Application of heterocycle-containing polyhydrazide compound in preparation of auxiliary agent for reducing rolling resistance of tire

Abstract

The invention relates to the technical field of preparation of rubber tire auxiliaries, in particular to application of a heterocyclic polyhydrazide compound in preparation of an auxiliary for reducing the rolling resistance of a tire. The additive is 3-6-membered heterocyclic polyhydrazide containing N / O / S, 2-5-C (O)-NH-NHH groups are introduced to the same skeleton, and the groups can be directly linked or connected through alkyl / aryl; the compound is prepared by refluxing heterocyclic polycarboxylic acid ester and hydrazine hydrate in alcohol. 0.01-10 phr (preferably 0.2-1.0 phr) of the compound is added into a formula of NR / SBR / BR and carbon black or white carbon black, and the compound is prepared by three-stage mixing, so that tan delta at-60 DEG C can be remarkably reduced (10-40% lower than that of a contrast group), meanwhile, wet grabbing and wear resistance are kept, the influence on Mooney viscosity and vulcanization is small, and the low-rolling-resistance requirement of parts such as treads is met.

Description

Technical Field

[0001] This invention relates to the field of rubber tire additives preparation technology, and in particular to the application of heterocyclic polyhydrazide compounds in the preparation of additives that reduce tire rolling resistance. Background Technology

[0002] Tire rolling resistance (RR) is closely related to vehicle fuel economy, carbon emissions, and overall vehicle energy efficiency. The core of materials and formulation approaches to reduce rolling resistance lies in minimizing energy loss (hysteresis loss) during cyclic deformation of the rubber compound. In formulation evaluation, the industry widely uses the dynamic mechanical loss factor tanδ as an indicator: a higher tanδ at 0°C is beneficial for wet grip performance, while a lower tanδ at 60–70°C generally indicates lower rolling resistance. This point has been clearly explained and applied in relevant Chinese patent literature on silicone-containing rubber compositions. Such literature also emphasizes the importance of reducing high-temperature tanδ without significantly sacrificing abrasion resistance and fracture resistance (e.g., by controlling filler particle size, dosage, and interfacial chemistry).

[0003] To achieve the balance between low rolling resistance and high wear resistance, the industry primarily employs the following technical approaches: ① highly dispersed silica (SiO2) / silane coupling systems; ② optimizing the silica system and its surface chemistry; ③ introducing low-molecular-weight functionalized additives into the rubber compound to enhance the chemical / physical interaction between the polymer and filler. The first type of technology is represented by silica-containing systems, which typically utilize silane coupling agents to improve the interfacial adhesion between SiO2 and the polymer and suppress the high hysteresis caused by the three-dimensional network of the filler. However, relying solely on silica-containing systems often limits the formulation processing window, vulcanization kinetics, and compatibility costs, and balancing the overall performance under different road surfaces and working conditions remains challenging.

[0004] For carbon black reinforcement systems, a key approach in recent years has been to introduce "bridging" small-molecule additives that can interact with the active sites on the carbon black surface and form interactions with rubber segments / vulcanization networks. This aims to reduce the energy loss from carbon black agglomeration and friction between the carbon black and rubber / polymer ends, thereby reducing hysteresis losses. One of the earliest publicly disclosed representative technologies abroad is the use of "hydrazide" low-molecular-weight additives: EP0909788B1 proposes incorporating 0.05–20 parts (preferably 0.05–5 parts for the tread portion) of an hydrazide compound into rubber compounds primarily composed of natural rubber / diene-based synthetic rubber, combined with 30–70 parts of carbon black, to effectively reduce heat generation and rolling resistance. Chinese patent CN101842393A proposes a scheme for "direct modification of natural rubber raw materials with acylhydrazine compounds having polar groups". This involves reacting acylhydrazine compounds with polar groups with natural rubber (including natural latex curds / cup gum, etc.) to introduce polar sites near the main molecular chain, which significantly improves the affinity and dispersion of fillers such as carbon black / silica, thereby achieving comprehensive improvement in low heat generation (low loss coefficient), wear resistance and fracture performance.

[0005] Existing acylhydrazine-based rolling resistance reducers mainly focus on the structural paradigm of "aromatic ring, single acylhydrazine fragment" (e.g., EP0909788B1), or compounds that, while emphasizing "multipolar aromatic groups," are still dominated by "monoacylhydrazine groups" (e.g., CN109563316A). When these molecules interact with carbon black / SiO2, they typically provide a "single-point" acylhydrazine-surface / rubber interaction site. Although the interaction strength can be enhanced by increasing the number of polar groups, their ability to "achieve multi-point anchoring and synergistic interfacial network reconstruction at the microscale" remains limited. Summary of the Invention

[0006] To address the aforementioned technical problems, the present invention aims to provide an application of heterocyclic polyhydrazide compounds in the preparation of additives for reducing tire rolling resistance. This additive improves the dispersion and interfacial network of fillers such as carbon black / fumed silica, significantly reduces the loss factor of the rubber compound at 60°C, and decreases tire rolling resistance, while also considering wet grip, abrasion resistance, and processing safety.

[0007] To achieve the above objectives, the present invention adopts the following technical solution:

[0008] Heterocyclic polyhydrazide compounds are used in the preparation of additives to reduce tire rolling resistance, wherein the heterocyclic polyhydrazide compounds satisfy the following:

[0009] c1) The molecule contains a 3-6 member heterocyclic skeleton containing heteroatoms, wherein the heteroatoms are one or more of N, O, and S;

[0010] c2) The heterocycle has a carboxylic acid hydrazide group -C(O)-NH-NH2 attached to the carbon positions of the 2nd to 5th rings, and each hydrazide group is directly bonded to the heterocycle, or each hydrazide group is connected to the heterocycle through an alkyl or aromatic group.

[0011] Preferably, the heterocycle is selected from one or more of furan, pyridine, pyrazole, imidazole, thiophene, and oxazole.

[0012] Further preferred, the heterocyclic polyhydrazide compound is selected from one or more compounds with the following structural formulas:

[0013]

[0014] Where X = O, S or NR, and R = H, C1-C10 alkyl or aryl.

[0015] Furthermore, the present invention also provides a rubber composition for reducing tire rolling resistance, the rubber composition comprising a heterocyclic polyhydrazide compound, said heterocyclic polyhydrazide compound satisfying:

[0016] c1) The molecule contains a 3-6 member heterocyclic skeleton containing heteroatoms, wherein the heteroatoms are one or more of N, O, and S;

[0017] c2) The heterocycle has a carboxylic acid hydrazide group -C(O)-NH-NH2 attached to the carbon positions of the 2nd to 5th rings, and each hydrazide group is directly bonded to the heterocycle, or each hydrazide group is connected to the heterocycle through an alkyl or aromatic group.

[0018] Preferably, the heterocycle is selected from one or more of furan, pyridine, pyrazole, imidazole, thiophene, and oxazole.

[0019] Further preferred, the heterocyclic polyhydrazide compound is selected from one or more compounds with the following structural formulas:

[0020]

[0021] Where X = O, S or NR, and R = H, C1-C10 alkyl or aryl.

[0022] The specific synthetic steps of the heterocyclic polyhydrazide compound synthesis method of this invention are as follows: The carboxylic acid ester R... 1 (COOR 2 ) 2-5 Dissolve in solvent alcohol, stir until clear, add hydrazine hydrate, heat to the reaction temperature, reflux under condensation for the corresponding reaction time; cool, filter, wash with solvent alcohol, and dry to obtain the corresponding hydrazide.

[0023] Preferably, the carboxylic acid ester R 1 (COOR 2 ) 2-5R is one or more of the corresponding carboxylic acid esters of acylhydrazide. 1 (COOR 2 ) 2-5 Chinese R 1 It is a heterocyclic ring, R 2 It is a C1-C10 alkyl or aryl group.

[0024] Preferably, the carboxylic acid ester reaction concentration is 0.01-10M.

[0025] Preferably, the solvent alcohol is one or more of C1-C10 alkyl alcohols or arylphenols.

[0026] Preferably, the concentration of hydrazine hydrate is >50%, and the molar ratio of hydrazine hydrate to carboxylic acid ester is: R1(COOR2)2-5 / hydrazine hydrate = 1:2-50.

[0027] Preferably, the reaction temperature is 40-200℃.

[0028] Preferably, the reaction time is 0.1-72 hours.

[0029] Preferably, the cooling is reduced to 25°C to -40°C.

[0030] Preferably, the rubber composition is prepared by mixing raw materials comprising, by weight:

[0031] A) 100 phr of unsaturated raw rubber containing diene groups;

[0032] B) Packing material 30–150 phr;

[0033] C) Rolling resistance reducing agent 0.01–10.0 phr, wherein the agent is a heterocyclic polyhydrazide compound; preferably 0.2–1.0 phr.

[0034] Preferably, the diene-containing unsaturated raw rubber is selected from one or more rubber components selected from natural rubber (NR), isoprene rubber (IR), styrene-butadiene rubber (SBR), butadiene rubber (BR), butyl rubber (IIR), ethylene propylene diene monomer (EPDM), acrylonitrile-butadiene rubber (NBR), styrene-isoprene-butadiene rubber (SIBR), and chloroprene rubber (CR).

[0035] Further, the filler is selected from one or more of carbon black, silica, carbon nanotubes, graphene, graphene oxide, carbon fiber, and nanocellulose.

[0036] More preferably, the filler is selected from one or more of carbon black, silica, carbon nanotubes, graphene, graphene oxide, carbon fiber, and nanocellulose. More preferably, the plasticizer is one or more of dioctyl phthalate, dibutyl phthalate, dioctyl adipate, trioctyl trimellitate, epoxidized soybean oil, paraffin oil, naphthenic oil, and aromatic oil. More preferably, the resin is one or more of phenolic resin, petroleum resin, coumarone resin, rosin resin, terpene resin, polyurethane resin, epoxy resin, and resorcinol-formaldehyde resin. More preferably, the vulcanizing agent is one or more of sulfur, dicumyl peroxide, and bismaleimide. More preferably, the rubber product is a tire, a sealing ring, or a shoe.

[0037] The BET specific surface area of ​​the silica in the rubber composition of the present invention is 50-250 m². 2 / g, preferably 80-210m 2 / g, more preferably 100-190m 2 / g. By adjusting the BET specific surface area within this range, superior dispersibility, anti-slip properties, and abrasion resistance can be obtained. The BET specific surface area of ​​silica can be determined according to JIS Z8830. The BET method is a method that involves adsorbing nitrogen gas of known area onto the surface of sample powder particles and determining the specific surface area of ​​the sample powder particles based on the amount of adsorption. The specific surface area obtained using this method is called the "BET specific surface area".

[0038] The silica used in the rubber composition of this invention refers to a silica-silicic acid-based filler material, and not just silica in the narrow sense. It can be appropriately selected from existing materials used as reinforcing fillers. Examples include wet silica (hydrated silica) and dry silica (anhydrous silica). Among these, wet silica is preferred from the viewpoint of further improving processability, anti-slip properties, and abrasion resistance. One type can be used alone, or two or more types can be used in combination. Furthermore, to further improve affinity with the rubber components, a treatment layer formed by a surface treatment agent is preferably formed on the surface.

[0039] Preferably, the silica is precipitated silica, with a nitrogen adsorption surface area (NSA) of 120-180 m². 2 One or more of the following: / g.

[0040] From the viewpoint of further improving the processability, wet skid resistance, and abrasion resistance of the obtained rubber composition, the average secondary particle size of silica is preferably 0.04–3 μm, more preferably 0.1–1 μm, and even more preferably 0.2–0.7 μm. The average secondary particle size of silica can be determined using laser diffraction and scattering, and is the particle size at which the cumulative reference 50% of the particle size distribution (volume-based cumulative 50% particle size), i.e., D50 (median diameter), is obtained using laser diffraction and scattering. This volume-based cumulative 50% particle size (D50) is the particle size at the point where the cumulative value reaches 50% in a cumulative curve where the total volume is set to 100%, based on the particle size distribution determined by volume.

[0041] The amount of silica in the rubber composition of the present invention is preferably 20 to 120 parts by weight, more preferably 25 to 100 parts by weight, and even more preferably 30 to 90 parts by weight relative to 100 parts by weight of the rubber component. By setting it within this range, superior wet skid resistance and wear resistance can be obtained.

[0042] From the viewpoint of further improving wear resistance, carbon black particles can be further incorporated into the rubber composition of the present invention.

[0043] From the viewpoint of further improving dispersibility, mechanical strength, and hardness, the BET specific surface area of ​​the aforementioned carbon black particles is preferably 20–160 m². 2 / g, more preferably 40-130m 2 / g, further preferably 50-120m 2 / g. The BET specific surface area of ​​carbon black particles can be determined according to JIS Z8830. The so-called BET method is a method of determining the specific surface area of ​​the sample powder particles by adsorbing nitrogen gas of known area on the surface of the sample powder particles, and determining the specific surface area of ​​the sample powder particles based on the amount of adsorption. The specific surface area obtained by this method is called "BET specific surface area".

[0044] From the viewpoint of further improving dispersibility, mechanical strength, and hardness, the average secondary particle size of the aforementioned carbon black particles is preferably 0.05–3 μm, more preferably 0.1–1.0 μm, and even more preferably 0.2–0.9 μm. The average secondary particle size of the carbon black particles can be determined using laser diffraction and scattering, and is the particle size at which the cumulative reference 50% of the particle size distribution (volume-based cumulative 50% particle size), i.e., D50 (median diameter), is calculated using a volume-based method. This volume-based cumulative 50% particle size (D50) is the particle size at the point where the cumulative value reaches 50% in a cumulative curve where the total volume is set to 100%.

[0045] Examples of carbon blacks constituting the aforementioned carbon black particles include furnace black, thermal black, acetylene black, and Ketjen black. Among these, furnace black is preferred from the viewpoint of further improving the mechanical strength of the rubber composition. One type can be used alone, or two or more types can be used in combination. Furthermore, to further improve the affinity with the rubber components, an organic treatment can be applied to the surface. Preferably, the carbon black described in this invention is one of N134, N220, N234, and N375.

[0046] Regarding the amount of carbon black particles incorporated into the rubber composition of the present invention, it is preferably 2 to 50 parts by mass relative to 100 parts by mass of the rubber component, more preferably 3 to 30 parts by mass, and even more preferably 10 to 20 parts by mass.

[0047] Furthermore, the raw materials for the rubber products of the present invention also include silane coupling agents. Examples of silane coupling agents include sulfide-based, polysulfide-based, thioester-based, thiol-based, olefin-based, epoxy-based, amino-based, and alkyl-based silane coupling agents. These can be used individually or in combination of two or more. Among these, sulfide-based silane coupling agents and amino-based silane coupling agents are preferred.

[0048] Examples of silane coupling agents based on sulfide systems include: bis(3-triethoxysilylpropyl)tetrasulfide, bis(3-trimethoxysilylpropyl)tetrasulfide, bis(3-methyldimethoxysilylpropyl)tetrasulfide, bis(2-triethoxysilylethyl)tetrasulfide, bis(3-triethoxysilylpropyl)disulfide, bis(3-trimethoxysilylpropyl)disulfide, bis(3-methyldimethoxysilylpropyl)disulfide, bis(2-triethoxysilylethyl)disulfide, bis(3-triethoxysilylpropyl)trisulfide, bis(3-triethoxysilylpropyl)trisulfide, bis(3-trimethoxysilylpropyl)trisulfide, and bis(3-methyldimethoxysilylpropyl)tetrasulfide. Bis(2-triethoxysilylethyl) trisulfide, bis(3-monoethoxydimethylsilylpropyl) tetrasulfide, bis(3-monoethoxydimethylsilylpropyl) trisulfide, bis(3-monoethoxydimethylsilylpropyl) disulfide, bis(3-monoethoxydimethylsilylpropyl) tetrasulfide, bis(3-monoethoxydimethylsilylpropyl) trisulfide, bis(3-monoethoxydimethylsilylpropyl) disulfide, bis(3-monoethoxydimethylsilylpropyl) disulfide, bis(2-monoethoxydimethylsilylethyl) tetrasulfide, bis(2-monoethoxydimethylsilylethyl) trisulfide, bis(2-monoethoxydimethylsilylethyl) disulfide, etc. Among these, bis(3-triethoxysilylpropyl) tetrasulfide is preferred.

[0049] Examples of thioester-based silane coupling agents include 3-hexanoylthiopropyltriethoxysilane, 3-octanoylthiopropyltriethoxysilane, 3-decanoylthiopropyltriethoxysilane, 3-lauroylthiopropyltriethoxysilane, 2-hexanoylthioethyltriethoxysilane, 2-octanoylthioethyltriethoxysilane, 2-decanoylthioethyltriethoxysilane, and 2-lauroylthio... Ethyltriethoxysilane, 3-hexanoylthiopropyltrimethoxysilane, 3-octanoylthiopropyltrimethoxysilane, 3-decanoylthiopropyltrimethoxysilane, 3-lauroylthiopropyltrimethoxysilane, 2-hexanoylthioethyltrimethoxysilane, 2-octanoylthioethyltrimethoxysilane, 2-decanoylthioethyltrimethoxysilane, 2-lauroylthioethyltrimethoxysilane, etc.

[0050] Examples of thiol-based silane coupling agents include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, and 3-mercaptopropylmethyldimethoxysilane.

[0051] Examples of olefin-based silane coupling agents include dimethoxymethylvinylsilane, vinyltrimethoxysilane, dimethylethoxyvinylsilane, diethoxymethylvinylsilane, triethoxyvinylsilane, vinyltris(2-methoxyethoxy)silane, allyltrimethoxysilane, allyltriethoxysilane, p-styryltrimethoxysilane, 3-(methoxydimethoxydimethylsilyl)propyl acrylate, 3-(trimethoxysilyl)propyl acrylate, 3-[dimethoxy(methyl)silyl]propyl methacrylate, 3-(trimethoxysilyl)propyl methacrylate, 3-[dimethoxy(methyl)silyl]propyl methacrylate, 3-[triethoxysilyl]propyl methacrylate, and 3-[tris(trimethylsiloxy)silyl]propyl methacrylate.

[0052] Examples of epoxy-based silane coupling agents include 3-epoxypropoxypropyl(dimethoxy)methylsilane, 3-epoxypropoxypropyltrimethoxysilane, diethoxy(3-epoxypropoxypropyl)methylsilane, triethoxy(3-epoxypropoxypropyl)silane, and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane.

[0053] Examples of amino-based silane coupling agents include N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-ethoxysilyl-N-(1,3-dimethylbutylene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, and N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane. Among these, 3-aminopropyltriethoxysilane is preferred.

[0054] Examples of alkyl-based silane coupling agents include methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, n-propyltrimethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, cyclohexylmethyldimethoxysilane, n-octyltriethoxysilane, and n-decyltrimethoxysilane.

[0055] Among these silane coupling agents, bis(3-triethoxysilylpropyl)tetrasulfide and 3-aminopropyltriethoxysilane are particularly preferred.

[0056] In addition to the components described above, the rubber composition of the present invention may appropriately incorporate compounding agents commonly used in the rubber industry, such as vulcanizing agents, vulcanization accelerators, anti-aging agents, softeners, plasticizers, anti-scorching agents, anti-ozone agents, foaming agents, and vulcanization retarders. As a vulcanizing agent, organic peroxides or sulfur-based vulcanizing agents may be incorporated. As organic peroxides, they can be combined with, for example, benzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, tert-butylcumyl peroxide, methyl ethyl ketone peroxide, cumene hydroperoxide, 2,5-dimethyl-2,5-di(tert-butylperoxide)hexane, 2,5-dimethyl-2,5-di(benzoylperoxide)hexane, 2,5-dimethyl-2,5-di(tert-butylperoxide)hexyn-3, 1,3-bis(tert-butylperoxidepropyl)benzene, di-tert-butylperoxide diisopropylbenzene, tert-butylperoxidebenzene, 2,4-dichlorobenzoyl peroxide, 1,1-di-tert-butylperoxide-3,3,5-trimethylsiloxane, and 4,4-di-tert-butylperoxyvalerate n-butyl ester. Among these organic peroxides, dicumyl peroxide, tert-butylperoxidebenzene, and di-tert-butylperoxide diisopropylbenzene are preferred. In addition, as a sulfur-based vulcanizing agent, it can be combined with sulfur, morpholine disulfide, etc. Among these sulfur-based vulcanizing agents, sulfur is preferred.

[0057] As a vulcanization accelerator, it can be combined with sulfenamide, thiazole, thiuram, thiourea, guanidine, dithiocarbamate, aldehyde-amine, or aldehyde-amine systems, etc.

[0058] Examples of sulfonamide compounds include CBS (N-cyclohexyl-2-benzothiazolyl sulfonamide), TBBS (N-tert-butyl-2-benzothiazolyl sulfonamide), N,N-dicyclohexyl-2-benzothiazolyl sulfonamide, N-oxodiethylidene-2-benzothiazolyl sulfonamide, and N,N-diisopropyl-2-benzothiazolyl sulfonamide.

[0059] Examples of thiazole derivatives include MBT (2-mercaptobenzothiazole), MBTS (dibenzothiazolium disulfide), sodium salts, zinc salts, copper salts, cyclohexylamine salts of 2-mercaptobenzothiazole, 2-(2,4-dinitrophenyl)mercaptobenzothiazole, and 2-(2,6-diethyl-4-morpholinothio)benzothiazole.

[0060] Examples of thiuram derivatives include TMTD (tetramethylthiuram disulfide), tetraethylthiuram disulfide, tetramethylthiuram monosulfide, diamylenethiuram disulfide, diamylenethiuram monosulfide, diamylenethiuram tetrasulfide, diamylenethiuram hexasulfide, tetrabutylthiuram disulfide, and diamylenethiuram tetrasulfide.

[0061] Examples of thiourea compounds include thiourea compounds such as thiouramide, diethylthiourea, dibutylthiourea, trimethylthiourea, and di-o-tolylthiourea.

[0062] Examples of guanidine compounds include diphenylguanidine, di-o-toluidine, triphenylguanidine, o-toluidine, and diphenylguanidine phthalate.

[0063] Examples of dithiocarbamate compounds include zinc ethylphenyl dithiocarbamate, zinc butylphenyl dithiocarbamate, sodium dimethyl dithiocarbamate, zinc dimethyl dithiocarbamate, zinc diethyl dithiocarbamate, zinc dibutyl dithiocarbamate, zinc dipentyl dithiocarbamate, zinc dipropyl dithiocarbamate, a coordination salt of zinc pentamethylene dithiocarbamate and piperidine, zinc hexadecyl isopropyl dithiocarbamate, zinc octadecyl isopropyl dithiocarbamate, zinc dibenzyl dithiocarbamate, sodium diethyl dithiocarbamate, piperidine pentamethylene dithiocarbamate, selenium dimethyl dithiocarbamate, tellurium diethyl dithiocarbamate, and cadmium dipentyl dithiocarbamate.

[0064] Examples of aldehyde-amine or aldehyde-amine compounds include acetaldehyde-aniline reactants, butyraldehyde-aniline condensates, hexamethylenetetramine, and acetaldehyde-amine reactants.

[0065] As an anti-aging agent, it can be combined with various compounds of amine, phenol, and imidazole systems, as well as carbamate metal salts, waxes, etc.

[0066] As a softener, it can be used in combination with petroleum-based softeners such as processing oils, lubricating oils, paraffin wax, liquid paraffin wax, petroleum asphalt, and petrolatum; fatty oil-based softeners such as castor oil, linseed oil, rapeseed oil, and coconut oil; waxes such as tall oil, substitute ointments, beeswax, carnauba wax, and lanolin; and fatty acids such as linoleic acid, palmitic acid, stearic acid, and lauric acid. By combining it with a softener, the compounding processability can be further improved.

[0067] As a plasticizer, it can be combined with DMP (dimethyl phthalate), DEP (diethyl phthalate), DBP (dibutyl phthalate), DHP (diheptyl phthalate), DOP (dioctyl phthalate), DINP (diisononyl phthalate), DIDP (diisodecyl phthalate), BBP (butyl benzyl phthalate), DLP (dilauryl phthalate), DCHP (dicyclohexyl phthalate), phthalic anhydride, DOZ (di-2-ethylhexyl azelate), DBS (dibutyl sebacate), DOS (dioctyl sebacate), triethyl acetylacetonate, tributyl acetylacetonate, DBM (dibutyl maleate), DOM (2-ethylhexyl maleate), DBF (dibutyl fumarate), etc.

[0068] As an anti-scorching agent, it can be combined with organic acids such as phthalic anhydride, salicylic acid, and benzoic acid; nitroso compounds such as N-nitrosodiphenylamine; and N-cyclohexylthiophthalimide.

[0069] Preferably, the rubber composition is prepared by mixing raw materials comprising, by weight:

[0070] Diene-containing unsaturated raw rubber: 100 phr, carbon black: 30-60 phr, heterocyclic polyhydrazide compound: 0.01-10 phr, protective wax: 1.0-4.5 phr, antioxidant: 0.5-4.0 phr, activator: 1.0-6.0 phr, vulcanizing agent: 0.5-3.0 phr, accelerator: 0.1-3.0 phr;

[0071] Preferably, the carbon black is one or more of N234, N330, or N375; the antioxidant is one or more of antioxidant 4020 or antioxidant RD; and the activator is stearic acid and zinc oxide.

[0072] Furthermore, the present invention also provides a method for mixing the rubber composition, the method comprising the following steps:

[0073] First stage of plasticizing: Add raw rubber, press with a roller, hold for 30 seconds, add carbon black, press with a roller, hold for 30 seconds, and discharge the rubber at 140-150℃;

[0074] Second stage of mixing: Add the first stage of plasticized rubber and the remaining reinforcing filler material, press and mix to 115℃-125℃, add the remaining compounding agents, press and mix for 25-35 seconds, lift and clean, then press and mix to 155℃-165℃ to discharge the rubber.

[0075] Third stage of mixing: Add the second stage compound and the final fines, press and hold for 30-40 seconds, lift and clean, press and hold for another 30-40 seconds, lift and clean, press and mix again to 105-115℃ and discharge the compound.

[0076] Furthermore, the present invention also provides a tire that reduces rolling resistance, wherein the components of the tire are prepared by vulcanization of the rubber composition described above, and the components are one or more of the tire tread, sidewall, and pad rubber.

[0077] This invention, by employing the aforementioned technical solution, introduces 2–5 carboxylic acid hydrazide groups onto the same heterocyclic skeleton (3–6-membered rings containing N / O / S), forming a "multi-site anchoring" structure that can interact at multiple points with oxygen-containing functional groups and rubber segments on the surface of carbon black / fumed silica. This significantly reduces the relative slippage and frictional energy consumption between fillers and between fillers and polymers even at low dosages (preferably 0.2–1.0 phr), manifested as a reduction in the Payne effect in the small strain region, a significant decrease in G” / tanδ@60℃ (approximately 10–40% relative to the blank), and a reduction in thermal heat generation. Simultaneously, the synergistic adsorption / hydrogen bond network of the heterocyclic π-skeleton and polyhydrazide is beneficial for improving the macro- and micro-dispersion and bounding properties of carbon black (N234 / N330 / N375) or fumed silica. The rubber ratio, while maintaining or slightly increasing tanδ@0℃, also ensures wet grip, and has minimal impact on Mooney viscosity, scorch safety, and vulcanization curve disturbance. Mechanical properties and DIN abrasion resistance are basically maintained within ±10% of the control. This additive is compatible with conventional activators / accelerators / vulcanizing agents and is suitable for three-stage mixing (preferably added in the later stage of the second stage). Thus, without changing the main system and process, it can significantly reduce tire rolling resistance and achieve a balanced improvement in overall performance. Attached Figure Description

[0078] Figure 1 , Figure 2 The hydrogen and carbon spectra of the compounds prepared in Example 1 are shown respectively. Detailed Implementation

[0079] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the protection scope of the present invention.

[0080] Example 1

[0081]

[0082] 2,5-furandicarboxylic acid dihydrazide

[0083] Dimethyl 2,5-furandicarboxylate (13.8 g, 75 mmol, 1.0 eq.) was dissolved in 125 mL of ethanol, and hydrazine hydrate (80%, 10 mL, 165 mmol, 2.2 eq.) was added. The mixture was heated to reflux and reacted for 24 hours. After cooling to room temperature, the mixture was filtered, washed with 125 mL of ethanol, and dried under vacuum to give 6.6 g of 2,5-furandicarboxylate dihydrazide, with a yield of 48%. ¹H NMR (400 MHz, DMSO-d6) δ 9.75 (s, 2H), 7.10 (s, 2H), 4.56 (s, 4H); ¹³C NMR (100 MHz, DMSO-d6) δ 167.0, 147.3, 114.0.

[0084] Example 2

[0085] Dimethyl 2,5-furandicarboxylate (13.8 g, 75 mmol, 1.0 eq.) was dissolved in 125 mL of ethanol, and hydrazine hydrate (80%, 13.6 mL, 225 mmol, 3.0 eq.) was added. The mixture was heated to reflux and reacted for 24 hours. After cooling to room temperature, the mixture was filtered, washed with 125 mL of ethanol, and dried under vacuum to give 10.4 g of 2,5-furandicarboxylate dihydrazide, with a yield of 75%.

[0086] Example 3

[0087] Dimethyl 2,5-furandicarboxylate (13.8 g, 75 mmol, 1.0 eq.) was dissolved in 125 mL of ethanol, and hydrazine hydrate (80%, 22.7 mL, 375 mmol, 5.0 eq.) was added. The mixture was heated to reflux and reacted for 24 hours. After cooling to room temperature, the mixture was filtered, washed with 125 mL of ethanol, and dried under vacuum to give 13.2 g of 2,5-furandicarboxylate dihydrazide, with a yield of 96%.

[0088] Example 4

[0089] Dimethyl 2,5-furandicarboxylate (13.8 g, 75 mmol, 1.0 eq.) was dissolved in 125 mL of ethanol, and hydrazine hydrate (80%, 45.4 mL, 750 mmol, 10.0 eq.) was added. The mixture was heated to reflux and reacted for 3 hours. After cooling to room temperature, the mixture was filtered, washed with 125 mL of ethanol, and dried under vacuum to give 13.1 g of 2,5-furandicarboxylate dihydrazide, with a yield of 95%.

[0090] Example 5

[0091] Dimethyl 2,5-furandicarboxylate (13.8 g, 75 mmol, 1.0 eq.) was dissolved in 75 mL of ethanol, and hydrazine hydrate (80%, 13.6 mL, 225 mmol, 3.0 eq.) was added. The mixture was heated to reflux and reacted for 24 hours. After cooling to room temperature, the mixture was filtered, washed with 125 mL of ethanol, and dried under vacuum to give 12.6 g of 2,5-furandicarboxylate dihydrazide, with a yield of 91%.

[0092] Example 6

[0093] Dimethyl 2,5-furandicarboxylate (13.8 g, 75 mmol, 1.0 eq.) was dissolved in 37.5 mL of ethanol, and hydrazine hydrate (80%, 13.6 mL, 225 mmol, 3.0 eq.) was added. The mixture was heated to reflux and reacted for 24 hours. After cooling to room temperature, the mixture was filtered, washed with 125 mL of ethanol, and dried under vacuum to give 13.1 g of 2,5-furandicarboxylate dihydrazide, with a yield of 95%.

[0094] Example 7

[0095] Dimethyl 2,5-furandicarboxylate (13.8 g, 75 mmol, 1.0 eq.) was dissolved in 37.5 mL of ethanol, and hydrazine hydrate (80%, 10 mL, 165 mmol, 2.2 eq.) was added. The mixture was heated to reflux and reacted for 24 hours. After cooling to room temperature, the mixture was filtered, washed with 125 mL of ethanol, and dried under vacuum to give 12.4 g of 2,5-furandicarboxylate dihydrazide, with a yield of 90%.

[0096] Example 8

[0097] Dimethyl 2,5-furandicarboxylate (13.8 g, 75 mmol, 1.0 eq.) was dissolved in 37.5 mL of ethanol, and hydrazine hydrate (80%, 10 mL, 165 mmol, 2.2 eq.) was added. The mixture was heated to reflux and reacted for 3 hours. After cooling to room temperature, the mixture was filtered, washed with 125 mL of ethanol, and dried under vacuum to give 7.9 g of 2,5-furandicarboxylate dihydrazide, with a yield of 57%.

[0098] Example 9

[0099] Dimethyl 2,5-furandicarboxylate (13.8 g, 75 mmol, 1.0 eq.) was dissolved in 37.5 mL of ethanol, and hydrazine hydrate (80%, 10 mL, 165 mmol, 2.2 eq.) was added. The mixture was heated to reflux and reacted for 6 hours. After cooling to room temperature, the mixture was filtered, washed with 125 mL of ethanol, and dried under vacuum to give 9.9 g of 2,5-furandicarboxylate dihydrazide, with a yield of 72%.

[0100] Example 10

[0101] Dimethyl 2,5-furandicarboxylate (13.8 g, 75 mmol, 1.0 eq.) was dissolved in 37.5 mL of ethanol, and hydrazine hydrate (80%, 10 mL, 165 mmol, 2.2 eq.) was added. The mixture was heated to reflux and reacted for 9 hours. After cooling to room temperature, the mixture was filtered, washed with 125 mL of ethanol, and dried under vacuum to give 10.5 g of 2,5-furandicarboxylate dihydrazide, with a yield of 76%.

[0102] Example 11

[0103] Dimethyl 2,5-furandicarboxylate (13.8 g, 75 mmol, 1.0 eq.) was dissolved in 37.5 mL of ethanol, and hydrazine hydrate (80%, 10 mL, 165 mmol, 2.2 eq.) was added. The mixture was heated to reflux and reacted for 12 hours. After cooling to room temperature, the mixture was filtered, washed with 125 mL of ethanol, and dried under vacuum to give 11.4 g of 2,5-furandicarboxylate dihydrazide, with a yield of 83%.

[0104] Example 12

[0105] Dimethyl 2,5-furandicarboxylate (13.8 g, 75 mmol, 1.0 eq.) was dissolved in 37.5 mL of ethanol, and hydrazine hydrate (80%, 10 mL, 165 mmol, 2.2 eq.) was added. The mixture was heated to reflux and reacted for 18 hours. After cooling to room temperature, the mixture was filtered, washed with 125 mL of ethanol, and dried under vacuum to give 11.9 g of 2,5-furandicarboxylate dihydrazide, with a yield of 86%.

[0106] Example 13

[0107]

[0108] 3,5-Pyridinedicarboxylic acid dihydrazide

[0109] Dimethyl 3,5-pyridinedicarboxylate (3.90 g, 20 mmol, 1.0 eq.) was dissolved in 80 mL of ethanol, and hydrazine hydrate (80%, 4 mL, 66 mmol, 3.3 eq.) was added. The mixture was heated to reflux and reacted for 24 hours. After cooling to room temperature, the mixture was filtered, washed with 100 mL of ethanol, and dried under vacuum to give 2.4 g of 3,5-pyridinedicarboxylate dihydrazide, with a yield of 62%. ¹H NMR (400 MHz, DMSO-d⁶) δ 10.06 (s, 2H), 9.05 (d, J = 2.1 Hz, 2H), 8.53 (t, J = 2.1 Hz, 1H), 4.56 (s, 4H); ¹³C NMR (100 MHz, DMSO-d⁶) δ 163.7, 149.9, 133.7, 128.8.

[0110] Example 14

[0111]

[0112] 1-Methyl-1H-pyrazole-3,5-dicarboxylic acid dihydrazide

[0113] Dimethyl 3,5-pyridinedicarboxylate (2.97 g, 15 mmol, 1.0 eq.) was dissolved in 5 mL of methanol, and hydrazine hydrate (80%, 4.5 mL, 75 mmol, 5.0 eq.) was added. The mixture was heated to reflux and reacted for 18 hours. After cooling to room temperature, the mixture was filtered, washed with 100 mL of ethanol, and dried under vacuum to give 2.9 g of 1-methyl-1H-pyrazole-3,5-dicarboxylic acid dihydrazide, with a yield of 98%. ¹H NMR (400 MHz, DMSO-d6) δ 9.86 (s, 1H), 9.42 (s, 1H), 7.14 (s, 1H), 4.48 (s, 4H), 4.08 (s, 3H); ¹³C NMR (100 MHz, DMSO-d6) δ 160.4, 158.6, 143.8, 135.5, 106.9, 39.3.

[0114] Example 15

[0115]

[0116] 2,6-Pyridinedicarboxylic acid dihydrazide

[0117] Dimethyl 2,6-pyridinedicarboxylate (3.90 g, 20 mmol, 1.0 eq.) was dissolved in 40 mL of methanol, and hydrazine hydrate (80%, 6 mL, 100 mmol, 5.0 eq.) was added. The mixture was heated to reflux and reacted for 18 hours. After cooling to room temperature, the mixture was filtered, washed with 100 mL of ethanol, and dried under vacuum to give 3.8 g of 2,6-pyridinedicarboxylate dihydrazide, with a yield of 97%. ¹H NMR (400 MHz, DMSO-d⁻⁶) δ 10.60 (s, 2H), 8.13 (s, 3H), 4.62 (s, 4H); ¹³C NMR (100 MHz, DMSO-d⁻⁶) δ 161.9, 148.4, 139.3, 123.7.

[0118] Application examples

[0119] I. Raw Materials and General Conditions

[0120] 1. Raw materials

[0121] Raw rubber: Natural rubber NR-3L.

[0122] Filler: Carbon black N234 (specific surface area approximately 120 m²) 2 / g).

[0123] Other compounding agents: zinc oxide (ZnO), stearic acid (SA), antioxidant 4020, microcrystalline wax, sulfur (S), accelerator NS.

[0124] The adjuvant of this invention is a heterocyclic polyhydrazide compound (examples: 3,5-pyridinedicarboxylic acid dihydrazide, 2,5-furandicarboxylic acid dihydrazide, 1-methyl-1H-pyrazole-3,5-dicarboxylic acid dihydrazide).

[0125] Commercially available rolling resistance reducing agent: DC-02 (industry-standard comparative agent).

[0126] 2. Mixing process (general): three-stage method.

[0127] Section 1: Internal mixer filling rate ≈ 0.70, rotor 60rpm, feeding sequence: NR→(30s)→N234→(30s)→heat to 140–150℃ and drop the glue.

[0128] Second stage: Add the first stage masterbatch and the remaining filler to 115–125℃, add the minor ingredients (including additives / antioxidants / activators), mix for 25–35 seconds, and heat to 155–165℃ to release the rubber; the additives are preferably added in the later stage of the second stage.

[0129] Three stages: Add the second stage rubber and final fines, press for 30–40 seconds (twice), and finally drop the rubber at 105–115℃.

[0130] Vulcanization conditions: t90 is measured according to MDR (150℃), and hot-press vulcanization is performed at t90 + 3 min (unless otherwise specified).

[0131] 3. Testing Methods (General)

[0132] MDR (150℃): ML, MH, tS2, t90.

[0133] Mooney viscosity: ML(1+4)@100℃.

[0134] DMA: 10Hz, 1% strain, temperature rise from -20 to 80℃; take tanδ@60℃ and tanδ@0℃.

[0135] RPA strain scan (60℃): Payne effect ΔG′ is obtained from G′@0.56% and G′@100%.

[0136] Bound Rubber (toluene, 25°C, 72h): determined by conventional methods.

[0137] Mechanical properties / DIN abrasion / hardness: ISO37 / ISO4649 / Shore A.

[0138] II. Comparative Example

[0139] Comparative Example 1 (blank control, without rolling resistance reducing agent)

[0140] The formulation of Comparative Example 1 is designed as follows: NR-3L 100 phr, N234 50 phr, ZnO 2.5 phr, stearic acid 1 phr, antioxidant 4020 0.5 phr, microcrystalline wax 0.2 phr, sulfur 1.1 phr, NS 0.9 phr.

[0141] Results (see Table 1): tanδ@60℃=0.1887; used as the benchmark for comparison of all application examples.

[0142] Comparative Example 2 (Commercial Additives Control)

[0143] Formula (phr): Based on Comparative Example 1, add 0.5 phr of DC-02. Results (see Table 1): tanδ@60℃=0.1719 (a decrease of approximately 8.9% compared to Comparative Example 1).

[0144] Comparative Example 3

[0145] Formula (phr): NR-3L 100, N234 50, ZnO 2.5, stearic acid 1.0, antioxidant 4020 0.5, microcrystalline wax 0.2, terephthalic acid dihydrazide 0.5, sulfur 1.1, NS 0.9.

[0146] Comparative Example 4

[0147] Formula (phr): NR-3L 100, N234 50, ZnO 2.5, stearic acid 1.0, antioxidant 4020 0.5, microcrystalline wax 0.2, pyromellitic trihydrazide 0.5, sulfur 1.1, NS 0.9.

[0148] III. Application Examples (of this invention)

[0149] Application Example 1 (Heterocyclic dihydrazide-pyridine skeleton, 0.5 phr)

[0150] Additive: 0.5 phr of 3,5-pyridinedicarboxylic acid dihydrazide.

[0151] Formulation: Same as Comparative Example 1, except that the amount of inert filler is replaced with an auxiliary agent (total phr remains constant).

[0152] Application Example 2 (Heterocyclic dihydrazide-furan skeleton, 0.5 phr)

[0153] Additive: 0.5 phr of 2,5-furandicarboxylic acid dihydrazide.

[0154] Application Example 3 (Dose Exploration—Furran Matrix, 1.0 phr)

[0155] Additive: 2,5-furandicarboxylic acid dihydrazide 1.0 phr.

[0156] Application Example 4 (Dose Exploration—Furran Matrix, 2.0 phr)

[0157] Additive: 2,5-furandicarboxylic acid dihydrazide 2.0 phr.

[0158] Application Example 5 (Heterocyclic dihydrazide-pyrazole skeleton, 0.5 phr, containing alkyl substitution)

[0159] Additive: 0.5 phr of 1-methyl-1H-pyrazole-3,5-dicarboxylic acid dihydrazide (as permitted by the claims in the case of "alkyl-linked / substituted").

[0160] IV. Comprehensive Data Table

[0161] Table 1 Key Dynamic Viscoelasticity and Interface Dispersion Related Indicators

[0162]

[0163] illustrate:

[0164] 1. The tanδ@60℃ data directly reflects the rolling resistance trend. The samples of this invention are significantly lower than the blank and commercial control; and decrease stepwise with the increase of dosage.

[0165] 2. The Payne effect (ΔG′) continuously decreases, indicating the weakening of the filler network and the improvement of dispersion; the BoundRubber increases, indicating the enhanced interaction between the filler and rubber interface—consistent with the mechanism of the decrease in tanδ.

[0166] 3. tanδ@0℃ remains basically flat (±1–2%), indicating no adverse effects on wet gripping; Mooney / mechanical / DIN values ​​remain within ±10% of the control, demonstrating acceptable processing and abrasion resistance.

[0167] V. Technical Conclusions

[0168] 1. Significant drag reduction at low dosages: At 0.5 phr, heterocyclic dihydrazides (pyridine / furan) reduced drag by 12.9–15.3% compared to the blank, which was superior to the commercial control (-8.9%). When the dosage was increased to 1.0–2.0 phr, the drag reduction further increased to 22.9–30.2%.

[0169] 2. The interface mechanism was confirmed by multiple indicators: synchronous with tanδ@60℃, ΔG′ continued to decrease and BoundRubber continued to increase, indicating that the "multi-site anchoring" of polyhydrazide + heterocyclic π skeleton effectively weakens the energy consumption of filler network and interface slip.

[0170] 3. Good performance balance: tanδ@0℃ basically does not decrease (wet grip maintains), Mooney / mechanical / DIN are within ±10% of the control, indicating that processing safety and service strength are not compromised.

[0171] The above description illustrates application examples of the present invention. Through this explanation, those skilled in the art will be able to implement or use the present invention. Various modifications to these application examples will be readily apparent to those skilled in the art. The general principles defined herein may be implemented in other application examples without departing from the spirit or scope of the invention. Therefore, the present invention is not to be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novelty disclosed herein.

Claims

1. The heterocyclic polyhydrazide compound is used in the preparation of additives to reduce tire rolling resistance, wherein the heterocyclic polyhydrazide compound satisfies: c1) the molecule contains a 3-6 member heterocyclic skeleton containing heteroatoms, wherein the heteroatoms are one or more of N, O, and S; c2) The heterocycle has a carboxylic acid hydrazide group -C(O)-NH-NH2 attached to the carbon positions of the 2nd to 5th rings, and each hydrazide group is directly bonded to the heterocycle, or each hydrazide group is connected to the heterocycle through an alkyl or aromatic group.

2. The application according to claim 1, characterized in that, The heterocycle is selected from one or more of furan, pyridine, pyrazole, imidazole, thiophene, and oxazole; preferably, the heterocyclic polyhydrazide compound is selected from one or more compounds with the following structural formulas: Where X = O, S or NR, and R = H, C1-C10 alkyl or aryl.

3. A rubber composition for reducing tire rolling resistance, characterized in that, The rubber composition contains a heterocyclic polyhydrazide compound, which satisfies the following: c1) The molecule contains a 3-6 member heterocyclic skeleton containing heteroatoms, wherein the heteroatoms are one or more of N, O, and S; c2) The heterocycle has a carboxylic acid hydrazide group -C(O)-NH-NH2 attached to the carbon positions of the 2nd to 5th rings, and each hydrazide group is directly bonded to the heterocycle, or each hydrazide group is connected to the heterocycle through an alkyl or aromatic group.

4. The rubber composition according to claim 3, characterized in that, The heterocycle is selected from one or more of furan, pyridine, pyrazole, imidazole, thiophene, and oxazole.

5. The rubber composition according to claim 3, characterized in that, Heterocyclic polyhydrazide compounds are selected from one or more compounds with the following structural formulas: Where X = O, S or NR, and R = H, C1-C10 alkyl or aryl.

6. The rubber composition according to any one of claims 3-5, characterized in that, The rubber composition is prepared by mixing the following raw materials in parts by weight: A) 100 phr of unsaturated raw rubber containing diene groups; B) Packing material 30–150 phr; C) Rolling resistance reducing agent 0.01–10.0 phr, wherein the agent is a heterocyclic polyhydrazide compound; preferably 0.2–1.0 phr.

7. The rubber composition according to claim 6, characterized in that, The dien-containing unsaturated raw rubber is selected from one or more of the following: natural rubber, styrene-butadiene rubber, cis-butadiene rubber, isoprene rubber, chloroprene rubber, ethylene propylene rubber, butyl rubber, silicone rubber, polyurethane rubber, acrylate rubber, chlorinated ether rubber, and chlorinated polyethylene rubber. And / or, the filler is selected from one or more of carbon black, silica, carbon nanotubes, graphene, graphene oxide, carbon fiber, and nanocellulose; Further optimization yields silica with a BET specific surface area of ​​50–250 m². 2 / g, preferably 80-210m 2 / g, more preferably 100-190m 2 / g; and / or, the average secondary particle size of silica is preferably 0.04-3μm, more preferably 0.1-1μm, and even more preferably 0.2-0.7μm; the amount of silica added relative to 100 parts by weight of rubber component is preferably 20-120 parts by weight, more preferably 25-100 parts by weight, and even more preferably 30-90 parts by weight; Further optimization is preferred, with the BET specific surface area of ​​the carbon black particles preferably ranging from 20 to 160 m². 2 / g, more preferably 40-130m 2 / g, further preferably 50-120m 2 / g, the average secondary particle size of the carbon black particles is preferably 0.05-3μm, more preferably 0.1-1.0μm, and even more preferably 0.2-0.9μm; the amount of carbon black particles in the formulation is preferably 2-50 parts by mass relative to 100 parts by mass of the rubber component, more preferably 3-30 parts by mass, and even more preferably 10-20 parts by mass.

8. The rubber composition according to claim 6, characterized in that, The rubber composition is prepared by mixing the following raw materials in parts by weight: Diene-containing unsaturated raw rubber: 100 phr, carbon black: 30-60 phr, heterocyclic polyhydrazide compound: 0.01-10 phr, protective wax: 1.0-4.5 phr, antioxidant: 0.5-4.0 phr, activator: 1.0-6.0 phr, vulcanizing agent: 0.5-3.0 phr, accelerator: 0.1-3.0 phr; Preferably, the carbon black is one or more of N234, N330, or N375; the antioxidant is one or more of antioxidant 4020 or antioxidant RD; and the activator is stearic acid and zinc oxide.

9. The method for mixing the rubber composition according to claim 8, characterized in that, The method includes the following steps: First stage of plasticizing: Add raw rubber, press with a roller, hold for 30 seconds, add carbon black, press with a roller, hold for 30 seconds, and discharge the rubber at 140-150℃; Second stage of mixing: Add the first stage of plasticized rubber and the remaining reinforcing filler material, press and mix to 115℃-125℃, add the remaining compounding agents, press and mix for 25-35 seconds, lift and clean, then press and mix to 155℃-165℃ to discharge the rubber. Third stage of mixing: Add the second stage compound and the final fines, press and hold for 30-40 seconds, lift and clean, press and hold for another 30-40 seconds, lift and clean, press and mix again to 105-115℃ and discharge the compound.

10. A tire with reduced rolling resistance, characterized in that, The components of the tire are prepared by vulcanization of the rubber composition according to any one of claims 3-9.

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