Rubber composition, preparation method therefor, and TBR tire using same

Abstract

The present application belongs to the technical field of rubber and specifically relates to a rubber composition, a preparation method therefor, and a TBR tire using same. The rubber composition comprises 100 parts by mass of a diene rubber, 0.2-1.5 parts by mass of a hydrazide compound, 0.2-1.5 parts by mass of a tetrazine compound multifunctional modifier, 0-30 parts by mass of a liquid rubber, 20-120 parts by mass of a reinforcing filler, 1-10 parts by mass of a silane coupling agent, a vulcanization accelerator, a vulcanization agent, an antioxidant, a vulcanization activator, a resin, and a plasticizer. The present application can significantly reduce the rolling resistance and heat generation of TBR all-steel tires while improving the cut and tear resistance of the tires.

Description

A rubber composition and its preparation method, and a TBR tire using the same.

[0001] Cross-reference to related applications

[0002] This application claims priority to Chinese Patent Application No. 2024115791930, filed on November 7, 2024, entitled "A rubber composition and a method for preparing the same, and a TBR tire using the same", and Chinese Patent Application No. 2025106920994, filed on May 27, 2025, entitled "A rubber composition and a method for preparing the same, and a TBR tire using the same", the entire contents of which are incorporated herein by reference. Technical Field

[0003] This application belongs to the field of rubber technology, specifically relating to a rubber composition and its preparation method, and a TBR tire using the same. Background Technology

[0004] During operation, TBR all-steel trucks expose the tire rubber to a heat-oxygen, fatigue, and cut-damage environment under load and cyclic deformation. Reducing tire heat generation and improving the tire rubber's cut resistance and tear resistance are crucial for extending tire life. Furthermore, with the increasing emphasis on dual-carbon and carbon neutrality policies, higher requirements are being placed on the rolling resistance (carbon emissions from fuel consumption) of TBR all-steel tires. The highest A-level TBR all-steel tires in the European Labelling Regulation (ECE117) are required to have a rolling resistance coefficient (RRC) of less than 4 N / kN; China's newly issued mandatory national standard GB9744 limits the RRC of TBR all-steel tires to less than 6.5 N / kN. However, using traditional methods, such as changing the rubber type or increasing the amount of silica used, to reduce tire rolling resistance and heat generation has many limitations in achieving a balanced overall performance. Low rolling resistance and low heat generation require rubber materials with low energy dissipation (hysteresis loss), while cut resistance and damage resistance under large deformation require high energy dissipation capacity. Therefore, low rolling resistance and low heat generation, and high cut and tear resistance are contradictory. Reducing rolling resistance and heat generation often leads to a decrease in cut and tear resistance, and improving one property often results in the loss of others. This makes it difficult to improve the overall tire lifespan. In practical applications, increasing the amount of silica or decreasing the amount of filler in the TBR all-steel tread composition can reduce rolling resistance, but it decreases cut and tear resistance, causing chipping and fragmentation problems that affect lifespan. Therefore, achieving simultaneous improvement in low rolling resistance and low heat generation, and high cut and tear resistance, is currently quite difficult.

[0005] To address this technological need, patent publications CN110392713B, CN108026332B, CN110382611B, CN110382612B, CN110382554B, and CN110461931B disclose rubber compositions and tires. By combining specific rubber components, tetrazine compounds represented by general formula (4) or their salts, and carbon black and carbon white, a rubber composition can be provided that not only imparts excellent low heat generation to the tire but also excellent wear resistance. However, these published patents do not describe or provide example data regarding cut and tear resistance. In addition, by using the rubber composition of the above invention to make tires, not only can the rolling resistance and heat generation of the tire be reduced, but wear resistance can also be improved. Therefore, low fuel consumption tires for large automobiles can be provided. However, abrasion resistance refers to the wear resistance under small deformations in non-harsh road conditions. This is not contradictory to the low heat generation due to the high dispersion of fillers in the rubber, but it contradicts the rubber's mechanism of action for cut and tear resistance under large deformations in harsh road conditions. Therefore, tires made from this rubber composition have weaker or even worse cut and tear resistance, failing to meet the requirements of low rolling resistance and improved cut and tear resistance for TBR all-steel tires.

[0006] Patent publication number CN102257056A discloses a rubber composition, a rubber material using multiple diene rubbers, an inorganic filler content greater than 50%, additives, and their application methods. It shows that using a dihydrazide compound alone can significantly reduce the heat generation performance of the rubber composition. However, it does not describe or provide example data regarding cut and tear resistance. Therefore, given the contradiction between low heat generation and cut and tear resistance, this rubber composition cannot meet the requirements of low rolling resistance and improved cut and tear resistance for TBR all-steel tires.

[0007] Patent publication number CN103261300A discloses a rubber composition with a carbon black content greater than 50%. This composition, obtained by mixing natural rubber and carbon black in a liquid phase and adding a dihydrazide compound, exhibits high dispersion and low heat generation. However, it also lacks descriptions and examples regarding cut and tear resistance. Therefore, given the inherent contradiction between low heat generation and cut and tear resistance, this rubber composition cannot meet the requirements of low rolling resistance and improved cut and tear resistance in TBR all-steel tires.

[0008] Patent publication number CN111592695A discloses a rubber composition consisting of 0-40 parts of natural rubber with the addition of the low rolling resistance additive 1-naphthylacetylhydrazine, high cis-butadiene rubber or solution-polymerized styrene-butadiene rubber, fillers, and additives. The primary purpose is to achieve low rolling resistance or low hysteresis without affecting abrasion performance. However, it lacks descriptions and examples regarding cut and tear resistance. Therefore, given the inherent contradiction between low heat generation and cut and tear resistance, this rubber composition cannot meet the requirements of low rolling resistance and improved cut and tear resistance in TBR all-steel tires.

[0009] Therefore, how to provide a rubber composition that reduces rolling resistance and heat generation while improving cut and tear resistance, and its preparation method, is a technical problem that urgently needs to be solved by those skilled in the art. Summary of the Invention

[0010] In view of this, the first objective of this application is to address the problems existing in the prior art by providing a rubber composition that can be used to reduce rolling resistance and heat generation in TBR all-steel tires while improving cut and tear resistance.

[0011] To achieve the above objectives, this application adopts the following technical solution:

[0012] A rubber composition comprising the following raw materials in parts by weight: 100 parts of diene rubber, 0.2-1.5 parts of acylhydrazine compound, 0.2-1.5 parts of tetrazine compound, 0-30 parts of liquid rubber, 20-120 parts of reinforcing filler, and 1-10 parts of silane coupling agent, wherein,

[0013] The structures of the acylhydrazine compounds are: R1-CO-NH-NH2 (1) NH2-NH-CO-R2-CO-NH-NH2 (2) R3-CO-NH-N=R4 (3)

[0014] R1, R2, R3, and R4 are each independently selected from: an aromatic hydrocarbon group having 6 to 30 carbon atoms or an alkane group having 6 to 30 carbon atoms, wherein the aromatic hydrocarbon is arbitrarily substituted with an alkyl, hydroxyl, or amino group having 1 to 20 carbon atoms;

[0015] The structure of the tetrazine compound is as follows:

[0016] Where X 1 X 2 This indicates a heterocyclic group that can have substituents, where the substituents are alkyl, aralkyl, or heterocyclic groups.

[0017] The structure of the liquid rubber is as follows:

[0018] Where l, m, and n are any integers from 1 to 1000.

[0019] It is worth noting that acylhydrazine compounds can react with natural rubber to reduce rolling resistance and heat generation; tetrazine compounds can undergo a trans-Diels-Alder reaction with the double bonds of synthetic diene rubbers, also reducing rolling resistance and heat generation. The combined use of tetrazine and acylhydrazine compounds can significantly reduce rolling resistance and heat generation in formulations combining natural and synthetic rubber, and the two exhibit a certain synergistic effect. Furthermore, the addition of liquid rubber containing specific functional groups alone does not improve resistance to damage, but when combined with other compounds, it significantly enhances resistance to damage and reduces rolling resistance and heat generation to some extent. Therefore, the rubber composition disclosed in this application can significantly reduce the rolling resistance and heat generation of TBR all-steel tires while improving the tire's cut and tear resistance.

[0020] Furthermore, the rubber composition also includes a vulcanization accelerator, a vulcanizing agent, an antioxidant, a vulcanization activator, a resin, and a plasticizer.

[0021] In this application, the vulcanization accelerator is one or a combination of thiazoles, thiurams, sulfenamides, dithiocarbamates, xanthic acids, guanidines, and thioureas. Preferably, it is diphenylguanidine or N-cyclohexyl-2-benzothiazole sulfenamide. The vulcanization accelerator accounts for 0.5-4 parts by weight in the rubber composition, preferably 0.8-3 parts by weight, and more preferably 1-2.5 parts by weight.

[0022] The vulcanizing agent is sulfur, and the proportion of the vulcanizing agent in the rubber composition is 0.5-5 parts by weight, preferably 0.8-3 parts by weight, and more preferably 1-2 parts by weight.

[0023] Furthermore, the antioxidant is 6PPD, and the vulcanization activator is zinc oxide and stearic acid. The rubber composition also includes a protective agent, microcrystalline wax.

[0024] Furthermore, the diene rubber is one or more of the following: modified or unmodified natural rubber, polyisoprene rubber, polybutadiene rubber, cis-butadiene rubber, styrene-butadiene copolymer rubber, ethylene-propylene-diene monomer copolymer, styrene-isoprene-styrene terblock copolymer rubber, and styrene-butadiene-styrene terblock copolymer rubber.

[0025] Furthermore, the diene rubber is composed of 50-100 parts by weight of any one or more of modified or unmodified natural rubber and polyisoprene rubber, and 0-50 parts by weight of any one or more of modified or unmodified styrene-butadiene copolymer rubber and polybutadiene rubber.

[0026] Preferably, the diene rubber is composed of 60-100 parts by weight of any one or more of modified or unmodified natural rubber and polyisoprene rubber, and 0-40 parts by weight of any one or more of modified or unmodified styrene-butadiene copolymer rubber and polybutadiene rubber.

[0027] In this application, the styrene-butadiene copolymer rubber contains 5%-40% wt styrene, and the styrene-butadiene copolymer rubber is one or more of the following elastomer substances: unmodified solution-polymerized styrene-butadiene rubber, unmodified emulsion-polymerized styrene-butadiene rubber, end-group modified solution-polymerized styrene-butadiene rubber, end-group modified emulsion-polymerized styrene-butadiene rubber, main-chain modified solution-polymerized styrene-butadiene rubber, and main-chain modified emulsion-polymerized styrene-butadiene rubber. The Tg of the styrene-butadiene copolymer rubber is -100 to 0°C, more preferably -90 to -15°C, and even more preferably -80 to -30°C.

[0028] It is worth noting that using the aforementioned rubbers can simultaneously reduce tire rolling resistance and heat generation, while improving cut resistance. Modified solution-polymerized styrene-butadiene rubber (SBR) is preferred among SBRs because it has better affinity with silica, improving silica dispersion and achieving a better balance between cut resistance, rolling resistance, heat generation, and processing performance. Nickel-catalyzed, lithium-catalyzed, and rare-earth-catalyzed polybutadiene rubber (PPB) systems are even more preferred, as the addition of modified PPB effectively balances wear resistance, rolling resistance, heat generation, processing performance, aging resistance, and fatigue crack propagation resistance.

[0029] Furthermore, the acylhydrazine compound includes one or more combinations of adipic acid dihydrazine, isophthalic acid dihydrazine, terephthalic acid dihydrazine, caprylic acid dihydrazine, sebacic acid dihydrazine, dodecanoic acid dihydrazine, benzoic acid dihydrazine, naphthoic acid dihydrazine, propionic acid dihydrazine, caprylic acid dihydrazine, stearic acid dihydrazine, hexanoic acid dihydrazine, decanoic acid dihydrazine, oleic acid dihydrazine, lauroic acid dihydrazine, palmitic acid dihydrazine, N'-(1,3-dimethylbutylene)-3-hydroxy-2-naphthoic acid dihydrazine, 2-hydroxy-naphthoic acid dihydrazine, and 2-hydroxy-benzoic acid dihydrazine, and the proportion of the acylhydrazine compound in the rubber composition is 0.3-1.2 parts by weight.

[0030] Furthermore, a combination of one or more of adipate dihydrazide, isophthalic dihydrazide, and N'-(1,3-dimethylbutylene)-3-hydroxy-2-naphthohydrazide is preferred, and a combination of one or more of isophthalic dihydrazide and N'-(1,3-dimethylbutylene)-3-hydroxy-2-naphthohydrazide is even more preferred. In this application, the amount of the hydrazide compound is 0.3-1.2 parts by weight, preferably 0.3-1 parts by weight, and even more preferably 0.3-0.8 parts by weight.

[0031] Furthermore, the tetrazine compound includes one or more combinations of 3,6-bis(2-pyridyl)-1,2,4,5-tetrazine, 3,6-bis(3-pyridyl)-1,2,4,5-tetrazine, and 3,6-bis(4-pyridyl)-1,2,4,5-tetrazine, and the tetrazine compound accounts for 0.3-1.2 parts by weight in the rubber composition.

[0032] In this application, the tetrazine compound is preferably 3,6-bis(2-pyridyl)-1,2,4,5-tetrazine. The tetrazine compound accounts for 0.3-1.2 parts by weight in the rubber composition, preferably 0.3-1 parts by weight, and more preferably 0.3-0.8 parts by weight.

[0033] Furthermore, the liquid rubber is one or more of the following: modified or unmodified liquid polyisoprene, liquid hydrogenated polyisoprene, liquid polybutadiene, liquid styrene-isoprene copolymer, liquid isoprene-butadiene copolymer, and liquid styrene-butadiene copolymer, and the molecular weight of the liquid rubber is 500-100000 g / mol, and the proportion of the liquid rubber in the rubber composition is 3-20 parts by mass.

[0034] In this application, the liquid rubber is preferably a combination of one or more of the following: maleic anhydride-modified liquid polyisoprene, carboxylic acid acrylate-modified liquid polyisoprene, maleic anhydride-modified liquid polybutadiene, carboxylic acid acrylate-modified liquid polybutadiene, and maleic anhydride monomethyl ester-modified liquid polyisoprene. More preferably, it is a combination of one or more of the following: maleic anhydride-modified liquid polyisoprene, maleic anhydride-modified liquid polybutadiene, carboxylic acid acrylate-modified liquid polyisoprene, and maleic anhydride monomethyl ester-modified liquid polyisoprene. The molecular weight of the liquid rubber is preferably 500-80000 g / mol, more preferably 500-50000 g / mol. The proportion of the liquid rubber in the rubber composition is preferably 5-15 parts by weight, more preferably 5-10 parts by weight.

[0035] It is worth noting that the above-mentioned acylhydrazine compounds and tetrazine compounds are used in this application to graft and modify natural rubber, styrene-butadiene rubber, and cis-butadiene rubber. The liquid rubber and acylhydrazine compounds or tetrazine compounds have a synergistic effect, which can improve or not affect the effect of reducing rolling resistance and heat generation, and further improve the cut resistance and tear resistance of the final product.

[0036] Furthermore, the reinforcing filler includes one or more combinations of modified or unmodified carbon black, acetylene black, silica, carbon nanotubes, graphite, and graphene; the silane coupling agent is one or more combinations of bis-[3-(triethoxysilyl)propyl]-tetrasulfide, bis-[3-(triethoxysilyl)propyl]-disulfide, 3-octanoylthio-1-propyltriethoxysilane, γ-mercaptopropylethoxybis-(propane-hexaethoxysiloxane), mercaptoalkoxy-ethoxysilane, and mercaptoalkoxy-methoxysilane.

[0037] In this application, the preferred reinforcing filler is one or a combination of carbon black and silica.

[0038] In some embodiments, the reinforcing filler is composed of 20-70 parts by weight of silica and 0-50 parts by weight of carbon black. Preferably, the reinforcing filler is composed of 10-50 parts by weight of silica and 0-50 parts by weight of carbon black.

[0039] Furthermore, the specific surface area of ​​the carbon black is 20-160 m². 2 / g, the specific surface area of ​​silica is 60-250m². 2 / g. More preferably, the specific surface area of ​​the carbon black is 40-140m². 2 / g, the specific surface area of ​​silica is 90-230m². 2 / g.

[0040] In this application, the carbon black is one or a combination of N110, N121, N134, N220, N231, N234, N242, N293, N299, N315, N326, N330, N332, N339, N343, N347, N351, N358, N375, N539, N550, N582, N630, N642, N650, N683, N754, N762, N765, N774, N787, N907, N908, N990, and N991; the iodine absorption value of the above carbon black is 5-150 g / kg, and the DBP absorption value is 30-150 cm⁻¹. 3 / 100g.

[0041] In this application, the silane coupling agent accounts for 1-8 parts by weight in the rubber composition.

[0042] Preferably, the silane coupling agent is one or a combination of bis-[3-(triethoxysilyl)propyl]-tetrasulfide (Si 69), bis-[3-(triethoxysilyl)propyl]-disulfide (Si 75), and 3-octanoylthio-1-propyltriethoxysilane (NXT), more preferably bis-[3-(triethoxysilyl)propyl]-disulfide (Si 75) or 3-octanoylthio-1-propyltriethoxysilane (NXT). Furthermore, the proportion of the silane coupling agent in the rubber composition is preferably 2-7 parts by weight, more preferably 3-6 parts by weight.

[0043] It is worth noting that by adjusting the types and amounts of silica, carbon black, and silane coupling agent, this application can better balance the low rolling resistance, low heat generation, and cut and tear resistance of the final product.

[0044] The second objective of this application is to provide a method for preparing a rubber composition as described above.

[0045] A method for preparing the rubber composition as described above includes the following steps:

[0046] Step (1) Accurately weigh diene rubber, hydrazide compounds, tetrazine compounds, liquid rubber, reinforcing filler, silane coupling agent, vulcanization accelerator, vulcanizing agent, antioxidant, vulcanization activator, resin and plasticizer;

[0047] Step (2) Mix diene rubber, hydrazide compound, tetrazine compound and reinforcing filler and react them at 120-180℃ for 60-300 seconds. After standing and cooling, material A is obtained, wherein the discharge temperature is 120-180℃.

[0048] Step (3) Mix liquid rubber, silane coupling agent, antioxidant, vulcanization activator, resin and plasticizer with material A, and react them at 120-180℃ for 60-300 seconds. After standing and cooling, material B is obtained, wherein the discharge temperature is 120-180℃.

[0049] Step (4) The vulcanizing agent and vulcanization accelerator are added to material B and then discharged after mixing to obtain the rubber composition.

[0050] It is worth noting that all tetrazine compounds and hydrazide compounds are added in step (2), while liquid rubber and antioxidants may be added partially or entirely in step (2), step (3), or step (4).

[0051] In some embodiments, carbon black in the reinforcing filler may be added in part or all in step (2) or step (3); silica and silane coupling agent in the reinforcing filler may be added in step (3).

[0052] In this application, the mixing reaction treatment at 120-180℃ in step (2) is preferably 120-300 seconds, more preferably 150-300 seconds; the discharge temperature is 120-180℃, preferably 130-170℃, more preferably 140-160℃.

[0053] In this application, the mixing reaction treatment at 120-180℃ in step (3) is preferably 120-300 seconds, more preferably 150-300 seconds; the discharge temperature is 120-180℃, preferably 130-170℃, more preferably 140-160℃.

[0054] It is worth noting that by adding small amounts of acylhydrazine compounds, tetrazine compounds, and liquid rubber, and by applying an optimized rubber mixing process that conforms to the reaction of acylhydrazine compounds, tetrazine compounds, and rubber, the composition can simultaneously reduce the hysteresis loss of rubber, reduce rolling resistance and heat generation, and at the same time improve cut resistance and tear resistance. The preparation method in this application is simple to operate and highly practical.

[0055] The third objective of this application is to provide a tire.

[0056] A TBR tire comprising the rubber composition described above.

[0057] In this application, the tire is suitable for TBR all-steel heavy-duty trucks, and the rubber composition can meet the requirements of low rolling resistance of TBR all-steel tires while improving cut resistance and tear resistance.

[0058] Compared with existing technologies, this application provides a method that can reduce the hysteresis, heat generation, and tire rolling resistance of rubber while simultaneously improving its cut and tear resistance, breaking through the traditional technical bottleneck of trade-offs. Attached Figure Description

[0059] To more clearly illustrate the technical solutions in the embodiments of this application or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only embodiments of this application. For those skilled in the art, other drawings can be obtained based on the provided drawings without creative effort.

[0060] Figure 1 shows the high-temperature slow tear energy test specimen provided in this application. Detailed Implementation

[0061] The technical solutions in the embodiments of this application will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of this application, and not all embodiments. Based on the embodiments in this application, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of this application.

[0062] The term "embodiment" used herein, as an example, is not necessarily to be construed as superior to or better than other embodiments. Performance testing in the embodiments of this application, unless otherwise specified, employs conventional testing methods in the art. It should be understood that the terminology used in this application is merely for describing particular implementations and is not intended to limit the scope of this disclosure.

[0063] Unless otherwise stated, the technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application pertains; other experimental methods and technical means not specifically mentioned herein refer to experimental methods and technical means commonly used by one of ordinary skill in the art.

[0064] To better illustrate the content of this application, numerous specific details are provided in the following detailed embodiments. Those skilled in the art should understand that this application can be implemented even without certain specific details. In the embodiments, some methods, means, instruments, and devices well-known to those skilled in the art are not described in detail in order to highlight the main points of this application.

[0065] Without conflict, the technical features disclosed in the embodiments of this application can be combined arbitrarily, and the resulting technical solution belongs to the content disclosed in the embodiments of this application.

[0066] This application provides a rubber composition and its preparation method, and a TBR tire using the same. The rubber composition (by mass parts) comprises 100 parts of diene rubber, 0.2-1.5 parts of acylhydrazine compound, 0.2-1.5 parts of tetrazine compound multifunctional modifier, 0-30 parts of liquid rubber, 20-120 parts of reinforcing filler, 1-10 parts of silane coupling agent, vulcanization accelerator, vulcanizing agent, antioxidant, vulcanization activator, resin, and plasticizer. The acylhydrazine compound can react with natural rubber to reduce rolling resistance and heat generation. The tetrazine compound can undergo a trans-Diels-Alder reaction with the double bonds of the synthetic diene rubber, also reducing rolling resistance and heat generation. The combined use of tetrazine compound and acylhydrazine compound can significantly reduce the rolling resistance and heat generation of formulations using a blend of natural and synthetic rubber, and the two compounds exhibit a certain synergistic effect. The addition of liquid rubber containing special functional groups alone does not improve the resistance to damage, but when added in combination, it significantly improves the resistance to damage and reduces rolling resistance and heat generation to some extent. This application can significantly reduce the rolling resistance and heat generation of TBR all-steel tires while improving the tire's cut and tear resistance.

[0067] To better understand this application, the following embodiments are provided for further detailed explanation, but they should not be construed as limiting the application. Any non-essential improvements and adjustments made by those skilled in the art based on the above application content are also considered to fall within the protection scope of this application.

[0068] The standards and methods for testing the rubber composition in this application are as follows in the following embodiments:

[0069] 1) Mooney viscosity: Refer to ASTM D1646-2007, test conditions are ML(1+4) 100℃. The higher the index, the higher the Mooney viscosity.

[0070] 2) Mooney scorch: According to ASTM D1646-2007, the test temperature is 130℃. The higher the index, the longer the scorch time.

[0071] 3) Hardness: Shore hardness test, refer to ASTM D2240-2010. The higher the index, the higher the hardness.

[0072] 4) MA100: 100% tensile modulus test, referring to ASTM D412-2006, taking the modulus at 100% elongation, the test environment temperature is 23±2℃. The larger the index, the higher the tensile modulus.

[0073] 5) Tensile strength and elongation at break: Refer to ASTM D412-2006. The sample is dumbbell-shaped. The test speed is 500 mm / min, and the test environment temperature is 23±2℃. The larger the index, the higher the tensile strength.

[0074] 6) Hysteresis Loss Factor: Tested using Metravib DMA at 60°C, 10Hz, dynamic deformation 0.07%-50%, and planar shear mode. The smaller the index, the smaller the hysteresis loss, and the lower the rolling resistance and heat generation.

[0075] 7) High-temperature slow-speed tear energy: A sample with a width of 40 mm, a height of 65 mm, and a notch of 10 mm was used (see Figure 1). The test speed was 50 mm / min, and the test environment temperature was 100 ± 5℃. The higher the index, the higher the high-temperature tear energy and the better the tear resistance.

[0076] 8) Dynamic cutting loss of rubber: Manufacturer: Beijing Wanhui Yifang; Test conditions: Impact frequency 120 / min; Rubber wheel speed 720rpm; Test method: The mass after 5min of pre-cutting of the rubber wheel is recorded as m0, and the mass after 20min of cutting is recorded as m1; Data record: Cutting loss mass per minute: Δm=(m0-m1) / 15min; Where the smaller the index, the smaller the cutting mass loss and the better the cutting resistance and tear resistance.

[0077] The raw materials used in this application embodiment are as follows:

[0078] Natural Rubber: TSR20, Sinochem International (Holdings) Co., Ltd.

[0079] NS712 (Styrene-Butadiene Rubber) - ZSE Corporation, Japan

[0080] BR9000 (Polybutadiene Rubber) Sinopec Qilu Petrochemical Company

[0081] Acylhydrazide derivatives: N'-(1,3-dimethylbutylene)-3-hydroxy-2-naphthohydrazide, Otsuka Chemical Co., Ltd. Tetraazine compounds: 3,6-bis(2-pyridyl)-1,2,4,5-tetraazine, Otsuka Chemical Co., Ltd.

[0082] Isophthalic acid dihydrazide: TCI (Shanghai) Chemical Industry Development Co., Ltd.

[0083] Adipic acid dihydrazide: TICE (Shanghai) Chemical Industry Development Co., Ltd.

[0084] Stearyl hydrazide: TCI (Shanghai) Chemical Industry Development Co., Ltd.

[0085] Liquid Rubber: Maleic Anhydride Monomethyl Ester Modified Liquid Polyisoprene, Kuraray Corporation

[0086] Liquid Rubber: Maleic Anhydride Modified Liquid Polybutadiene, Yichuang Chemical Co., Ltd.

[0087] HD165MP, HD200MP (Silica) - Wuxi Quecheng Silicon Co., Ltd.

[0088] N234, N220, N330, N115: Cabot Carbon Black

[0089] Si69, Si75: Nanjing Shuguang Chemical Group Co., Ltd.

[0090] NXT: Momentive Advanced Materials Group

[0091] 6PPD (Antioxidant) Shandong Shangshun Chemical Co., Ltd.

[0092] Stearic acid: Sichuan Tianyu Oil & Chemical Co., Ltd.

[0093] Zinc oxide: Dalian Zinc Oxide Co., Ltd.

[0094] Microcrystalline wax: Yanggu Huatai Chemical Co., Ltd.

[0095] NS (N-tert-butyl-2-benzothiazole sulfenamide) Shandong Shangshun Chemical Co., Ltd.

[0096] Sulfur: Shandong Shangshun Chemical Co., Ltd.

[0097] Example 1

[0098] The raw materials used in Comparative Examples 1-1 to 1-4 and Examples 1-1 to 1-4 of this application are shown in the table below, all in parts by mass. Among them, Examples 1-1 to 1-4 are rubber compositions using 3,6-bis(2-pyridyl)-1,2,4,5-tetraazine and N'-(1,3-dimethylbutylene)-3-hydroxy-2-naphthohydrazide together.

[0099] Table 1: Formulations of Comparative Examples 1-1 to 1-4 and Examples 1-1 to 1-4

[0100] The above schemes all adopt the following preparation method:

[0101] Step (1) Weigh the raw materials according to the above-mentioned mass; Step (2) Mix natural rubber, NS712 and BR9000 for 30 seconds, add hydrazide compounds, tetrazine compounds and carbon black, and perform a mixing reaction at 130-160℃ for 150 seconds, then discharge the rubber at 160℃ to obtain material A; Step (3) Mix the remaining raw materials except for the vulcanizing agent and vulcanization accelerator with material A, perform a mixing reaction at 140-160℃ for 150 seconds, and discharge the rubber at 160℃ to obtain material B; Step (4) Add the vulcanizing agent and vulcanization accelerator to material B and mix in a mixer for about 180 seconds, then discharge the material at 110℃ to obtain a rubber composition for reducing the rolling resistance and heat generation of TBR all-steel tires while improving cut and tear resistance. Then, vulcanize the rubber composition at 150℃ for 30 minutes for testing.

[0102] Performance tests were conducted on Examples 1-1, 1-2, 1-3, 1-4 and Comparative Examples 1-1, 1-2, 1-3, 1-4 before and after aging at 100℃ for 72 hours. The results are shown in Table 2 below.

[0103] Table 2: Performance Comparison of Examples 1-1 to 1-4, Comparative Examples 1-2 to 1-4, and Comparative Example 1-1

[0104] *The test results for the rubber composition are expressed in exponential form.

[0105] The calculation formula is: Test item = (Example / Comparative Example 1-1) × 100.

[0106] Compared with Comparative Examples 1-1, 1-2, 1-3, and 1-4, Examples 1-1, 1-2, 1-3, and 1-4 showed increased tensile strength and minimal change in elongation at break, with little change in hardness. Compared with Comparative Examples 1-1, 1-2, 1-3, and 1-4, the hysteresis loss factors of Examples 1-1, 1-2, 1-3, and 1-4 decreased by 8%, 21%, 25%, and 21%, respectively. The reduction in hysteresis loss factors was more significant in examples where natural rubber was blended with synthetic styrene-butadiene rubber or synthetic cis-butadiene rubber. Compared with Comparative Examples 1-1, 1-2, 1-3, and 1-4, the unaged cutting loss of Examples 1-1, 1-2, 1-3, and 1-4 decreased by 1%, 8%, 19%, and 8%, respectively; the aged cutting loss decreased by 0%, 4%, 5%, and 7%, respectively. The slow tear energy at high temperature before aging increased by 109%, 30%, 35%, and 31%, respectively. After aging, the high-temperature slow tear resistance was improved by 9%, 50%, 39%, and 93%, respectively. Therefore, when 3,6-bis(2-pyridyl)-1,2,4,5-tetraazine and N'-(1,3-dimethylbutylene)-3-hydroxy-2-naphthohydrazide are used together in TBR all-steel tires, they can improve cut and tear resistance while reducing rolling resistance and heat generation.

[0107] Example 2

[0108] The raw materials used in Comparative Example 2-1 and Examples 2-1 to 2-6 of this application are shown in Table 3 below, all in parts by mass. Example 2-1 is a rubber composition using a combination of 3,6-bis(2-pyridyl)-1,2,4,5-tetraazine and N'-(1,3-dimethylbutylene)-3-hydroxy-2-naphthoylhydrazine. Examples 2-2 to 2-5 are rubber compositions using a combination of 3,6-bis(2-pyridyl)-1,2,4,5-tetraazine, N'-(1,3-dimethylbutylene)-3-hydroxy-2-naphthoylhydrazine, and maleic anhydride monomethyl ester modified liquid polyisoprene. Examples 2-6 are polybutadiene grafted with 3,6-bis(2-pyridyl)-1,2,4,5-tetraazine, N'-(1,3-dimethylbutylene)-3-hydroxy-2-naphthoylhydrazine, and maleic anhydride.

[0109] Table 3: Formulations of Comparative Example 2-1 and Examples 2-1 to 2-6

[0110] The above schemes all adopt the following preparation method:

[0111] Step (1) Weigh the raw materials according to the above-mentioned mass; Step (2) Mix natural rubber and NS712 for 30 seconds, add hydrazide compounds and tetrazine compounds, carbon black, and perform a mixing reaction at 140-160℃ for 150 seconds, then discharge the rubber at 160℃ to obtain material A; Step (3) Mix the remaining raw materials except for the vulcanizing agent and vulcanization accelerator with material A, perform a mixing reaction at 140-160℃ for 150 seconds, and discharge the rubber at 160℃ to obtain material B; Step (4) Add the vulcanizing agent and vulcanization accelerator to material B and mix in a mixer for about 180 seconds, then discharge the material at 110℃ to obtain a rubber composition for reducing the rolling resistance and heat generation of TBR all-steel tires while improving cut and tear resistance. Then, vulcanize the rubber composition at 150℃ for 30 minutes for testing.

[0112] Performance tests were conducted on Comparative Example 2-1 and Examples 2-1, 2-2, 2-3, 2-4, 2-5, and 2-6, respectively, before and after aging at 100°C for 72 hours. The results are shown in Table 4 below.

[0113] Table 4: Performance Comparison of Examples 2-1 to 2-6 with Comparative Example 2-1

[0114] *The test results for the rubber composition are expressed in exponential form.

[0115] The calculation formula is: Test item = (Example / Comparative Example 2-1) × 100.

[0116] Compared to Comparative Example 2-1, the Mooney viscosity and scorch time of Examples 2-1 to 2-6 were all increased, with the increase in Mooney viscosity being more significant in Examples 2-1 and 2-2. The examples showed improvements in tensile strength and elongation at break while maintaining relatively stable hardness. Compared to Comparative Example 2-1, Examples 2-1 to 2-6 exhibited reductions in hysteresis loss factors of 22%, 21%, 17%, 19%, 17%, and 11%, respectively, and reductions in shear loss of 2%, 16%, 26%, 19%, and 23%, respectively; after 45% aging, the shear loss was reduced by 1%, 11%, 22%, 17%, 22%, and 23%, respectively. Specifically, with the increase in the amount of maleic anhydride monomethyl ester modified liquid polyisoprene, the shear loss in Example 2-3 was further reduced, but the hysteresis loss factor increased to some extent, although it still showed a significant improvement compared to the comparative example. Therefore, when N'-(1,3-dimethylbutylene)-3-hydroxy-2-naphthohydrazide, 3,6-bis(2-pyridyl)-1,2,4,5-tetraazine, and maleic anhydride-modified liquid polyisoprene are used together in TBR all-steel tires, they can improve cut and tear resistance while reducing rolling resistance and heat generation.

[0117] Example 3

[0118] The raw materials used in Comparative Examples 3-1, 3-2, 3-3, 3-4 and Examples 3-1, 3-2, 3-3, 3-4, 3-5, 3-6 of this application are shown in Table 5 below, all in parts by mass. Examples 3-1 to 3-3 are rubber compositions using 3,6-bis(2-pyridyl)-1,2,4,5-tetraazine in combination with isophthalic acid dihydrazide, adipate dihydrazide, and stearic acid dihydrazide. Examples 3-4 to 3-6 are rubber compositions using 3,6-bis(2-pyridyl)-1,2,4,5-tetraazine in combination with isophthalic acid dihydrazide, adipate dihydrazide, stearic acid dihydrazide, and maleic anhydride monomethyl ester modified liquid polyisoprene.

[0119] Table 5: Formulations of Comparative Examples 3-1 to 3-4 and Examples 3-1 to 3-6

[0120] The above schemes all adopt the following preparation method:

[0121] Step (1) Weigh the raw materials according to the above-mentioned mass; Step (2) Mix natural rubber and BR9000 for 30 seconds, add hydrazide compounds and tetrazine compounds, carbon black, and perform a mixing reaction at 140-160℃ for 150 seconds, then discharge the rubber at 160℃ to obtain material A; Step (3) Mix the remaining raw materials except for the vulcanizing agent and vulcanization accelerator with material A, perform a mixing reaction at 140-160℃ for 150 seconds, and discharge the rubber at 160℃ to obtain material B; Step (4) Add the vulcanizing agent and vulcanization accelerator to material B and mix in a mixer for about 180 seconds, then discharge the material at 110℃ to obtain a rubber composition for reducing the rolling resistance and heat generation of TBR all-steel tires while improving cut and tear resistance. Then, vulcanize the rubber composition at 150℃ for 30 minutes for testing.

[0122] Performance tests were conducted on Comparative Examples 3-1, 3-2, 3-3, 3-4 and Examples 3-1, 3-2, 3-3, 3-4, 3-5, 3-6 before and after aging at 100℃ for 72 hours. The results are shown in Table 6 below.

[0123] Table 6: Comparison of performance results between Comparative Examples 3-1 to 3-4 and Examples 3-1 to 3-6

[0124] *The test results for the rubber composition are expressed in exponential form.

[0125] The calculation formula is: Test item = (Example / Comparative Example 3-1) × 100.

[0126] Compared to Comparative Example 3-1, Comparative Examples 3-2, 3-3, and 3-4 showed higher Mooney viscosity and shorter scorch times. Examples 3-1 to 3-6 also showed significantly higher Mooney viscosity and shorter scorch times. The hardness, tensile strength, and elongation at break of the comparative examples and examples did not change significantly.

[0127] Compared with Comparative Example 3-1, Comparative Examples 3-2, 3-3, and 3-4 showed a decrease in hysteresis loss factors of 20%, 17%, and 10%, respectively, and an increase in cutting loss of 7%, 7%, and -3%, respectively. Except for Comparative Example 3-4, which showed a slight improvement, the cutting resistance of Comparative Examples 3-2 and 3-3 deteriorated, and the trend after aging was also the same.

[0128] Compared with Comparative Example 3-1, Examples 3-1, 3-2, and 3-3 showed a reduction in hysteresis loss factors of 29%, 31%, and 20%, respectively. The cutting loss was also improved compared with Comparative Examples 3-2, 3-3, and 3-4, and compared with Comparative Example 1. The aging behavior was also similar. Therefore, when isophthalic acid dihydrazide, adipic acid dihydrazide, and 3,6-bis(2-pyridyl)-1,2,4,5-tetraazine are used in TBR all-steel tires, they can stabilize the cut resistance and significantly reduce rolling resistance and heat generation.

[0129] Compared with Comparative Example 3-1, Examples 3-4, 3-5, and 3-6 show a hysteresis loss factor reduction of 26%, 25%, and 12%, respectively, and a cut loss reduction of 15%, 10%, and 29%, respectively, with similar trends observed after aging. Therefore, when liquid polyisoprene modified with isophthalic acid dihydrazide, adipate dihydrazide, 3,6-bis(2-pyridyl)-1,2,4,5-tetraazine, and maleic anhydride monomethyl ester is used together in TBR all-steel tires, it can improve cut resistance while reducing rolling resistance and heat generation.

[0130] The above description of the disclosed embodiments enables those skilled in the art to make or use this application. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of this application. Therefore, this application is not to be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A rubber composition, characterized in that, The raw materials include the following parts by weight: 100 parts diene rubber, 0.2-1.5 parts acylhydrazine compounds, 0.2-1.5 parts tetrazine compounds, 0-30 parts liquid rubber, 20-120 parts reinforcing fillers, and 1-10 parts silane coupling agent, wherein... The structure of the acylhydrazine compound is as follows: R1-CO-NH-NH2 (1) NH2-NH-CO-R2-CO-NH-NH2 (2) R3-CO-NH-N=R4 (3) R1, R2, R3, and R4 are each independently selected from: an aromatic hydrocarbon group having 6 to 30 carbon atoms or an alkane group having 6 to 30 carbon atoms, wherein the aromatic hydrocarbon is arbitrarily substituted with an alkyl, hydroxyl, or amino group having 1 to 20 carbon atoms; The structure of the tetrazine compound is as follows: Where X 1 X 2 This indicates a heterocyclic group that can have substituents, where the substituents are alkyl, aralkyl, or heterocyclic groups. The structure of the liquid rubber is as follows: Where l, m, and n are any integers from 1 to 1000.

2. The rubber composition according to claim 1, characterized in that, It also includes vulcanization accelerators, vulcanizing agents, antioxidants, vulcanization activators, resins, and plasticizers.

3. The rubber composition according to claim 1, characterized in that, The diene rubber is one or more of the following: modified or unmodified natural rubber, polyisoprene rubber, polybutadiene rubber, cis-butadiene rubber, styrene-butadiene copolymer rubber, ethylene-propylene-diene monomer copolymer, styrene-isoprene-styrene terblock copolymer rubber, and styrene-butadiene-styrene terblock copolymer rubber.

4. The rubber composition according to claim 3, characterized in that, The diene rubber is composed of 50-100 parts by weight of any one or more of modified or unmodified natural rubber and polyisoprene rubber, and 0-50 parts by weight of one or more of modified or unmodified styrene-butadiene copolymer rubber and polybutadiene rubber.

5. The rubber composition according to claim 1, characterized in that, The acylhydrazide compounds include one or more combinations of adipic acid dihydrazide, isophthalic acid dihydrazide, terephthalic acid dihydrazide, caprylic acid dihydrazide, sebacic acid dihydrazide, dodecanoic acid dihydrazide, benzoic acid dihydrazide, naphthoic acid dihydrazide, propionic acid dihydrazide, caprylic acid dihydrazide, stearic acid dihydrazide, hexanoic acid dihydrazide, decanoic acid dihydrazide, oleic acid dihydrazide, lauroic acid dihydrazide, palmitic acid dihydrazide, N'-(1,3-dimethylbutylene)-3-hydroxy-2-naphthoic acid dihydrazide, 2-hydroxy-naphthoic acid dihydrazide, and 2-hydroxy-benzoic acid dihydrazide, and the proportion of the acylhydrazide compounds in the rubber composition is 0.3-1.2 parts by weight.

6. The rubber composition according to claim 1, characterized in that, The tetrazine compound includes one or more combinations of 3,6-bis(2-pyridyl)-1,2,4,5-tetrazine, 3,6-bis(3-pyridyl)-1,2,4,5-tetrazine, and 3,6-bis(4-pyridyl)-1,2,4,5-tetrazine, and the tetrazine compound accounts for 0.3-1.2 parts by weight in the rubber composition.

7. The rubber composition according to claim 1, characterized in that, The liquid rubber is one or more of the following: modified or unmodified liquid polyisoprene, liquid hydrogenated polyisoprene, liquid polybutadiene, liquid styrene-isoprene copolymer, liquid isoprene-butadiene copolymer, and liquid styrene-butadiene copolymer. The molecular weight of the liquid rubber is 500-100000 g / mol, and the mass percentage of the liquid rubber in the rubber composition is 3-20 parts.

8. The rubber composition according to claim 1, characterized in that, The reinforcing filler includes one or more combinations of modified or unmodified carbon black, acetylene black, silica, carbon nanotubes, graphite, and graphene. The silane coupling agent is one or more of the following: bis-[3-(triethoxysilyl)propyl]-tetrasulfide, bis-[3-(triethoxysilyl)propyl]-disulfide, 3-octanoylthio-1-propyltriethoxysilane, γ-mercaptopropylethoxybis-(propane-hexaethoxysiloxane), mercaptoalkoxy-ethoxysilane, and mercaptoalkoxy-methoxysilane.

9. The method for preparing the rubber composition according to any one of claims 1-8, characterized in that, Includes the following steps: Step (1) Accurately weigh diene rubber, hydrazide compounds, tetrazine compounds, liquid rubber, reinforcing filler, silane coupling agent, vulcanization accelerator, vulcanizing agent, antioxidant, vulcanization activator, resin and plasticizer; Step (2) Mix diene rubber, hydrazide compound, tetrazine compound and reinforcing filler and react them at 120-180℃ for 60-300 seconds. After standing and cooling, material A is obtained, wherein the discharge temperature is 120-180℃. Step (3) Mix liquid rubber, silane coupling agent, antioxidant, vulcanization activator, resin and plasticizer with material A, and react them at 120-180℃ for 60-300 seconds. After standing and cooling, material B is obtained, wherein the discharge temperature is 120-180℃. Step (4) The vulcanizing agent and vulcanization accelerator are added to material B and then discharged after mixing to obtain the rubber composition.

10. A TBR tire, characterized in that, Includes the rubber composition as described in any one of claims 1-8.

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