃ and the polymerization reaction time is 30-40 min;
in the step S150, the type of the coaxial needle is 22G/17G, and the injection speed is 0.03mm/S; the coagulation bath temperature was 80 ℃.
8. The preparation method of the aramid tire tread rubber according to claim 1, wherein the nano attapulgite in the step S100 is subjected to plasma modification, acid modification and sodium salt modification in sequence, and specifically comprises the following steps:
Step S111, plasma modification: putting the nano attapulgite into an arc plasma generator, performing plasma activation for 5-10 min under the direct current voltage of 30-50 kV, then cleaning with deionized water, and finally filtering and drying to obtain the plasma modified attapulgite;
step S112, acid modification: adding the plasma modified attapulgite into a dilute hydrochloric acid solution with the concentration of 0.5-1 wt%, and performing ultrasonic dispersion for 1-1.5 hours at the temperature of 60-80 ℃ to obtain acid modified attapulgite;
Step S113, sodium salt modification: and (3) dropwise adding a sodium hydroxide solution into the acid modified attapulgite at 65-75 ℃, regulating the pH value to 4-5, continuing ultrasonic dispersion for 1-2 hours, and washing, filtering and drying to obtain the modified nano attapulgite.
9. An aramid tire tread rubber characterized in that the aramid tire tread rubber is prepared by the preparation method of any one of claims 1-8.
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| CN103938458A (en) * | 2014-05-20 | 2014-07-23 | 贵州大学 | Method for modifying aramid fiber surface and application of method to enhancement of natural rubber |
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