CN116285046A - Fly ash microbead modified rubber composition and preparation method thereof - Google Patents
Fly ash microbead modified rubber composition and preparation method thereof Download PDFInfo
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- 239000010881 fly ash Substances 0.000 title claims abstract description 90
- 229920001971 elastomer Polymers 0.000 title claims abstract description 78
- 239000005060 rubber Substances 0.000 title claims abstract description 78
- 239000000203 mixture Substances 0.000 title claims abstract description 65
- 239000011325 microbead Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229920003051 synthetic elastomer Polymers 0.000 claims abstract description 21
- 239000005061 synthetic rubber Substances 0.000 claims abstract description 21
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 16
- 230000003712 anti-aging effect Effects 0.000 claims abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 12
- 239000002270 dispersing agent Substances 0.000 claims abstract description 9
- 235000021355 Stearic acid Nutrition 0.000 claims abstract description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 8
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims abstract description 8
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000008117 stearic acid Substances 0.000 claims abstract description 8
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 8
- 239000011593 sulfur Substances 0.000 claims abstract description 8
- 239000011787 zinc oxide Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 26
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 18
- 239000004005 microsphere Substances 0.000 claims description 17
- 239000002994 raw material Substances 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 8
- 229910021536 Zeolite Inorganic materials 0.000 claims description 6
- 239000012670 alkaline solution Substances 0.000 claims description 6
- 239000000084 colloidal system Substances 0.000 claims description 6
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000010457 zeolite Substances 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000002440 industrial waste Substances 0.000 claims description 4
- 239000002808 molecular sieve Substances 0.000 claims description 4
- 229920000867 polyelectrolyte Polymers 0.000 claims description 4
- 229920001195 polyisoprene Polymers 0.000 claims description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 3
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 claims description 3
- 229940005642 polystyrene sulfonic acid Drugs 0.000 claims description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 3
- 239000000899 Gutta-Percha Substances 0.000 claims description 2
- 229920000459 Nitrile rubber Polymers 0.000 claims description 2
- 240000000342 Palaquium gutta Species 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- URAZVWXGWMBUGJ-UHFFFAOYSA-N di(propan-2-yl)azanium;chloride Chemical compound [Cl-].CC(C)[NH2+]C(C)C URAZVWXGWMBUGJ-UHFFFAOYSA-N 0.000 claims description 2
- 229920000588 gutta-percha Polymers 0.000 claims description 2
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 238000007873 sieving Methods 0.000 claims description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 2
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- FBBATURSCRIBHN-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyldisulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSCCC[Si](OCC)(OCC)OCC FBBATURSCRIBHN-UHFFFAOYSA-N 0.000 claims description 2
- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 claims description 2
- 239000011324 bead Substances 0.000 claims 1
- 125000003396 thiol group Chemical class [H]S* 0.000 claims 1
- 239000006229 carbon black Substances 0.000 abstract description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 10
- 239000012744 reinforcing agent Substances 0.000 abstract description 4
- 230000032683 aging Effects 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 229920005830 Polyurethane Foam Polymers 0.000 abstract 1
- 239000000919 ceramic Substances 0.000 abstract 1
- 239000011496 polyurethane foam Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 20
- 238000003825 pressing Methods 0.000 description 13
- 238000007599 discharging Methods 0.000 description 9
- 238000005299 abrasion Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000011231 conductive filler Substances 0.000 description 4
- 230000020169 heat generation Effects 0.000 description 4
- 238000005096 rolling process Methods 0.000 description 4
- 238000009825 accumulation Methods 0.000 description 3
- 239000003738 black carbon Substances 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 239000005062 Polybutadiene Substances 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
- 239000004636 vulcanized rubber 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
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Abstract
The invention belongs to the technical field of rubber preparation, and particularly relates to a rubber composition modified by ceramic microbeads (called fly ash microbeads for short) prepared from fly ash. The rubber composition comprises: the modified polyurethane foam comprises, by weight, 100.0 parts of synthetic rubber, 50.0-80.0 parts of fly ash microbeads, 5.0-10.0 parts of silane coupling agents, 1.0-10.0 parts of dispersing agents, 0.5-3.0 parts of anti-aging agents, 0.8-3.5 parts of accelerators, 0.5-3.5 parts of stearic acid, 2.0-5.0 parts of nano zinc oxide and 0.75-2.0 parts of sulfur. According to the invention, the fly ash microbeads are used as the reinforcing agent to replace the technical scheme of preparing the rubber composition by carbon black and white carbon black in the traditional production process, so that the hardness, wear resistance and ageing resistance of the rubber composition can be greatly improved. The invention further provides a preparation method of the composition.
Description
Technical Field
The invention belongs to the technical field of rubber preparation, and particularly relates to a fly ash microbead modified rubber composition and a preparation method thereof.
Background
With the development of the automobile industry, the performance requirements of the masses on the wear resistance, the ageing resistance and the impact resistance of rubber are increased. During running, a large amount of heat is generated during running due to the large weight of the vehicle body, so that the deformation of the tire rubber is possible, and the service performance of the tire is likely to be affected. The automobile rubber needs a rubber composition with small density and good rigidity, and white carbon black and carbon black are mostly used for preparing the rubber composition in the market at present, but the white carbon black has poor conductivity, is easy to cause charge accumulation, is likely to cause accidents along with time accumulation, has higher cost and cannot completely meet the market demand.
There are also methods on the market at present for alleviating the above problems by adding conductive fillers, such as filled graphene, carbon nanotubes, etc., but because of the large specific surface area of this type of material, the problem of charge accumulation is solved, but the amount of heat generated is increased at the same time, and the mechanical properties of rubber are affected by adding fillers. Therefore, the addition of the conductive filler does not solve the problem comprehensively.
The patent with publication number CN 112409657B provides a conductive rubber composition and a preparation method thereof, wherein carbon nano tubes and graphene are used as main conductive fillers, and the fillers are more dispersed in rubber by using plasticizers, so that the fillers are uniformly distributed in the rubber.
The patent with publication number CN202211597959 provides a rubber composition and a preparation method thereof, and the interface compatibility of a blend of solution polymerized styrene-butadiene rubber (SBR) and polybutadiene rubber (BR) is improved by utilizing a multiple smelting method, and the rubber composition has low rolling resistance, high wear resistance and good tensile resistance, but relatively high cost.
Disclosure of Invention
The technical problems in the prior art are that the cost of rubber preparation is high, the conductivity is poor, the heat generation is more and the rubber is easy to crack.
In order to solve the technical problems, a novel method for using the microbead fly ash as a reinforcing agent tire composition is provided. The method has the advantages of low raw material cost, good conductivity and less heat generation, comprehensively solves the problem that rubber products existing in other methods are easy to crack, and can effectively reduce the pollution of the fly ash to the environment, and the application provides the following technical scheme:
the invention provides a fly ash microbead modified rubber composition, which comprises the following raw materials in parts by mass: 100 parts of synthetic rubber, 50-80 parts of fly ash microbeads, 5-10 parts of silane coupling agent, 1-10 parts of dispersing agent, 0.5-3 parts of anti-aging agent, 0.8-3.5 parts of accelerator, 0.5-3.5 parts of stearic acid, 2-5 parts of nano zinc oxide and 0.75-2 parts of sulfur.
Preferably, the synthetic rubber is selected from one or more of solution polymerized styrene-butadiene rubber (CAS: 9003-55-8), butadiene rubber, cis-polyisoprene, trans-polyisoprene, gutta percha and nitrile rubber.
Preferably, the anti-aging agent is selected from one or more of anti-aging agent 6PPD, anti-aging agent 4010, anti-aging agent RD, and anti-aging agent 4020.
Preferably, the accelerator is selected from one or more of accelerator NS, accelerator DM, accelerator TMTD, accelerator DPG and accelerator CZ.
Preferably, the silane coupling agent is one or more of bis (gamma-triethoxysilylpropyl) tetrasulfide, bis (gamma-triethoxysilylpropyl) disulfide and mercapto silane coupling agent.
Preferably, the particle size of the fly ash microbeads is 0.5-10 μm, and the specific surface area is 0.8-3.7m 2 /g。
Preferably, the fly ash microbeads are prepared from industrial waste fly ash.
Preferably, the fly ash microbeads are prepared by the following preparation method:
s11: adsorbing the fly ash microsphere raw material in polyelectrolyte solution to obtain the adsorbed fly ash microsphere; the fly ash microsphere raw material is obtained by a method of sieving industrial waste residue fly ash and then floating with boiling water;
s12: adsorbing the adsorbed fly ash microspheres in zeolite colloid solution, washing and drying to obtain seed crystal modified microspheres;
s13: reacting the seed crystal modified microsphere with an alkaline solution, washing and drying to obtain the fly ash microsphere; the alkaline solution comprises NaOH and NaAlO 2 And water.
Further, the diameter of the fly ash microsphere raw material is 5-80 mu m, and the thickness of the spherical shell is 2-4 mu m.
Further, the polyelectrolyte solution is an aqueous solution of polydimethyl diisopropyl ammonium chloride (PDDA) and an aqueous solution of polystyrene sulfonic acid (PSS).
Further, in the step S13, naOH and NaAlO are contained in the alkaline solution 2 The molar ratio of (3) to (10): 1.
further, the zeolite colloid solution is prepared by the following method:
s21: adding sodium aluminate into an alkali solution, stirring, adding silica sol, stirring, and crystallizing by a hydrothermal method to prepare a molecular sieve;
s22: and after solid-liquid separation of the molecular sieve, dispersing the solid in water to obtain the zeolite colloid solution.
The invention also provides a preparation method of the fly ash microbead modified rubber composition, which comprises the following steps:
s31: adding synthetic rubber, stearic acid, a silane coupling agent and nano zinc oxide into an internal mixer, mixing for 20-30s, adding part of fly ash microbeads, mixing for 20-30s at 105-135 ℃, pressing a bolt after lifting the bolt for 10-30s, mixing for 20-30s at 140-155 ℃, discharging tablets, and cooling to room temperature (25+/-5 ℃) to obtain a section of master batch; the part of the fly ash microbeads are 45-70% of the total amount of the fly ash microbeads;
s32: mixing the primary master batch, the dispersing agent and the anti-aging agent for 10-30s, adding the rest fly ash microbeads, pressing and mixing at 105-135 ℃, pressing and mixing at 10-30s for lifting bolts, pressing and mixing at 140-155 ℃, discharging tablets, and cooling to room temperature to obtain the secondary master batch;
s33: adding the two-stage masterbatch, sulfur and accelerator into an internal mixer, lifting bolts for 10-30s, pressing bolts for 1-30s, lifting bolts for 10-30s, reducing bolts at 90-115 ℃ for mixing, discharging tablets, and cooling to room temperature to obtain the rubber composition.
Further, the processing interval time between the step S31, the step S32 and the step S33 is 8-16h.
Further, in the step S31, the step S32 and the step S33, the sheet is discharged by a twin screw extruder.
Specifically, the preparation method of the fly ash microbead modified rubber composition comprises the following steps:
step 1, adding synthetic rubber, stearic acid, a silane coupling agent and nano zinc oxide into an internal mixer, mixing for 20-30s, then injecting fly ash microbeads accounting for a certain proportion of the total mass, mixing to 105-135 ℃, maintaining for 20-30s, lifting bolts for 10-30s, pressing bolts, mixing to 140-155 ℃, maintaining for 20-30s, discharging by adopting a double screw extruder, and naturally cooling to room temperature to obtain a first-stage masterbatch;
and 3, adding the second-stage masterbatch, sulfur and an accelerator into an internal mixer, lifting a bolt for 10-30s, pressing a bolt for 10-30s, lifting the bolt for 10-30s, lowering the bolt, mixing to 90-115 ℃, discharging tablets by a double-screw extruder, and cooling to room temperature to obtain the fly ash microbead modified rubber composition.
Through the technical scheme, the problems that the conductivity of the white carbon black used in the current market is poor and the heat generation amount of the conductive filler is increased are effectively solved. And the fly ash serving as a raw material is extremely easy to obtain, can be directly obtained from a thermal power plant, and greatly reduces the cost of the raw material. The size range of the fly ash microbeads used in the scheme is selected to be 5000-8000 meshes, and the diameter reaches the micro-nano level; when 45% -70% of fly ash microbeads are added, the smelting temperature is preferably 105-135 ℃. The dispersing agent is added in the invention, so that the fly ash microbeads are distributed more uniformly, and the performance of the produced rubber composition is more stable. The fly ash microbeads have strong rigidity and low density, and the fly ash microbeads are used as rubber tire reinforcing agents to ensure that the overall performance of the obtained rubber tires is far superior to that of the existing combined rubber tires on the market. In addition, the method mainly adopts the raw materials prepared from the industrial waste residue and the fly ash, reduces the pollution of the fly ash to the environment, can greatly reduce the cost and achieves better technical effects.
Compared with the prior art, the technical scheme of the invention has the following advantages:
the fly ash microbeads are added in the rubber composition, so that the heat generation amount of rubber can be effectively reduced, the binding force between the fly ash microbeads and the rubber can be enhanced, the fly ash microbeads have higher reinforcing and elastic effects, the performance of rubber products is improved, and the fly ash microbeads have the advantages of smooth surface of rubber compound, good vulcanized rubber elasticity, low compression heat rise and aging resistance. In addition, the fly ash used in the method is rich in source of main raw materials, low in cost and capable of compounding the green development requirement, low in cost (fly ash microbeads replace white carbon black, and the production cost of tires can be reduced by about 50-70%), tires with higher quality are produced, a large amount of material cost is saved for enterprises, and profit margin of enterprise products can be improved.
Drawings
FIG. 1 is a scanning electron microscope image of fly ash microbeads.
FIG. 2 is a graph comparing impact resistance with rubber prepared from polypropylene.
FIG. 3 is a tread of a rubber tire modified with fly ash microbeads.
FIG. 4 is a scanning electron microscope image of micro-nano fly ash microbeads.
Detailed Description
The present invention will be further described with reference to the accompanying drawings and specific examples, which are not intended to be limiting, so that those skilled in the art will better understand the invention and practice it.
Example 1
A rubber composition using fly ash microbeads as reinforcing agent and a preparation method thereof. Step 1, mixing synthetic rubber, stearic acid, a silane coupling agent and nano zinc oxide, and adding the mixture into an internal mixer to obtain a mixture I, wherein the synthetic rubber is as follows: stearic acid: silane coupling agent: the mass ratio of the nano zinc oxide is 100:3.5:10.0:5.0, mixing for 30 seconds to obtain a precursor II. Injecting 70% fly ash microbeads into precursor II, wherein precursor II: the mass ratio of the fly ash microbeads is 118.5:67.5, mixing to 105 ℃, maintaining for 30 seconds, lifting bolts, maintaining for 30 seconds, pressing bolts, mixing to 140 ℃, maintaining for 30 seconds, then discharging by adopting a double-screw extruder, and naturally cooling to room temperature to obtain master batch III; step 2, adding the masterbatch III, a dispersing agent and an anti-aging agent into an internal mixer, wherein the masterbatch III: dispersing agent: the mass ratio of the anti-aging agent is 118.5:10.0:3.0, mixing for 30 seconds, adding the rest fly ash microbeads, pressing and mixing to 105 ℃, lifting the bolts and keeping for 30 seconds, then pressing and mixing again to 140 ℃, discharging sheets by adopting a double-screw extruder, and cooling to room temperature to obtain master batch IV; step 3, adding the masterbatch IV, sulfur and an accelerator into an internal mixer, wherein the masterbatch IV: sulfur: the mass ratio of the accelerator is 131.5:2.0:3.5, lifting the bolts for 30 seconds, pressing the bolts for 30 seconds, lifting the bolts for 30 seconds, lowering the bolts, mixing to 115 ℃, discharging the sheet by adopting a double-screw extruder again, and cooling to room temperature to obtain the rubber composition.
Example 2
According to the method of example 1, the properties of the rubber composition can be adjusted by changing the mass ratio of the fly ash microbeads added in step 1, the total mass ratio of the fly ash and the synthetic rubber component, so as to obtain rubber compositions with different elasticity and different wear resistance, and the concrete is shown in table 1.
TABLE 1 raw material formulation table for synthetic rubber in examples 1-5
Example 3
According to the method of example 1, the properties of the rubber composition can be adjusted by changing the mass ratio of the fly ash microbeads added in step 1, the total mass ratio of the fly ash and the synthetic rubber component, so as to obtain rubber compositions with different elasticity and different wear resistance, and the concrete is shown in table 1.
Example 4
According to the method of example 1, the properties of the rubber composition can be adjusted by changing the mass ratio of the fly ash microbeads added in step 1, the total mass ratio of the fly ash and the synthetic rubber component, so as to obtain rubber compositions with different elasticity and different wear resistance, and the concrete is shown in table 1.
Example 5
According to the method of example 1, the properties of the rubber composition can be adjusted by changing the mass ratio of the fly ash microbeads added in step 1, the total mass ratio of the fly ash and the synthetic rubber component, so as to obtain rubber compositions with different elasticity and different wear resistance, and the concrete is shown in table 1.
Example 6
According to the method of example 1, except that the mass ratio of the fly ash microbeads added in step 1, the total mass ratio of the fly ash and the synthetic rubber component are changed, the properties of the rubber composition can be adjusted to obtain rubber compositions with different elasticity and different wear resistance, and the specific properties are shown in table 2.
TABLE 2 raw material formulation table for synthetic rubber in examples 6-8
Example 7
According to the method of example 1, except that the mass ratio of the fly ash microbeads added in step 1, the total mass ratio of the fly ash and the synthetic rubber component are changed, the properties of the rubber composition can be adjusted to obtain rubber compositions with different elasticity and different wear resistance, and the specific properties are shown in table 2.
Example 8
According to the method of example 1, except that the mass ratio of the fly ash microbeads added in step 1, the total mass ratio of the fly ash and the synthetic rubber component are changed, the properties of the rubber composition can be adjusted to obtain rubber compositions with different elasticity and different wear resistance, and the specific properties are shown in table 2.
Comparative example 1
According to the method of patent CN102171285a, white carbon black, black carbon black and rubber composition were prepared to obtain samples to be tested, and specific components are shown in table 3.
Comparative example 2
According to the method of patent CN102171285a, white carbon black, black carbon black and rubber composition were prepared to obtain samples to be tested, and specific components are shown in table 3.
Comparative example 3
According to the method of patent CN102171285a, white carbon black, black carbon black and rubber composition were prepared to obtain samples to be tested, and specific components are shown in table 3.
Comparative example 4
According to the method of patent CN201210401997.2, a modified white carbon black and a rubber composition are prepared by using a lower pressurizing pressure, and a sample to be tested is obtained, and specific components are shown in table 3.
Comparative example 5
According to the method of patent CN201210401997.2, a modified white carbon black and a rubber composition are prepared by using a lower pressurizing pressure, and a sample to be tested is obtained, and specific components are shown in table 3.
Comparative example 6
The sample to be tested in comparative example 6 was prepared according to the method of patent CN202110047833.3 using scheme a, the specific ingredients are shown in table 3.
Comparative example 7
The sample to be tested in comparative example 7 was prepared according to the method of patent CN202110047833.3 using protocol B, the specific ingredients are shown in table 4.
TABLE 3 raw material formulation table for synthetic rubber in comparative examples 1 to 5
Table 4 Table of raw materials for synthetic rubber in comparative examples 6 and 7
Effect evaluation 1
As can be seen from the effect examples, the hardness, the Aldrich loss factor and the tensile strength of the rubber products obtained in each example are remarkably improved compared with the existing high-performance tire rubber composition.
Effect example the properties of the rubber compositions prepared in examples 1 to 8 and comparative examples 1 to 7 were tested; the product obtained in comparative example 3 was selected as a reference (the data obtained in comparative example 3 is comparable to the data of the present high-performance tire rubber composition), and the remaining examples and comparative examples were compared with the data obtained in comparative example 3; specifically, the tensile strength was measured at 25℃at a tensile speed of 500mm/min; measuring the amount of acle abrasion at 25 ℃; hysteresis loss tan delta of DMA (10 Hz, 0.25%) was measured at 60 ℃; wherein the tensile index= (tensile strength of each rubber composition)/(tensile strength of comparative example 3) ×100, the greater the tensile index, the greater the tensile strength; low rolling resistance index= (tan δ of comparative example 3)/(tan δ of each rubber composition) ×100, the larger the low rolling resistance index is, the smaller the rolling resistance is; abrasion resistance index= (acle abrasion amount of comparative example 3)/(acle abrasion amount of each rubber composition) ×100, the larger the abrasion index, the smaller the abrasion; the data obtained are shown in Table 5.
Table 5 comparison of physical Property parameters of examples and comparative examples
Note that: all samples were tested under equivalent test conditions. "-" indicates that it was not detected.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations and modifications of the present invention will be apparent to those of ordinary skill in the art in light of the foregoing description. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the present invention.
Claims (10)
1. The fly ash microbead modified rubber composition is characterized by comprising the following raw materials in parts by mass: 100 parts of synthetic rubber, 50-80 parts of fly ash microbeads, 5-10 parts of silane coupling agent, 1-10 parts of dispersing agent, 0.5-3 parts of anti-aging agent, 0.8-3.5 parts of accelerator, 0.5-3.5 parts of stearic acid, 2-5 parts of nano zinc oxide and 0.75-2 parts of sulfur.
2. The fly ash microbead-modified rubber composition of claim 1, wherein said synthetic rubber is selected from one or more of solution polymerized styrene-butadiene rubber, cis-polyisoprene, trans-polyisoprene, gutta percha, and nitrile rubber.
3. The fly ash microbead-modified rubber composition according to claim 1, wherein the silane coupling agent is one or more of bis (γ -triethoxysilylpropyl) tetrasulfide, bis (γ -triethoxysilylpropyl) disulfide and mercapto-based silane coupling agent.
4. The fly ash microbead-modified rubber composition according to claim 1, wherein the particle size of the fly ash microbead is 0.5 to 10 μm and the specific surface area is 0.8 to 3.7m 2 /g。
5. The fly ash microbead-modified rubber composition of claim 1, wherein said fly ash microbeads are prepared by the following preparation method:
s11: adsorbing the fly ash microsphere raw material in polyelectrolyte solution to obtain the adsorbed fly ash microsphere; the fly ash microsphere raw material is obtained by a method of sieving industrial waste residue fly ash and then floating with boiling water;
s12: adsorbing the adsorbed fly ash microspheres in zeolite colloid solution, washing and drying to obtain seed crystal modified microspheres;
s13: reacting the seed crystal modified microsphere with an alkaline solution, washing and drying to obtain the fly ash microsphere; the alkaline solution comprises NaOH and NaAlO 2 And water.
6. The fly ash microsphere modified rubber composition of claim 5, wherein the fly ash microsphere material has a diameter of 5 to 80 μm and a spherical shell thickness of 2 to 4 μm.
7. The fly ash microbead-modified rubber composition according to claim 5, wherein the polyelectrolyte solution is an aqueous solution of polydimethyl diisopropylammonium chloride and an aqueous solution of polystyrene sulfonic acid.
8. The fly ash bead modified rubber composition according to claim 5, wherein in said step S13, naOH and NaAlO are contained in said alkaline solution 2 The molar ratio of (3) to (10): 1.
9. the fly ash microbead-modified rubber composition of claim 5, wherein said zeolite colloid solution is prepared by the following method:
s21: adding sodium aluminate into an alkali solution, stirring, adding silica sol, stirring, and crystallizing by a hydrothermal method to prepare a molecular sieve;
s22: and after solid-liquid separation of the molecular sieve, dispersing the solid in water to obtain the zeolite colloid solution.
10. A method of preparing a fly ash microbead-modified rubber composition according to any of claims 1-9, comprising the steps of:
s31: adding synthetic rubber, stearic acid, a silane coupling agent and nano zinc oxide into an internal mixer, mixing for 20-30s, adding part of fly ash microbeads, mixing for 20-30s at 105-135 ℃ and mixing for 20-30s at 140-155 ℃, and cooling to room temperature to obtain a section of master batch; the weight of the part of the fly ash microbeads is 45-70% of the total weight of the fly ash microbeads;
s32: mixing the primary master batch, the dispersing agent and the anti-aging agent for 10-30s, adding the rest fly ash microbeads, mixing at 105-135 ℃ and 140-155 ℃, and cooling to room temperature to obtain secondary master batch;
s33: and mixing the two-stage master batch, sulfur and the accelerator at 90-115 ℃, and cooling to room temperature to obtain the rubber composition.
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