CN118910477B - Porous three-phase alloy and its application, high bio-based elastomer tire apex rubber composition - Google Patents
Porous three-phase alloy and its application, high bio-based elastomer tire apex rubber composition Download PDFInfo
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- CN118910477B CN118910477B CN202411377110.XA CN202411377110A CN118910477B CN 118910477 B CN118910477 B CN 118910477B CN 202411377110 A CN202411377110 A CN 202411377110A CN 118910477 B CN118910477 B CN 118910477B
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 158
- 239000005060 rubber Substances 0.000 title claims abstract description 114
- 239000000203 mixture Substances 0.000 title claims abstract description 51
- 239000000806 elastomer Substances 0.000 title claims abstract description 44
- 239000006229 carbon black Substances 0.000 claims abstract description 69
- 239000000843 powder Substances 0.000 claims abstract description 64
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 24
- -1 aluminum-silicon-carbon Chemical compound 0.000 claims abstract description 19
- 239000002245 particle Substances 0.000 claims abstract description 17
- 239000011148 porous material Substances 0.000 claims abstract description 15
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 7
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 5
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims description 82
- 238000003825 pressing Methods 0.000 claims description 30
- 238000004073 vulcanization Methods 0.000 claims description 30
- 239000003795 chemical substances by application Substances 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 24
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 24
- 230000003712 anti-aging effect Effects 0.000 claims description 20
- 239000011347 resin Substances 0.000 claims description 18
- 229920005989 resin Polymers 0.000 claims description 18
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 18
- 241000209094 Oryza Species 0.000 claims description 17
- 235000007164 Oryza sativa Nutrition 0.000 claims description 17
- 235000009566 rice Nutrition 0.000 claims description 17
- 239000000725 suspension Substances 0.000 claims description 17
- 230000008569 process Effects 0.000 claims description 15
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 14
- 229910052717 sulfur Inorganic materials 0.000 claims description 14
- 239000011593 sulfur Substances 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 claims description 12
- 235000019743 Choline chloride Nutrition 0.000 claims description 12
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 12
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 claims description 12
- 229960003178 choline chloride Drugs 0.000 claims description 12
- 238000005507 spraying Methods 0.000 claims description 12
- 244000043261 Hevea brasiliensis Species 0.000 claims description 11
- 229920003052 natural elastomer Polymers 0.000 claims description 11
- 229920001194 natural rubber Polymers 0.000 claims description 11
- 239000011592 zinc chloride Substances 0.000 claims description 9
- 235000005074 zinc chloride Nutrition 0.000 claims description 9
- 239000003208 petroleum Substances 0.000 claims description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- 230000003213 activating effect Effects 0.000 claims description 6
- 230000002776 aggregation Effects 0.000 claims description 6
- 238000004220 aggregation Methods 0.000 claims description 6
- 230000005496 eutectics Effects 0.000 claims description 6
- RCHKEJKUUXXBSM-UHFFFAOYSA-N n-benzyl-2-(3-formylindol-1-yl)acetamide Chemical compound C12=CC=CC=C2C(C=O)=CN1CC(=O)NCC1=CC=CC=C1 RCHKEJKUUXXBSM-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 5
- 239000012190 activator Substances 0.000 claims description 4
- 239000000956 alloy Substances 0.000 claims description 4
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 235000021355 Stearic acid Nutrition 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- CMAUJSNXENPPOF-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)-n-cyclohexylcyclohexanamine Chemical compound C1CCCCC1N(C1CCCCC1)SC1=NC2=CC=CC=C2S1 CMAUJSNXENPPOF-UHFFFAOYSA-N 0.000 claims description 3
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 claims description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 3
- 239000008117 stearic acid Substances 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- 238000013329 compounding Methods 0.000 claims 1
- 230000009286 beneficial effect Effects 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 12
- 238000012360 testing method Methods 0.000 description 9
- 230000001976 improved effect Effects 0.000 description 8
- 239000011324 bead Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 238000011161 development Methods 0.000 description 6
- 230000018109 developmental process Effects 0.000 description 6
- 230000007613 environmental effect Effects 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000009472 formulation Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000002708 enhancing effect Effects 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 239000002803 fossil fuel Substances 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 230000020169 heat generation Effects 0.000 description 3
- 239000010903 husk Substances 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 241001441571 Hiodontidae Species 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- 230000008646 thermal stress Effects 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 101000666657 Homo sapiens Rho-related GTP-binding protein RhoQ Proteins 0.000 description 1
- 102100038339 Rho-related GTP-binding protein RhoQ Human genes 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C21/00—Alloys based on aluminium
- C22C21/02—Alloys based on aluminium with silicon as the next major constituent
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/08—Alloys with open or closed pores
-
- 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
- C08K3/16—Halogen-containing compounds
- C08K2003/168—Zinc halides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- 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)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a porous three-phase alloy and application thereof, and a high bio-based elastomer tire apex rubber composition, and particularly relates to the technical field of tire manufacturing. The porous three-phase alloy is mainly prepared from carbon black and natural ore powder through high-temperature jet, wherein the content of silicon dioxide in the natural ore powder is 40-60%, the content of aluminum oxide is 30-40%, the specific surface area of the natural ore powder is 30-70 m 2/g, the pore volume is 0.20-0.40 cm 3/g, the pore number is 1-3 hundred million/g, and the D50 particle size is 0.25-5 mu m. The porous three-phase alloy provided by the invention is a novel aluminum-silicon-carbon aggregate, not only has high hardness and wear resistance, but also has a low thermal expansion coefficient, and is beneficial to maintaining the dimensional stability of a rubber composition in a high-temperature environment. The aluminum-silicon-carbon aggregate has good performance on interface bonding, and reduces interface thermal resistance, thereby improving the heat conduction efficiency of the aggregate.
Description
Technical Field
The invention relates to the technical field of tire manufacturing, in particular to a porous three-phase alloy and application thereof, and a high bio-based elastomer tire apex rubber composition.
Background
The triangular rubber is used as a key component part on two sides of the central line of the tire tread, the triangular design of the triangular rubber not only realizes transition between the tire side and the bead ring, but also effectively protects the tire and prolongs the service life of the tire by enhancing the rigidity and the wear resistance of the tread. However, during the running of the tire, friction between the apex and the bead ring and the heat generated by the bead ring can cause heat build up, increasing the risk of overheating the tire. The long-time high-temperature environment can cause the ageing or performance degradation of the triangular glue, so that the performance and the service life of the tire are influenced, and even the driving safety is influenced.
In the existing preparation process of the triangular glue, the heat conduction performance of the used raw materials is poor, the heat resistance is insufficient, the performance of the final product cannot meet higher requirements, the service life of the tire is influenced, the replacement frequency is increased, and the use experience is reduced.
In addition, most of the raw materials for preparing the triangular glue are derived from petroleum and petrochemical products, do not meet the requirements of bio-based raw materials, are difficult to meet the requirements of green and environmental protection, and can have negative influence on the environment after the service life of the tire is finished. Meanwhile, when an attempt is made to use bio-based carbon as a substitute raw material, problems such as slow sulfur rate, low thermal conductivity and the like are caused. Even if the amount of vulcanizing agent is increased to increase the sulfur speed, the rubber becomes brittle, and the heat resistance and physical properties become poor, further affecting the overall performance of the apex.
In view of this, the present invention has been made.
Disclosure of Invention
It is an object of the present invention to provide a porous three-phase alloy that alleviates at least one of the above-mentioned technical problems of the prior art.
It is a further object of the present invention to provide a porous three-phase alloy for use.
The invention further aims at providing a high bio-based elastomer tire apex rubber composition.
The fourth object of the invention is to provide a high bio-based elastomer tire apex rubber.
In order to solve the technical problems, the invention adopts the following technical scheme:
In a first aspect of the invention, a porous three-phase alloy is provided, which is mainly obtained from carbon black and natural ore powder by high temperature jet.
The content of silicon dioxide in the natural ore powder is 40-60%, and the content of aluminum oxide is 30-40%.
The natural ore powder has a rich micropore structure, the specific surface area is 30-70 m 2/g, the pore volume is 0.20-0.40 cm 3/g, the pore number is 1-3 hundred million/g, and the D50 particle size is 0.25-5 mu m.
Further, the mass ratio of the carbon black to the natural ore powder is 5-9:1-5.
The carbon black comprises at least one of the designations N134, N220, N234, N330, N375, and N550.
Further, the high temperature jet process includes:
spraying natural ore powder suspension mixed by a jet system into a carbon black reaction furnace, reacting carbon black and natural ore powder to generate an aluminum-silicon-carbon structure, and forming an aluminum-silicon-carbon aggregate through aggregation to obtain the porous three-phase alloy.
The concentration of the natural ore powder suspension is 15-25wt%.
The spraying flow of the natural ore powder suspension is 4000-6000 kg/h.
The reaction temperature is 1000-1500 ℃.
The invention also provides an application of the porous three-phase alloy in preparing a high bio-based elastomer tire apex rubber composition.
The invention provides a high bio-based elastomer tire apex rubber composition, which comprises the following components in parts by weight:
100 parts of natural rubber, 5-20 parts of the porous three-phase alloy in the first aspect, 20-40 parts of rice hull ash carbon black, 1-4 parts of a silane coupling agent, 3-6 parts of an activating agent, 2-6 parts of an anti-aging agent, 1-3 parts of a tackifying resin, 2.5-4.7 parts of insoluble sulfur, 0.8-1.5 parts of an accelerator and 0.1-0.5 part of a super vulcanization assistant.
Further, the super vulcanization aid is a eutectic solvent.
The super vulcanization assistant is mainly prepared from zinc chloride, choline chloride and thiourea according to a molar ratio of 1-3:1-3:3-6.
Further, the specific surface area of the rice hull ash white carbon black is 165-240 m 2/g, and the particle size is 0.8-7.8 mu m.
The brand of the silane coupling agent comprises at least one of TESPT, si75 and Si 747.
The activator comprises stearic acid and/or zinc oxide.
The brand of the anti-aging agent comprises at least one of anti-aging agent 4020, anti-aging agent RD and anti-aging agent 4010 NA.
The tackifying resin comprises at least one of a tertiary butyl phenol aldehyde resin, an alkyl phenol aldehyde resin, and a petroleum resin.
Preferably, the petroleum resin comprises a C5 and/or C9 designation.
The brand of the accelerator comprises at least one of accelerator NS, accelerator CZ and accelerator DZ.
The fourth aspect of the invention provides a high bio-based elastomer tire apex rubber, which is obtained by mixing the high bio-based elastomer tire apex rubber composition in the main third aspect.
Further, the mixing method comprises the following steps:
mixing natural rubber, a porous three-phase alloy material, rice hull ash white carbon black, a silane coupling agent, an anti-aging agent and tackifying resin, and performing one-stage mixing to obtain first masterbatch;
then carrying out two-stage mixing on the first masterbatch to obtain a second masterbatch;
And finally adding insoluble sulfur, an accelerator and a super vulcanization assistant into the second masterbatch, mixing, and then carrying out three-stage mixing to obtain the high bio-based elastomer tire apex rubber.
Further, the one-stage mixing comprises mixing for 30-50 s, lifting bolt and pressing bolt mixing for 20-30 s according to sequence, and then lifting bolt and pressing bolt mixing to 140-155 ℃ rubber discharge.
The two-stage mixing comprises mixing for 30-50 s, lifting bolts and pressing bolts for mixing for 20-30 s according to sequence, and then lifting bolts and pressing bolts for mixing to 135-145 ℃ for rubber discharge.
The three-stage mixing comprises mixing for 30-50 s, lifting bolts and pressing bolts for mixing for 20-30 s according to sequence, and then lifting bolts and pressing bolts for mixing to 95-105 ℃ rubber discharge.
Compared with the prior art, the invention has at least the following beneficial effects:
The porous three-phase alloy provided by the invention forms a novel aluminum-silicon-carbon aggregate by endowing the dominant performance of carbon black to natural ore powder. The aggregate not only has high hardness and wear resistance, but also has a low thermal expansion coefficient, which is beneficial to maintaining the dimensional stability of the rubber composition in a high-temperature environment. At the same time, the aggregate exhibits excellent high temperature resistance, being able to maintain its mechanical properties under extreme temperature conditions. The high heat conductivity coefficient of aluminum ensures that the formed aluminum-silicon-carbon aggregate has good performance on interface combination, reduces interface thermal resistance, and improves the heat conduction efficiency of the aggregate. In addition, the coefficients of thermal expansion of aluminum, silicon and carbon are relatively matched, which reduces thermal stress caused by uneven thermal expansion and further promotes stable transfer of heat energy. The role of the silicon and carbon particles in the aggregate is to reduce thermal resistance, promote the efficiency of the heat conduction path, and make the overall aggregate excellent in heat conduction.
By applying the porous three-phase alloy provided by the invention, the prepared high-biobased elastomer tire apex rubber composition has better heat conduction capacity, mechanical strength and lower thermal expansion coefficient in view of the advantages of the porous three-phase alloy.
The high bio-based elastomer tire apex rubber composition provided by the invention is based on natural rubber, so that the bio-based content in the rubber composition is improved, and the dependence on fossil fuel is reduced. Meanwhile, the addition of the bio-based carbon black reduces the use cost of the carbon black, reduces the environmental pollution, saves fossil resources and realizes the sustainable development of the rubber industry. The problems of poor physical properties, low sulfur speed and low efficiency caused by the bio-based carbon black can be perfectly solved by using the super vulcanization assistant, and the vulcanization efficiency and the vulcanization quality are improved. Meanwhile, the addition of the porous three-phase alloy enables the rubber composition to have low heat generation, high heat conduction and excellent heat resistance, and the performance of the rubber product is improved. The raw materials in the composition are matched with each other, so that the rubber composition has remarkable technical effects in improving rubber performance and enhancing environmental friendliness.
The high-biobased elastomer tire apex rubber provided by the invention has the advantages of the rubber composition, so that the prepared apex rubber is better in performance and more environment-friendly, meets the performance requirements of different fields, and promotes the development of the tire industry.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is a scanning electron microscope image at one magnification obtained in characterization example 1;
FIG. 2 is a scanning electron microscope image at another magnification obtained in characterization example 1;
fig. 3 is a scanning electron microscope image at a third magnification obtained in the characterization example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. The components of embodiments of the present invention may be arranged and designed in a wide variety of different configurations.
It is noted that relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
In a first aspect of the invention, a porous three-phase alloy is provided, which is mainly obtained from carbon black and natural ore powder by high temperature jet.
The content of silicon dioxide in the natural ore powder is 40-60%, and the content of aluminum oxide is 30-40%.
The natural ore powder has a rich micropore structure, the specific surface area is 30-70 m 2/g, the pore volume is 0.20-0.40 cm 3/g, the pore number is 1-3 hundred million/g, and the D50 particle size is 0.25-5 mu m.
The porous three-phase alloy provided by the invention forms a novel aluminum-silicon-carbon aggregate by endowing the dominant performance of carbon black to natural ore powder. The aggregate not only has high hardness and wear resistance, but also has a low thermal expansion coefficient, which is beneficial to maintaining the dimensional stability of the rubber composition in a high-temperature environment. At the same time, the aggregate exhibits excellent high temperature resistance, being able to maintain its mechanical properties under extreme temperature conditions. The high heat conductivity coefficient of aluminum ensures that the formed aluminum-silicon-carbon aggregate has good performance on interface combination, reduces interface thermal resistance, and improves the heat conduction efficiency of the aggregate. In addition, the coefficients of thermal expansion of aluminum, silicon and carbon are relatively matched, which reduces thermal stress caused by uneven thermal expansion and further promotes stable transfer of heat energy. The role of the silicon and carbon particles in the aggregate is to reduce thermal resistance, promote the efficiency of the heat conduction path, and make the overall aggregate excellent in heat conduction.
The invention limits the content of silicon dioxide and aluminum oxide in natural ore powder to ensure the reasonable proportion of each raw material in the aluminum-silicon-carbon aggregate, thereby optimizing the performance of the porous three-phase alloy.
Typically, but not by way of limitation, the natural ore fines may have a silica content of 40%, 45%, 50%, 55%, 60%, or any value in the range of 40% to 60%, and the alumina content may have a silica content of 30%, 35%, 40%, or any value in the range of 30% to 40%.
The invention limits the specific surface area, pore volume, pore number and D50 particle size of the natural ore powder, so as to ensure the rich pore structure of the natural ore powder, thus improving the growth of the primary carbon black particles on the surface of the pores, being beneficial to the combination of the tail ends of rubber molecular chains and the pores, and thirdly, forming gradient particle size distribution of the particle size of the ore powder and the particle size of the carbon black.
Further, the mass ratio of the carbon black to the natural ore powder is 5-9:1-5.
The mass ratio of the carbon black to the natural ore powder is controlled within the range of 5-9:1-5, so that the original particles of the carbon black are ensured to be coated on the surface of the natural ore powder with a pore structure, the carbon black is not coated by the natural ore powder, and the prepared filler has a good reinforcing effect.
Typically, but not by way of limitation, the mass ratio of carbon black to natural ore fines may be specifically 5:5, 6:4, 7:3, 8:2, 9:1, or any value within the range of 5-9:1-5.
The carbon black comprises at least one of the designations N134, N220, N234, N330, N375, and N550.
Further, the high temperature jet process includes:
spraying natural ore powder suspension mixed by a jet system into a carbon black reaction furnace, reacting carbon black and natural ore powder to generate an aluminum-silicon-carbon structure, and forming an aluminum-silicon-carbon aggregate through aggregation to obtain the porous three-phase alloy.
The concentration of the natural ore powder suspension is 15-25wt%.
The spraying flow of the natural ore powder suspension is 4000-6000 kg/h.
The reaction temperature is 1000-1500 ℃.
In the high-temperature jet process, carbon black particles grow in situ on the porous material to form a carbon black coating.
Typically, but not by way of limitation, the concentration of the natural ore powder suspension may be 15wt.%, 16wt.%, 17wt.%, 18wt.%, 19wt.%, 20wt.%, 21wt.%, 22wt.%, 23wt.%, 24wt.%, or 25wt.%, or any value in the range of 15wt.% to 25 wt.%.
Typically, but not by way of limitation, the jet flow rate of the natural ore powder suspension may be 4000 kg/h, 4500 kg/h, 5000 kg/h, 5500 kg/h, 6000 kg/h, or any value within the range 4000 kg/h to 6000 kg/h.
Likewise, the temperature of the reaction may be 1000 ℃, 1100 ℃, 1200 ℃, 1300 ℃, 1400 ℃, 1500 ℃, or any value in the range of 1000 ℃ to 1500 ℃.
The invention also provides an application of the porous three-phase alloy in preparing a high bio-based elastomer tire apex rubber composition.
By applying the porous three-phase alloy provided by the invention, the prepared high-biobased elastomer tire apex rubber composition has better heat conduction capacity, mechanical strength and lower thermal expansion coefficient in view of the advantages of the porous three-phase alloy.
The invention provides a high bio-based elastomer tire apex rubber composition, which comprises the following components in parts by weight:
100 parts of natural rubber, 5-20 parts of the porous three-phase alloy in the first aspect, 20-40 parts of rice hull ash carbon black, 1-4 parts of a silane coupling agent, 3-6 parts of an activating agent, 2-6 parts of an anti-aging agent, 1-3 parts of a tackifying resin, 2.5-4.7 parts of insoluble sulfur, 0.8-1.5 parts of an accelerator and 0.1-0.5 part of a super vulcanization assistant.
The high bio-based elastomer tire apex rubber composition provided by the invention is based on natural rubber, so that the bio-based content in the rubber composition is improved, and the dependence on fossil fuel is reduced. Meanwhile, the addition of the bio-based carbon black reduces the use cost of the carbon black, reduces the environmental pollution, saves fossil resources and realizes the sustainable development of the rubber industry. The problems of poor physical properties, low sulfur speed and low efficiency caused by the bio-based carbon black can be perfectly solved by using the super vulcanization assistant, and the vulcanization efficiency and the vulcanization quality are improved. Meanwhile, the addition of the porous three-phase alloy enables the rubber composition to have low heat generation, high heat conduction and excellent heat resistance, and the performance of the rubber product is improved. The raw materials in the composition are matched with each other, so that the rubber composition has remarkable technical effects in improving rubber performance and enhancing environmental friendliness.
The high bio-based elastomer tire apex rubber composition realizes remarkable technical effects through a carefully designed formula and process, and is specifically discussed as follows:
The composition is based on natural rubber, which is a large amount of commercial bio-based rubber obtained directly from nature, so that the whole composition has high bio-based content, is beneficial to reducing the dependence on fossil fuel, and meets the requirements of sustainable development and environmental protection. By adding the porous three-phase alloy, the wear resistance of the rubber is obviously improved, the high hardness and wear resistance of the porous three-phase alloy effectively improve the wear resistance of the rubber, and the service life of a rubber product is prolonged.
The addition of the rice husk ash white carbon black not only improves the hardness and the wear resistance of the rubber, but also obviously improves the thermal stability of the rubber, so that the rubber can keep stable size and performance in a high-temperature environment. The addition of the silane coupling agent and the activating agent improves the processability of the rubber, so that the rubber is easier to operate in the mixing and forming process, simultaneously, the combination of the filler and the rubber base material is enhanced, and the mechanical property of the rubber is improved.
The addition of the anti-aging agent effectively delays the aging process of the rubber, prolongs the service life of the rubber, inhibits oxidation reaction by capturing free radicals, and reduces the aging phenomenon of the rubber caused by ultraviolet irradiation or high temperature. The addition of tackifying resins improves the adhesion of the rubber, making it more excellent in bonding with other materials, which is important for application scenarios where high adhesion properties are required.
The combined use of the insoluble sulfur, the accelerator and the super vulcanization aid optimizes the vulcanization process of the rubber, improves the vulcanization efficiency and the vulcanization quality, and is favorable for forming a more uniform and stable cross-linked structure in the vulcanization process of the rubber, thereby improving the comprehensive performance of the rubber.
In addition, the porous three-phase alloy, the rice husk ash white carbon black and other materials used in the rubber composition have better environmental friendliness, and the rice husk ash white carbon black serving as a bio-based carbon black can be hardly dissolved in soil, so that the environmental pollution is reduced.
Through reasonable proportioning and optimized formula, the rubber composition not only has excellent basic performance on rubber products, but also can be adjusted according to specific application requirements, and meets the performance requirements of different fields. In a word, the high bio-based elastomer tire apex rubber composition has remarkable technical effects in the aspects of improving rubber performance, enhancing environmental friendliness, promoting sustainable development and the like.
Typically, but not limited to, the rubber composition may comprise 100 parts of natural rubber, 5, 10, 15 or 20 parts of porous three-phase alloy, 20, 25, 30, 35 or 40 parts of rice husk-ash carbon black, 1,2,3 or 4 parts of silane coupling agent, 3,4,5 or 6 parts of activator, 2,3,4,5 or 6 parts of age inhibitor, 1,2 or 3 parts of tackifying resin, 0.2, 3.0, 4.0 or 4.7 parts of insoluble sulfur, 0.8, 1.2 or 1.5 parts of accelerator, and 0.1, 2, 3.0, 0.4 or 4.5 parts of super-vulcanizing aid.
Further, the super vulcanization aid is a eutectic solvent.
The super vulcanization assistant is mainly prepared from zinc chloride, choline chloride and thiourea according to a molar ratio of 1-3:1-3:3-6.
The eutectic solvent is prepared by mixing zinc chloride, choline chloride and thiourea according to a certain proportion, and forming a liquid molten state at a temperature lower than the melting point of each individual substance, wherein the melting point of the obtained eutectic solvent is lower than the melting point of each component.
Typically, but not by way of limitation, the molar ratio of zinc chloride, choline chloride and thiourea may be 1:1:3, 1:2:4, 1:3:6 or 3:3:6, or any combination of ratios in the range of 1-3:1-3:3-6.
Further, the specific surface area of the rice hull ash white carbon black is 165-240 m 2/g, and the particle size is 0.8-7.8 mu m.
Typically, but not by way of limitation, the rice hull ash carbon black may have a specific surface area of 165 m2/g、170 m2/g、180 m2/g、190 m2/g、200 m2/g、210 m2/g、220 m2/g、230 m2/g or 240 m 2/g, or any value within the range of 165 m 2/g ~240 m2/g, and the rice hull ash carbon black may have a particle size of 0.8 μm, 1.0 μm, 1.5 μm, 2.0 μm, 3.0 μm, 4.0 μm, 5.0 μm, 6.0 μm, or 7.8 μm, or any value within the range of 0.8 μm to 7.8 μm.
The brand of the silane coupling agent comprises at least one of TESPT, si75, OTES and Si 747.
The activator comprises stearic acid and/or zinc oxide.
The brand of the anti-aging agent comprises at least one of anti-aging agent 4020, anti-aging agent RD and anti-aging agent 4010 NA.
The tackifying resin comprises at least one of a tertiary butyl phenol aldehyde resin, an alkyl phenol aldehyde resin, and a petroleum resin.
Preferably, the petroleum resin comprises a C5 and/or C9 designation.
The brand of the accelerator comprises at least one of accelerator NS, accelerator CZ and accelerator DZ.
The fourth aspect of the invention provides a high bio-based elastomer tire apex rubber, which is obtained by mixing the high bio-based elastomer tire apex rubber composition in the main third aspect.
The high-biobased elastomer tire apex rubber provided by the invention has the advantages of the rubber composition, so that the prepared apex rubber is better in performance and more environment-friendly, meets the performance requirements of different fields, and promotes the development of the tire industry.
Further, the mixing method comprises the following steps:
mixing natural rubber, a porous three-phase alloy material, rice hull ash white carbon black, a silane coupling agent, an anti-aging agent and tackifying resin, and performing one-stage mixing to obtain first masterbatch;
then carrying out two-stage mixing on the first masterbatch to obtain a second masterbatch;
And finally adding insoluble sulfur, an accelerator and a super vulcanization assistant into the second masterbatch, mixing, and then carrying out three-stage mixing to obtain the high bio-based elastomer tire apex rubber.
Further, the one-stage mixing comprises mixing for 30-50 s, lifting bolt and pressing bolt mixing for 20-30 s according to sequence, and then lifting bolt and pressing bolt mixing to 140-155 ℃ rubber discharge.
The two-stage mixing comprises mixing for 30-50 s, lifting bolts and pressing bolts for mixing for 20-30 s according to sequence, and then lifting bolts and pressing bolts for mixing to 135-145 ℃ for rubber discharge.
The three-stage mixing comprises mixing for 30-50 s, lifting bolts and pressing bolts for mixing for 20-30 s according to sequence, and then lifting bolts and pressing bolts for mixing to 95-105 ℃ rubber discharge.
Typically, but not by way of limitation, the temperature and time of the one-stage mixing process may be such that the initial mixing stage may last for 30s, 35s, 40s or 50s, followed by a plug-extracting, plug-pressing mixing stage which may last for 20s, 25s or 30s. After the plug extraction and pressing mixing is completed, mixing is continued until the temperature of the rubber reaches 140 ℃, 143 ℃, 145 ℃ or 155 ℃ to discharge the rubber.
Typically, but not by way of limitation, the temperature and time of the two-stage mixing process may be such that the initial mixing stage may last for 30s, 35s, 40s or 50s, followed by a plug-extracting, plug-pressing mixing stage which may last for 20s, 25s or 30s. After the bolt lifting and pressing mixing is completed, mixing is continued until the temperature of the rubber reaches 135 ℃, 138 ℃, 141 ℃ or 145 ℃ to discharge the rubber.
Typically, but not by way of limitation, the temperature and time of the three-stage mixing process may be such that the initial mixing stage may last for 30s, 35s, 40s or 50s, followed by a plug-extracting, plug-pressing mixing stage which may last for 20s, 25s or 30s. After the bolt lifting and pressing mixing is finished, mixing is continued until the temperature of the rubber reaches 95 ℃, 98 ℃, 101 ℃ or 105 ℃ and rubber is discharged.
Some embodiments of the present invention will be described in detail below with reference to examples. The following embodiments and features of the embodiments may be combined with each other without conflict.
The raw materials used in examples and comparative examples are shown in table 1 below.
TABLE 1
Example 1
The embodiment provides a porous three-phase alloy, and the preparation method comprises the following steps:
In a jet system, natural ore powder and process water are uniformly mixed by a powder injection technology, and the concentration of natural ore powder suspension is controlled to be 20 wt%. And spraying the natural ore powder suspension into a carbon black reaction furnace by a jet system, wherein the spraying flow is 5000kg/h, the mass ratio of carbon black to natural ore powder is controlled to be 8:2, and the temperature in the carbon black reaction furnace is set to be 1000 ℃. The carbon black reacts with the natural ore powder to generate an aluminum-silicon-carbon structure, and the porous three-phase alloy is obtained through aggregation to form an aluminum-silicon-carbon aggregate.
Example 2
The embodiment provides a porous three-phase alloy, and the preparation method comprises the following steps:
In a jet system, natural ore powder and process water are uniformly mixed by a powder injection technology, and the concentration of natural ore powder suspension is controlled to be 15 wt%. And spraying the natural ore powder suspension into a carbon black reaction furnace by a jet system, wherein the spraying flow is 6000kg/h, the mass ratio of carbon black to natural ore powder is controlled to be 8:2, and the temperature in the carbon black reaction furnace is set to be 1200 ℃. The carbon black reacts with the natural ore powder to generate an aluminum-silicon-carbon structure, and the porous three-phase alloy is obtained through aggregation to form an aluminum-silicon-carbon aggregate.
Example 3
The embodiment provides a porous three-phase alloy, and the preparation method comprises the following steps:
In a jet system, natural ore powder and process water are uniformly mixed by a powder injection technology, and the concentration of natural ore powder suspension is controlled to be 25 wt%. And spraying the natural ore powder suspension into a carbon black reaction furnace by a jet system, wherein the spraying flow is 4000kg/h, the mass ratio of carbon black to natural ore powder is controlled to be 8:2, and the temperature in the carbon black reaction furnace is set to be 1500 ℃. The carbon black reacts with the natural ore powder to generate an aluminum-silicon-carbon structure, and the porous three-phase alloy is obtained through aggregation to form an aluminum-silicon-carbon aggregate.
Example 4
The embodiment provides a porous three-phase alloy, which is different from the embodiment in that the mass ratio of carbon black to natural ore powder is 7:3, and the rest raw materials and steps are the same as those of the embodiment 1, and are not repeated here.
Example 5
The embodiment provides a porous three-phase alloy, which is different from the embodiment in that the mass ratio of carbon black to natural ore powder is 9:1, and the rest raw materials and steps are the same as those of the embodiment 1, and are not repeated here.
Example 6
The embodiment provides a porous three-phase alloy, which is different from the embodiment in that the mass ratio of carbon black to natural ore powder is 6:4, and the rest raw materials and steps are the same as those of the embodiment 1, and are not repeated here.
Example 7
The embodiment provides a porous three-phase alloy, which is different from the embodiment in that the mass ratio of carbon black to natural ore powder is 5:5, and the rest raw materials and steps are the same as those of the embodiment 1, and are not repeated here.
Example 8
The embodiment provides a porous three-phase alloy, which is different from the embodiment in that the mass ratio of carbon black to natural ore powder is 2:8, and the rest raw materials and steps are the same as those of the embodiment 1, and are not repeated here.
Test example 1
The porous three-phase alloy obtained in examples 1 to 8 was subjected to performance test, specifically including measurement of thermal conductivity and thermal expansion coefficient.
The thermal conductivity was measured as specified in GB/T8722-2019 and the thermal expansion was measured as specified in GB/T9966.16-2021.
The results obtained are shown in Table 2 below.
TABLE 2
As can be seen from Table 2, the porous three-phase alloy has a thermal conductivity of 0.223W/mK to 0.288W/mK and a thermal expansion coefficient of 0.11/°C to 0.18/°C.
Characterization example 1
The porous three-phase alloy obtained in example 1 was subjected to scanning electron microscopy, and the obtained pictures are shown in fig. 1,2 and 3. As can be seen from fig. 1-3, the carbon black is organically complexed with the porous ore fines.
Examples 9 to 13 and comparative examples 1 to 2
These examples provide a high biobased elastomer-tire apex rubber made using a high biobased elastomer-tire apex rubber composition formulated as shown in table 3 below. The porous three-phase alloy used therein was the porous three-phase alloy provided in example 4.
TABLE 3 Table 3
Note that "/" indicates that no such material was added.
The super vulcanization aid DES in the above examples 9-13 is zinc chloride, and the molar ratio of choline chloride to thiourea is 1:1:4, and the super vulcanization aid DES is obtained after eutectic melting.
Example 14
The present embodiment provides a high bio-based elastomer tire apex rubber, wherein the formulation of the high bio-based elastomer tire apex rubber composition is different from that of embodiment 9 in that the super vulcanization aid DES is zinc chloride, and the co-melted choline chloride and thiourea are obtained after the co-melted choline chloride and thiourea are co-melted according to a molar ratio of 1:1:3, and other raw materials and methods are the same as those of embodiment 9, and are not repeated herein.
Example 15
The present embodiment provides a high bio-based elastomer tire apex rubber, wherein the formulation of the high bio-based elastomer tire apex rubber composition is different from that of embodiment 9 in that the super vulcanization aid DES is zinc chloride, and the co-melted choline chloride and thiourea are obtained after the co-melted choline chloride and thiourea are co-melted according to a molar ratio of 1:1:2, and other raw materials and methods are the same as those of embodiment 9, and are not repeated herein.
Example 16
The present embodiment provides a high bio-based elastomer tire apex rubber, wherein the formulation of the high bio-based elastomer tire apex rubber composition is different from that of embodiment 9 in that the super vulcanization aid DES is zinc chloride, and the co-melted choline chloride and thiourea are obtained after the co-melted choline chloride and thiourea are co-melted according to a molar ratio of 1:1:1, and other raw materials and methods are the same as those of embodiment 9, and are not repeated herein.
Comparative example 3
This comparative example provides a high bio-based elastomer bead apex rubber, wherein the formulation of the high bio-based elastomer bead apex rubber composition is different from example 9 in that the porous three-phase alloy is replaced with the same amount of natural ore powder, and other materials and methods are the same as in example 9, and are not described herein.
Comparative example 4
This comparative example provides a high bio-based elastomer bead apex rubber, wherein the formulation of the high bio-based elastomer bead apex rubber composition is different from example 9 in that no porous three-phase alloy is added, and other materials and methods are the same as example 9, and are not described here again.
Examples 9 to 16 and comparative examples 1 to 4 were prepared according to the following preparation method:
And (3) starting an internal mixer, setting the rotating speed to be 45-55 revolutions, adding natural rubber, porous three-phase alloy, rice hull ash white carbon (or carbon black), a silane coupling agent, an activating agent, an anti-aging agent and tackifying resin according to a formula, mixing for 40 seconds, lifting bolts, pressing bolts, mixing for 25 seconds, lifting bolts, pressing bolts, mixing to 147 ℃ and discharging rubber to obtain the first master batch.
And starting the internal mixer, setting the rotating speed to be 25-35 revolutions, adding the first internal mixer, mixing for 40 seconds, lifting bolts, pressing bolts, mixing for 25 seconds, lifting bolts, pressing bolts, mixing to 140 ℃ and discharging rubber to obtain the second internal mixer.
And (3) starting the internal mixer, setting the rotating speed to be 25-35 revolutions, adding the second master batch, insoluble sulfur, the accelerator and the super vulcanization aid DES, mixing for 40 seconds, lifting bolts, pressing bolts, mixing for 25 seconds, lifting bolts, pressing bolts, mixing to 100 ℃ and discharging rubber to obtain the high bio-based elastomer triangular rubber.
Test example 2
In the preparation of the apex rubbers of examples 9-16 and comparative examples 1-4, the compounds were tested to include low mooney value ML, high mooney value MH, ts2 time, 10% cure time TC10, 30% cure time TC30, 60% cure time TC60, 90% cure time TC90, and R97 index.
The test conditions were 151 ℃ x 60min.
The data obtained are shown in table 4 below.
TABLE 4 Table 4
It can be seen from table 4 that the sulfur rate problem can be effectively solved by using the super vulcanization aid DES without affecting the MH value, as can be seen from example 9 and comparative example 1. It can be seen from example 9 and comparative example 3 that the MH using the natural ore powder was low.
Test example 3
The apex rubbers obtained in examples 9 to 16 and comparative examples 1 to 4 were subjected to physical properties and dynamic mechanical properties testing.
Specifically included are 300% tensile stress M300, tensile strength TB, elongation at break E.B% and tangent tan delta/60℃of the loss angle at 60 ℃.
The 300% elongation stress M300 was determined as specified in GB/T528-1998, the tensile strength TB was determined as specified in GB/T528-1998, the elongation at break E.B% was determined as specified in GB/T528-1998, and the loss tangent tan delta at 60℃and 60℃were determined at a frequency of 20Hz and a strain of 10% + -2.
The data obtained from the test are shown in table 5 below.
TABLE 5
As can be seen from Table 5, the ore powder is adopted to achieve low stretching and high heat generation, the porous three-phase alloy is removed, and the sizing material is subjected to stretching reduction.
Test example 4
The apex rubbers obtained in examples 9 to 16 and comparative examples 1 to 4 were subjected to thermal conductivity test.
The thermal conductivity lambda and the thermal diffusion coefficient alpha are specified in GB T11205-2009, wherein the thermal conductivity lambda is specified in GB T11205-2009, and the thermal diffusion coefficient alpha is specified in GB T11205-2009.
The data obtained from the test are shown in table 6 below.
TABLE 6
As can be seen from table 6, the same thermal conductivity as carbon black can be achieved with the use of the porous three-term alloy, and the use of the rice hull ash carbon black reduces the thermal conductivity.
It should be noted that the above embodiments are merely for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the above embodiments, it should be understood by those skilled in the art that the technical solution described in the above embodiments may be modified or some or all of the technical features may be equivalently replaced, and these modifications or substitutions do not make the essence of the corresponding technical solution deviate from the scope of the technical solution of the embodiments of the present invention.
Claims (8)
1. An application of porous three-phase alloy in preparing high bio-based elastomer tire apex rubber composition;
The porous three-phase alloy is obtained by high-temperature jet flow of carbon black and natural ore powder;
the mass content of silicon dioxide in the natural ore powder is 40-60%, and the mass content of aluminum oxide is 30-40%;
the natural ore powder has a rich micropore structure, the specific surface area is 30-70 m 2/g, the pore volume is 0.20-0.40 cm 3/g, the pore number is 1-3 hundred million/g, and the D50 particle size is 0.25-5 mu m;
the mass ratio of the carbon black to the natural ore powder is 5-9:1-5;
The high temperature jet process includes:
spraying natural ore powder suspension mixed by a jet system into a carbon black reaction furnace, reacting carbon black and natural ore powder to generate an aluminum-silicon-carbon structure, and forming an aluminum-silicon-carbon aggregate through aggregation to obtain the porous three-phase alloy;
The concentration of the natural ore powder suspension is 15-25wt%;
The spraying flow of the natural ore powder suspension is 4000-6000 kg/h;
the reaction temperature is 1000-1500 ℃.
2. The use of claim 1, wherein the carbon black comprises at least one of the designations N134, N220, N234, N330, N375, and N550.
3. The high bio-based elastomer tire apex rubber composition is characterized by comprising the following components in parts by weight:
100 parts of natural rubber, 5-20 parts of the porous three-phase alloy according to claim 1 or 2, 20-40 parts of rice hull ash white carbon black, 1-4 parts of a silane coupling agent, 3-6 parts of an activating agent, 2-6 parts of an anti-aging agent, 1-3 parts of tackifying resin, 2.5-4.7 parts of insoluble sulfur, 0.8-1.5 parts of an accelerator and 0.1-0.5 part of a super vulcanization assistant.
4. The high biobased elastomer tire apex rubber composition of claim 3, wherein the super vulcanization aid is a eutectic solvent;
the super vulcanization assistant is prepared from zinc chloride, choline chloride and thiourea according to a molar ratio of 1-3:1-3:3-6.
5. The high biobased elastomer tire apex rubber composition according to claim 3, wherein the rice hull ash carbon black has a specific surface area of 165-240 m 2/g and a particle size of 0.8-7.8 μm;
the brand of the silane coupling agent comprises at least one of TESPT, si75 and Si 747;
The activator comprises stearic acid and/or zinc oxide;
the brand of the anti-aging agent comprises at least one of anti-aging agent 4020, anti-aging agent RD and anti-aging agent 4010 NA;
The tackifying resin comprises at least one of tertiary butyl phenol aldehyde resin, alkyl phenol aldehyde resin and petroleum resin;
the petroleum resin comprises C5 and/or C9;
the brand of the accelerator comprises at least one of accelerator NS, accelerator CZ and accelerator DZ.
6. The high bio-based elastomer tire apex rubber is characterized in that the apex rubber is obtained by mixing the high bio-based elastomer tire apex rubber composition according to any one of claims 3-5.
7. The high biobased elastomer tire apex rubber of claim 6, wherein the compounding process comprises the steps of:
Mixing natural rubber, a porous three-phase alloy material, rice hull ash white carbon black, a silane coupling agent, an activating agent, an anti-aging agent and tackifying resin, and performing one-stage mixing to obtain first masterbatch;
then carrying out two-stage mixing on the first masterbatch to obtain a second masterbatch;
And finally adding insoluble sulfur, an accelerator and a super vulcanization assistant into the second masterbatch, mixing, and then carrying out three-stage mixing to obtain the high bio-based elastomer tire apex rubber.
8. The high biobased elastomer tire apex rubber of claim 7, wherein the one-stage mixing comprises mixing for 30-50 s, lifting bolt pressing mixing for 20-30 s, and lifting bolt pressing mixing to 140-155 ℃ for rubber discharge;
the two-stage mixing comprises mixing for 30-50 s, lifting bolts and pressing bolts for mixing for 20-30 s according to the sequence, and then lifting bolts and pressing bolts for mixing to 135-145 ℃ for rubber discharge;
The three-stage mixing comprises mixing for 30-50 s, lifting bolts and pressing bolts for mixing for 20-30 s according to sequence, and then lifting bolts and pressing bolts for mixing to 95-105 ℃ rubber discharge.
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| FR2997409B1 (en) * | 2012-10-30 | 2015-01-23 | Michelin & Cie | PNEUMATIC IMPROVED ICE ADHESION |
| CN106674658A (en) * | 2016-12-08 | 2017-05-17 | 赛轮金宇集团股份有限公司 | Tire tread rubber produced by utilizing renewable rice husk source white carbon black and preparation process of tire tread rubber |
| CN107876730B (en) * | 2017-11-13 | 2019-09-03 | 宁波海瑞时新材料有限公司 | The light metal-based composite material of wear-resistant material, local enhancement and preparation method |
| WO2020049815A1 (en) * | 2018-09-07 | 2020-03-12 | 富山住友電工株式会社 | Metal porous body, fuel cell, and production method for metal porous body |
| CN111607134A (en) * | 2020-06-01 | 2020-09-01 | 中策橡胶集团有限公司 | All-steel radial tire bead filler rubber composition with low heat generation and high stretching stability, preparation method thereof and tire |
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| CN104703944A (en) * | 2012-10-08 | 2015-06-10 | 陶氏环球技术有限公司 | Improved porous bodies comprised of mullite and methods of forming them |
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