Multi-dimensional filler, rubber composite material as well as preparation method and application of multi-dimensional filler and rubber composite material

Abstract

The invention provides a multi-dimensional filler, a rubber composite material and a preparation method and application of the multi-dimensional filler and the rubber composite material. The multi-dimensional filler is obtained by mixing and reacting at least two fillers with different dimensions; the filler is a three-dimensional filler, a two-dimensional filler or a one-dimensional filler, and the surface of the filler contains hydroxyl. The preparation method of the multi-dimensional filler comprises the following steps: dispersing filler comprising at least two different dimensions into a solvent, and carrying out condensation reaction to obtain the multi-dimensional filler. The multi-dimensional filler can be used for preparing a rubber composite material, and the prepared multi-dimensional filler rubber composite material can be applied to tires. The prepared multi-dimensional filler is better in compatibility and dispersity, when the rubber composite material is prepared, the dispersity of the multi-dimensional filler in a rubber matrix can be effectively improved, the temperature rise and rolling resistance of the composite material are effectively reduced, and the wet skid resistance of the composite material is improved.

Description

Technical Field

[0001] This invention relates to the field of rubber composite materials technology, and more specifically, to a multidimensional filler, a rubber composite material, its preparation method, and its application. Background Technology

[0002] Tires are a crucial component of modern automobiles, playing a vital role in load-bearing, traction, and braking. During driving, tires continuously deform, and under alternating loads, heat is generated due to hysteresis losses, causing internal temperatures to rise. This reduces tire airtightness and the bonding strength with the carcass material. Furthermore, increased deformation leads to increased rolling resistance and fatigue damage to the rubber system, potentially resulting in safety accidents. Therefore, selecting appropriate materials and adjusting the formulation of rubber composite systems to reduce tire rolling resistance and dynamic heat generation is of significant practical importance.

[0003] In the processing and production of rubber products, various fillers are typically added to reinforce and modify the rubber in order to improve its overall performance. Fillers with different properties are used to achieve reinforcement effects in specific directions. In the past, single fillers were mainly used for reinforcement. However, with the emergence of nanomaterials and the increasing demands on rubber performance, single reinforcement systems are difficult to meet the requirements. Researchers have begun to explore more comprehensive filler compound systems. The selection of reinforcing fillers is also diverse, with different filler compound systems chosen based on actual conditions and needs.

[0004] Carbon black, silica, and other fillers are widely used in the processing and production of rubber products due to their excellent properties. However, because of their high surface activity, adding a single filler can lead to the formation of agglomerates of varying degrees in the rubber matrix, resulting in uneven filler dispersion. This makes it difficult to fully utilize the filler's superior properties and significantly impacts the formation of the filler network and the reinforcing effect. Adding two or more fillers with similar properties to the rubber matrix can achieve a better reinforcing effect. Different fillers can form a synergistic effect through physicochemical adsorption, promoting filler dispersion in the rubber matrix, establishing a more complete filler network, and making the reinforcing effect more pronounced.

[0005] Chinese invention patent CN116178801A discloses a low rolling resistance and low temperature rise tire tread compound material and its preparation method, comprising 1,4-trans-polyisoprene rubber, natural rubber, silica, carbon black, silica, silane coupling agent, stearic acid, zinc oxide, antioxidant, accelerator, naphthenic oil, and sulfur. Because silica can reduce the temperature rise of the surface and core of the vulcanized product under alternating loads, it lowers the Mooney viscosity of the compound while ensuring good performance of the rubber. Therefore, the vulcanized product of the composite material prepared with silica generates less heat under alternating loads, resulting in a smaller temperature rise of the surface and core, and better mechanical properties, thus ensuring the quality of the final product. However, this formulation only uses a simple physical blending method to mix the filler with the matrix rubber, and the dispersion of the filler in the rubber matrix is ​​not effectively improved.

[0006] Therefore, it is necessary to study a filler that improves its surface polarity, thereby enhancing its compatibility and dispersibility in rubber, enabling it to disperse better in the rubber matrix, thus improving the performance of rubber composites. When used in tread compounds, it can reduce tire rolling resistance and dynamic heat rise. Summary of the Invention

[0007] In order to solve the technical problems existing in the prior art, the present invention provides a multidimensional filler, a rubber composite material, a preparation method thereof, and its application.

[0008] Most rubbers used in tires are non-polar rubbers, while common fillers contain hydroxyl groups on their surfaces. This leads to poor dispersion of the fillers in the rubber, affecting tire performance. The multidimensional filler of this invention induces a dehydration condensation reaction between fillers of different dimensions containing hydroxyl groups, reducing the polar functional groups on the filler surface and lowering its polarity, thus improving compatibility. Furthermore, in composites of two or more fillers, one filler can act as a physical barrier, preventing the aggregation of other fillers and improving dispersion, resulting in even better dispersibility. Because the multidimensional filler improves the compatibility and dispersibility between the filler and rubber, it effectively improves the dispersion of the multidimensional filler in the rubber matrix during the preparation of rubber composites, effectively reducing the temperature rise and rolling resistance of the composite material, and enhancing the composite material's anti-skid performance.

[0009] One objective of this invention is to provide a multidimensional filler, which is obtained by mixing and reacting fillers comprising at least two different dimensions; the filler is a three-dimensional filler, a two-dimensional filler, or a one-dimensional filler, and the surface of the filler contains hydroxyl groups.

[0010] Fillers of different dimensions refer to a mixture of fillers containing at least two fillers of different dimensions, such as one-dimensional and two-dimensional, one-dimensional and three-dimensional, two-dimensional and three-dimensional, etc. Multidimensional fillers prepared using chemical methods with two or more fillers of different dimensions exhibit superior performance. First, they reduce the surface polarity of the filler, resulting in better compatibility. Second, one filler can act as a physical barrier, preventing the aggregation of other fillers and thus improving dispersion. Third, the advantages of fillers of different dimensions can be complementary. For example, vulcanizates filled with silica have lower hysteresis loss, effectively reducing tire rolling resistance. However, at the same time, compounds filled with large amounts of silica suffer from static electricity that cannot be discharged; the simultaneous use of graphene can solve the problem of static electricity accumulation in the compound.

[0011] In a preferred embodiment of the present invention,

[0012] The one-dimensional filler is at least one of carbon fiber, wollastonite, carbon nanotubes, and halloysite nanotubes, preferably at least one of carbon nanotubes and wollastonite; and / or,

[0013] The two-dimensional filler is at least one selected from montmorillonite, talc, graphene, graphene oxide, boron nitride, kaolin, and mica flakes, preferably at least one selected from montmorillonite and graphene; and / or,

[0014] The three-dimensional filler is at least one of carbon black, silica, barium sulfate, and alumina, preferably at least one of carbon black and silica.

[0015] A second objective of this invention is to provide a method for preparing multidimensional fillers, comprising the following steps:

[0016] The multidimensional filler is obtained by dispersing fillers comprising at least two different dimensions in a solvent and then performing a condensation reaction.

[0017] The hydroxyl groups on the surfaces of two or more fillers with different dimensions undergo a condensation reaction, and the fillers are mutually anchored through chemical bonds to obtain the multidimensional filler.

[0018] In a preferred embodiment of the present invention,

[0019] When the multidimensional filler is obtained by reacting a mixture of two fillers with different dimensions, the mass ratio of the two fillers is 1:(0.01~100), preferably 1:(0.1~8); when the multidimensional filler is obtained by reacting a mixture of three or more fillers with different dimensions, at least two of the fillers have different dimensions, and the mass of any one dimension filler accounts for not less than 1% of the total mass of the multidimensional filler, preferably not less than 10%; and / or,

[0020] The solvent is at least one selected from water, ethanol, benzene, toluene, xylene, dichloromethane, dichloroethane, cyclohexane, and n-hexane, preferably at least one of deionized water and ethanol; and / or,

[0021] The ratio of the total mass of the filler to the volume of the solvent is 1–100 g filler / 100 mL solvent, preferably 6–30 g filler / 100 mL solvent, such as 6, 8, 10, 12, 15, 20, 25, 30 g filler / 100 mL solvent or any two of the above values, for example 10–30 g filler / 100 mL solvent; and / or,

[0022] The condensation reaction is carried out under stirring, preferably at a stirring speed of 100–800 rpm, more preferably at 300–500 rpm; even more preferably, the stirring is carried out in at least one of a mechanical stirrer, a high-speed disperser, and an ultrasonic cleaner; and / or,

[0023] The condensation reaction is performed at a temperature of 20–100°C, preferably 50–80°C; and / or,

[0024] The condensation reaction takes 0.5–12 hours, preferably 5–9 hours; and / or,

[0025] The product is post-processed after the reaction, including separation and removal of solvent and drying; preferably, the separation method is at least one of filtration, centrifugation, and sedimentation, preferably centrifugation; and / or, the drying method is at least one of vacuum drying, atmospheric pressure drying, microwave drying, spray drying, and freeze drying.

[0026] The third objective of this invention is to provide an application of the above-mentioned multidimensional filler or the multidimensional filler obtained by the above-mentioned preparation method in rubber composite materials.

[0027] The fourth objective of this invention is to provide a multidimensional filler rubber composite material, comprising the following components based on 100 parts by weight of rubber:

[0028] 100 parts by weight of rubber;

[0029] Multidimensional filler: 20-100 parts by weight; preferably 60-80 parts by weight;

[0030] 0.2 to 15 parts by weight of silane coupling agent; preferably 1.2 to 8 parts by weight;

[0031] Activator: 1-10 parts by weight; preferably 3-8 parts by weight;

[0032] Plasticizer: 0.5 to 5 parts by weight; preferably 1 to 3 parts by weight;

[0033] Anti-aging agent: 1-5 parts by weight; preferably 2-4 parts by weight;

[0034] Accelerator: 1-8 parts by weight; preferably 2-6 parts by weight;

[0035] Vulcanizing agent: 0.5 to 4 parts by weight; preferably 1 to 3 parts by weight.

[0036] The multidimensional filler is the multidimensional filler described above or the multidimensional filler prepared by the above method.

[0037] In a preferred embodiment of the present invention,

[0038] The rubber is at least one selected from solution-polymerized styrene-butadiene rubber, emulsion-polymerized styrene-butadiene rubber, nitrile rubber, acrylate rubber, polyurethane rubber, polyisoprene rubber, ethylene propylene rubber, chloroprene rubber, cis-butadiene rubber, butyl rubber, fluororubber, and natural rubber; and / or,

[0039] The silane coupling agent is at least one of γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, bis-[γ-(triethoxysilyl)propyl]tetrasulfide, 3-(trimethoxysilyl)propyl methacrylate, (3-glycidoxy)trimethoxysilane, bis-[3-(triethoxysilyl)propyl]disulfide, and 3-mercaptopropylethoxybis(tetrazylpentaethoxysiloxane); and / or,

[0040] The activator is at least one selected from zinc oxide, stearic acid, zinc fatty acid, lead oxide, magnesium oxide, and amines; the amine is at least one selected from ethylenediamine phosphate, propylenediamine phosphate, ammonium sulfate, and ammonium chloride; and / or,

[0041] The plasticizer is at least one of petroleum-based plasticizers, fatty oil-based plasticizers, and pine oil-based plasticizers; preferably at least one of paraffin wax, aromatic oils, and naphthenic oils; and / or...

[0042] The antioxidant is at least one of p-phenylenediamine, phenol, and organosulfur antioxidants; preferably at least one of antioxidant 4010NA, antioxidant 4020NA, and antioxidant RD; and / or

[0043] The accelerator is at least one selected from sulfenamides, thiazoles, guanidines, thiurams, and thiocarbamates, preferably at least one selected from N-cyclohexyl-2-benzothiazole sulfenamide and diphenylguanidine; and / or,

[0044] The vulcanizing agent is at least one of di-tert-butyl peroxide, sulfur, bis(2,5) vulcanizing agent, and dicumyl peroxide.

[0045] The fifth objective of this invention is to provide a method for preparing a multidimensional filler rubber composite material, comprising the following steps:

[0046] (1) Mix the components including the multidimensional filler, rubber, silane coupling agent, activator, plasticizer, and antioxidant to obtain mixture A;

[0047] (2) After heat treatment, the mixture A obtained in step (1) is mixed with vulcanizing agent and accelerator to obtain mixture B;

[0048] (3) The mixture B obtained in step (2) is vulcanized to obtain the multidimensional filler rubber composite material.

[0049] In a preferred embodiment of the present invention,

[0050] In step (1),

[0051] The mixing method can be any of the mixing methods commonly used in rubber processing in the prior art, preferably mechanical mixing, more preferably mechanical mixing using at least one of a two-roll mill, a mixer, or a screw mixer; and / or,

[0052] The mixing temperature is 20–60℃; and / or,

[0053] The mixing time is 5–120 min, preferably 5–20 min; and / or,

[0054] In step (2),

[0055] The heat treatment temperature is 140–160°C; and / or,

[0056] The heat treatment time is 5–10 min; and / or,

[0057] The mixing temperature is 20–60℃; and / or,

[0058] The mixing time is 2–30 min, preferably 5–10 min; and / or,

[0059] In step (3),

[0060] Mixture B is left to stand for 12–24 hours before vulcanization; and / or,

[0061] The vulcanization in step (3) can be carried out using conventional rubber vulcanization equipment and processes, preferably room temperature vulcanization or high temperature vulcanization; if high temperature vulcanization is used, preferably, the vulcanization temperature is 120-170℃, preferably 140-160℃; and / or, the vulcanization pressure is 10-20MPa, preferably 12-15MPa; and / or, the vulcanization time is the normal vulcanization time.

[0062] The sixth objective of this invention is to provide an application of the above-mentioned multidimensional filler rubber composite material or the multidimensional filler rubber composite material obtained by the above-mentioned preparation method in tires, preferably in tread rubber.

[0063] Compared with existing technologies, the technical advantages of this invention are:

[0064] Most rubbers used in tires are non-polar rubbers, while common fillers contain hydroxyl groups on their surfaces. This leads to poor dispersion of the fillers in the rubber, affecting tire performance. The multidimensional filler of this invention induces a condensation reaction between fillers of different dimensions containing hydroxyl groups, reducing the polarity of the filler surface and thus improving compatibility. Furthermore, in composites of two or more fillers, one filler can act as a physical barrier, preventing the aggregation of other fillers and improving dispersion. Because the multidimensional filler improves the compatibility and dispersibility between the filler and rubber, it effectively improves the dispersion of the multidimensional filler in the rubber matrix during the preparation of rubber composites, reducing the temperature rise and rolling resistance of the composite material and enhancing its wet skid resistance.

[0065] The multidimensional filler prepared by this invention combines the advantages of fillers with different dimensions. By preparing two or more fillers with different dimensions through chemical methods, the resulting multidimensional filler has better performance. In addition to improving compatibility and dispersibility, the advantages of fillers with different dimensions can complement each other. For example, vulcanizates filled with silica have lower hysteresis loss, thereby effectively reducing the rolling resistance of tires. However, at the same time, there is a problem of static electricity not being able to be discharged in rubber compounds filled with a large amount of silica. The simultaneous use of graphene can solve the problem of static electricity accumulation in rubber compounds.

[0066] The multidimensional filler rubber composite material prepared by this invention, when applied to tire treads, offers enhanced safety while reducing fuel consumption. The preparation method of this invention is simple, quick, and easy to operate, facilitating its widespread application. Detailed Implementation

[0067] The present invention will now be described in detail with reference to specific embodiments. It should be noted that the following embodiments are only used to further illustrate the present invention and should not be construed as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made by those skilled in the art based on the content of the present invention are still within the scope of protection of the present invention.

[0068] Unless otherwise specified, the raw materials used in the embodiments and comparative examples of this invention are all disclosed in the prior art, such as those that can be directly purchased or prepared according to the preparation methods disclosed in the prior art.

[0069] Test method:

[0070] The strain was tested at 60°C using a rubber processing strain scanner (RPA; RPA2000, Gotech Testing Machines Inc., China); at a frequency of 1 Hz, the strain range of the compound was 0.28–200%; at a frequency of 10 Hz, the strain range of the vulcanizate was 0.28–42%.

[0071] The static mechanical properties of the nanocomposite material were tested using an electronic tensile testing machine (CMT4104, SANS Testing Machine Co., Ltd., Shenzhen, China) at room temperature and a tensile rate of 500 mm / min, in accordance with GB / T528-2009 standard.

[0072] The composite material was tested in tension mode using a dynamic mechanical thermal analyzer (DMTA; DMA 1, Mettler Toledo Instruments Co., Ltd., Shanghai, China). The test conditions were: strain 0.1%, frequency 10 Hz, heating rate 3℃ / min, and temperature range -80 to 80℃. The abrasion resistance of the composite material was tested using an Akron abrasion testing machine (MZ-4061, Jiangsu Mingzhu Testing Machinery Co., Ltd.) according to GB / T1689-2014 standard.

[0073] In the following examples and comparative examples, the number of parts refers to parts by weight.

[0074] Example 1

[0075] (1) 60g of silica (SiO2) (VN3) and 20g of montmorillonite (MMT) (K-10) were placed in beakers containing 500ml of deionized water and 200ml of anhydrous ethanol, respectively. The solutions were dispersed in an ultrasonic cleaner for 50min. Then, the two solutions were mixed and reacted in an 80℃ constant temperature water bath at 400rpm for 8h. The resulting sample was then centrifuged and washed at 5000rpm for 13min using a high-speed centrifuge. Finally, the sample was freeze-dried to obtain the multidimensional filler SiO2@MMT.

[0076] (2) Take 100 parts of solution-polymerized styrene-butadiene rubber and plasticize it in a two-roll mill (with cooling water). Then, add 80 parts of SiO2@MMT in multiple batches and mix to ensure the filler is fully and evenly dispersed. Mix 8 parts of Si69, 3 parts of zinc oxide, 2 parts of stearic acid, 2 parts of antioxidant 4010NA and 1.5 parts of paraffin wax in the two-roll mill for 15 minutes. After mixing evenly, heat treat it at 150℃ for 5 minutes on the hot rolls of the two-roll mill. After cooling, add 2 parts of accelerator CZ, 2 parts of accelerator D and 1.5 parts of sulfur, and continue mixing at room temperature for 5 minutes in the two-roll mill to obtain the compound. After standing for 12 hours, vulcanize the compound at 150℃ and 15MPa, and designate it as material 1#.

[0077] Example 2

[0078] (1) 70g of silica (SiO2) (VN3) and 10g of montmorillonite (MMT) (KSF) were placed in beakers containing 500ml of deionized water and 200ml of anhydrous ethanol, respectively. The solutions were dispersed in an ultrasonic cleaner for 50min. Then, the two solutions were mixed and reacted in an 80℃ constant temperature water bath at 400rpm for 8h with continuous stirring. The resulting sample was then centrifuged and washed at 5000rpm for 13min using a high-speed centrifuge. Finally, the sample was freeze-dried to obtain the multidimensional filler SiO2@MMT.

[0079] (2) Take 100 parts of solution-polymerized styrene-butadiene rubber and plasticize it in a two-roll mill (with cooling water). Then, add 80 parts of SiO2@MMT in multiple batches and mix to ensure the filler is fully and evenly dispersed. Mix 8 parts of Si69, 3 parts of zinc oxide, 2 parts of stearic acid, 2 parts of antioxidant 4010NA and 1.5 parts of paraffin wax in the two-roll mill for 15 minutes. After mixing evenly, heat treat it at 150℃ for 5 minutes on the hot rolls of the two-roll mill. After cooling, add 2 parts of accelerator CZ, 2 parts of accelerator D and 1.5 parts of sulfur, and continue mixing at room temperature for 5 minutes in the two-roll mill to obtain the compound. After standing for 12 hours, vulcanize the compound at 150℃ and 15MPa, and designate it as material 2#.

[0080] Example 3

[0081] (1) 50g of silica (SiO2) (1165) and 30g of montmorillonite (MMT) (K-10) were placed in beakers containing 500ml of deionized water and 200ml of anhydrous ethanol, respectively. The solutions were dispersed in an ultrasonic cleaner for 50min. Then, the two solutions were mixed and reacted in an 80℃ constant temperature water bath at 400rpm for 8h with continuous stirring. The resulting sample was then centrifuged and washed at 5000rpm for 13min using a high-speed centrifuge. Finally, the sample was freeze-dried to obtain the multidimensional filler SiO2@MMT.

[0082] (2) Take 100 parts of solution-polymerized styrene-butadiene rubber and plasticize it in a two-roll mill (with cooling water). Then, add 80 parts of SiO2@MMT in multiple batches and mix to ensure the filler is fully and evenly dispersed. Mix 8 parts of Si69, 3 parts of zinc oxide, 2.5 parts of stearic acid, 3 parts of antioxidant 4010NA and 1.5 parts of paraffin wax in the two-roll mill for 15 minutes. After mixing evenly, heat treat it at 150℃ for 5 minutes on the hot rolls of the two-roll mill. After cooling, add 2 parts of accelerator CZ, 2 parts of accelerator D and 1.5 parts of sulfur, and continue mixing at room temperature for 5 minutes in the two-roll mill to obtain the compound. After standing for 12 hours, vulcanize the compound at 150℃ and 15MPa, and designate it as material 3#.

[0083] Example 4

[0084] (1) 60g of silica (SiO2) (383) and 20g of talc (Tl) (Mistron) were placed in beakers containing 500ml of deionized water and 200ml of anhydrous ethanol, respectively. The mixtures were dispersed in an ultrasonic cleaner for 50min. Then, the two solutions were mixed and stirred continuously at 400rpm for 8h in a constant temperature water bath at 80℃. The resulting sample was then centrifuged and washed at 5000rpm for 13min using a high-speed centrifuge. Finally, the sample was freeze-dried to obtain the multidimensional filler SiO2@Tl.

[0085] (2) Take 100 parts of solution-polymerized styrene-butadiene rubber and plasticize it in a two-roll mill (with cooling water). Then, add 80 parts of SiO2@Tl in multiple batches and mix to ensure the filler is fully and evenly dispersed. Mix 8 parts of Si69, 3 parts of zinc oxide, 2 parts of stearic acid, 2 parts of antioxidant 4010NA and 2 parts of paraffin wax in the two-roll mill for 15 minutes. After mixing evenly, heat treat it at 150℃ for 5 minutes on the hot rolls of the two-roll mill. After cooling, add 2 parts of accelerator CZ, 2 parts of accelerator D and 1.5 parts of sulfur, and continue mixing at room temperature for 5 minutes in the two-roll mill to obtain the compound. After standing for 12 hours, vulcanize the compound at 150℃ and 15MPa, and designate it as material 4#.

[0086] Example 5

[0087] (1) 60g of carbon black (CB) (N330) and 20g of carbon nanotubes (CNT) (NC7000) were placed in beakers containing 500ml of deionized water and 200ml of anhydrous ethanol, respectively. The mixtures were dispersed in an ultrasonic cleaner for 50min. Then, the two solutions were mixed and reacted in an 80℃ constant temperature water bath at 400rpm for 8h. The resulting sample was then centrifuged and washed at 5000rpm for 13min using a high-speed centrifuge. Finally, the sample was dried using a spray dryer to obtain the multidimensional filler CB@CNT.

[0088] (2) Take 100 parts of solution-polymerized styrene-butadiene rubber and plasticize it in a two-roll mill (with cooling water). Then, add 80 parts of CB@CNT in batches and mix to ensure the filler is fully and evenly dispersed. Mix 8 parts of Si69, 5 parts of zinc oxide, 3 parts of stearic acid, 2 parts of antioxidant 4010NA and 2 parts of paraffin wax in the two-roll mill for 15 minutes. After mixing evenly, heat treat it at 150℃ for 5 minutes on the hot rolls of the two-roll mill. After cooling, add 2 parts of accelerator CZ, 3 parts of accelerator D and 1.5 parts of sulfur, and continue mixing at room temperature for 5 minutes in the two-roll mill to obtain the compound. After standing for 12 hours, vulcanize the compound at 150℃ and 15MPa, and designate it as material 5#.

[0089] Example 6

[0090] (1) 60g of silica (SiO2) (JF555) and 20g of carbon nanotubes (CNTs) (Flotube9000) were placed in beakers containing 500ml of deionized water and 200ml of anhydrous ethanol, respectively. The mixtures were dispersed in an ultrasonic cleaner for 50min. Then, the two solutions were mixed and reacted in a constant temperature water bath at 80℃ with continuous stirring at 400rpm for 8h. The resulting sample was then filtered through a funnel. Finally, the sample was freeze-dried using a freeze dryer to obtain the multidimensional filler SiO2@CNT.

[0091] (2) Take 100 parts of natural rubber and plasticize it in a two-roll mill (with cooling water). Then, add 80 parts of SiO2@CNT in batches and mix to ensure the filler is fully and evenly dispersed. Mix 8 parts of Si69, 4 parts of zinc oxide, 2 parts of stearic acid, 3 parts of antioxidant 4010NA and 1.5 parts of paraffin wax in the two-roll mill for 15 minutes. After mixing evenly, heat treat it at 150℃ for 5 minutes on the hot rolls of the two-roll mill. After cooling, add 2 parts of accelerator CZ, 2 parts of accelerator D and 1.5 parts of sulfur, and continue mixing at room temperature for 5 minutes in the two-roll mill to obtain the compound. After standing for 12 hours, vulcanize the compound at 150℃ and 15MPa, and designate it as material 6#.

[0092] Example 7

[0093] (1) 60g of carbon black (CB)(N220), 10g of carbon nanotubes (CNT)(MWCNT), and 10g of montmorillonite (MMT)(KSF) were placed in beakers containing 200ml of deionized water and 35ml of anhydrous ethanol, respectively. The solutions were dispersed in an ultrasonic cleaner for 50min. Then, the two solutions were mixed and reacted in a constant temperature water bath at 50℃ with continuous stirring at 400rpm for 6h. The resulting sample was then centrifuged and washed at 5000rpm for 13min. Finally, the sample was dried using a spray dryer to obtain the multidimensional filler CB@CNT@MMT.

[0094] (2) Take 100 parts of butadiene rubber and plasticize it in a two-roll mill (with cooling water). Then, add 60 parts of CB@CNT@MMT in multiple batches and mix to ensure the filler is fully and evenly dispersed. Mix 1.2 parts of 3-mercaptopropylethoxybis(tetranylpentaethoxysiloxane), 3 parts of zinc oxide, 3 parts of stearic acid, 4 parts of antioxidant 4010NA, and 3 parts of paraffin wax in the two-roll mill for 20 minutes. After mixing evenly, heat treat it at 160℃ for 10 minutes on the hot rolls of the two-roll mill. After cooling, add 2 parts of accelerator CZ, 2 parts of accelerator D, and 3 parts of sulfur. Continue mixing at room temperature in the two-roll mill for 10 minutes to obtain the compound. After standing for 12 hours, vulcanize the compound at 160℃ and 15MPa. This compound is designated as material 7#.

[0095] Example 8

[0096] (1) Mix 90g of carbon black (CB)(N326) and 30g of halloysite nanotubes (HNT)(Dragonite) TM The samples were placed in beakers containing 300 ml of deionized water and 100 ml of anhydrous ethanol, respectively, and dispersed in an ultrasonic cleaner for 40 min. Then, the two solutions were mixed and reacted in a 70°C water bath with continuous stirring at 500 rpm for 9 h. The resulting sample was then washed by centrifugation at 6000 rpm for 10 min. Finally, the sample was dried in a vacuum oven to obtain the multidimensional filler CB@HNT.

[0097] (2) Take 100 parts of solution-polymerized styrene-butadiene rubber and plasticize it in a two-roll mill (with cooling water). Then, add 70 parts of CB@HNT in multiple batches and mix to ensure the filler is fully and evenly dispersed. Mix 1.5 parts of γ-aminopropyltriethoxysilane, 3 parts of zinc oxide, 2 parts of stearic acid, 4 parts of antioxidant 4010NA, and 3 parts of paraffin wax in the two-roll mill for 5 minutes. After mixing evenly, heat-treat at 150℃ for 5 minutes on the hot rolls of the two-roll mill. After cooling, add 2 parts of accelerator CZ, 2 parts of accelerator D, and 1.5 parts of sulfur. Continue mixing at room temperature for 5 minutes in the two-roll mill to obtain the compound. After standing for 12 hours, vulcanize the compound at 150℃ and 15MPa. This compound is designated as material 8#.

[0098] Comparative Example 1

[0099] The difference from Example 1 is that 80 parts of the multidimensional filler SiO2@MMT in Example 1 were replaced with 80 parts of precipitated silica VN3.

[0100] The preparation conditions of the rubber composite material in Comparative Example 1 were the same as those in Example 1, and the vulcanized rubber composite material was obtained, denoted as material a#.

[0101] Comparative Example 2

[0102] The difference from Example 1 is that 60 parts of silica VN3 + 20 parts of montmorillonite (K-10) replaced the 80 parts of multidimensional filler SiO2@MMT in Example 1;

[0103] The preparation conditions of the rubber composite material in Comparative Example 2 were the same as those in Example 1, and the vulcanized rubber composite material was obtained, denoted as material b#.

[0104] Table 1. Performance test results of the rubber composite materials prepared in Examples 1-8 and Comparative Examples 1-2.

[0105]

[0106] RPA-tanδ(7%) refers to the loss tangent at a strain of 7%, which is usually used to describe the magnitude of rolling resistance. The smaller the value, the smaller the rolling resistance. DMA-tanδ(0℃) is usually used to describe the wet skid resistance of a material. The larger the value, the better the wet skid resistance.

[0107] As shown in Table 1, different proportions of SiO2@MMT were added in Examples 1-3, and the study found that SiO2@MMT has good dispersibility in solution-polymerized styrene-butadiene rubber. Furthermore, with the increase of MMT content, SiO2@MMT exhibits better dispersion in solution-polymerized styrene-butadiene rubber, increasing elongation and wet slip resistance, while gradually decreasing rolling resistance.

[0108] Compared with Comparative Example 1, Examples 1 and 2 show significantly improved elongation and wet skid resistance of the composite material; furthermore, Examples 1 and 2 exhibit higher DMA-tanδ peak values, indicating that the multidimensional filler prepared in Examples 1 and 2 has better filler dispersibility compared to silica. Compared with Comparative Example 2, Examples 1 and 2 show significantly improved elongation and wet skid resistance of the composite material; furthermore, Example 1 exhibits a higher DMA-tanδ peak value, indicating that the multidimensional filler prepared in Example 1 has better filler dispersibility compared to a direct blend of equal amounts of silica and montmorillonite.

[0109] The RPA-tanδ (7%) of Example 1 was 0.132, the RPA-tanδ (7%) of Example 2 was 0.129, the RPA-tanδ (7%) of Comparative Example 1 was 0.145, and the RPA-tanδ (7%) of Comparative Example 2 was 0.140. Compared with Comparative Example 1, the rolling resistance of Examples 1-2 was lower; compared with Comparative Example 2, the rolling resistance of Example 1 was lower; and the RPA-tanδ (7%) of Examples 1-8 was 0.125-0.138, indicating that the rolling resistance of the multidimensional filler rubber composite material prepared by the present invention is low.

[0110] The compression fatigue temperature rise of Example 1 was 26.5℃, that of Example 2 was 25.4℃, that of Comparative Example 1 was 27.6℃, and that of Comparative Example 2 was 27.8℃. Compared with Comparative Example 1, Examples 1-2 had lower heat generation and lower compression fatigue temperature rise; compared with Comparative Example 2, Examples 1 had lower heat generation and lower compression fatigue temperature rise; the compression fatigue temperature rise of Examples 1-8 was 24.6-26.5℃, indicating that the multidimensional filler rubber composite material prepared by the present invention has lower heat generation and lower compression fatigue temperature rise.

[0111] The wear in Example 1 was 0.255 cm. 3 The wear rate in Example 2 was 0.246 cm. 3 The wear of Comparative Example 1 was 0.296 cm. 3 The wear of Comparative Example 2 was 0.285 cm. 3 Compared with Comparative Example 1, Examples 1-2 showed better wear resistance; compared with Comparative Example 2, Example 1 showed better wear resistance; the wear of Examples 1-8 was 0.237-0.255 cm. 3 This indicates that the multidimensional filler rubber composite material prepared by the present invention has good wear resistance.

[0112] Based on the test data in Table 1, the multidimensional filler rubber composite materials prepared in Examples 1 to 8 have low heat generation, good wear resistance, good wet skid resistance, and low rolling resistance, making them a high-performance rubber composite material for tire treads.

Claims

1. A multidimensional filler, obtained by reacting a mixture of at least two fillers of different dimensions; wherein the filler is a three-dimensional filler, a two-dimensional filler or a one-dimensional filler, and the surface of the filler contains hydroxyl groups.

2. The multidimensional packing material as described in claim 1, characterized in that: The one-dimensional filler is at least one of carbon fiber, wollastonite, carbon nanotubes, and halloysite nanotubes; and / or, The two-dimensional filler is at least one selected from montmorillonite, talc, graphene, graphene oxide, boron nitride, kaolin, and mica sheets; and / or, The three-dimensional filler is at least one of carbon black, silica, barium sulfate, and alumina.

3. A method for preparing the multidimensional filler as described in claim 1 or 2, comprising the following steps: The multidimensional filler is obtained by dispersing fillers comprising at least two different dimensions in a solvent and then performing a condensation reaction.

4. The method for preparing the multidimensional filler as described in claim 3, characterized in that: When the multidimensional filler is obtained by reacting a mixture of two fillers with different dimensions, the mass ratio of the two fillers is 1:(0.01~100), preferably 1:(0.1~8); when the multidimensional filler is obtained by reacting a mixture of three or more fillers with different dimensions, at least two of the fillers have different dimensions, and the mass of any one dimension filler accounts for not less than 1% of the total mass of the multidimensional filler, preferably not less than 10%; and / or, The solvent is at least one selected from water, ethanol, benzene, toluene, xylene, dichloromethane, dichloroethane, cyclohexane, and n-hexane; and / or, The ratio of the total mass of the filler to the volume of the solvent is 1–100 g filler / 100 mL solvent, preferably 6–30 g filler / 100 mL solvent; and / or, The condensation reaction is carried out under stirring, preferably at a stirring speed of 100–800 rpm, more preferably at 300–500 rpm; even more preferably, the stirring is carried out in at least one of a mechanical stirrer, a high-speed disperser, and an ultrasonic cleaner; and / or, The condensation reaction is performed at a temperature of 20–100°C, preferably 50–80°C; and / or, The condensation reaction takes 0.5–12 hours, preferably 5–9 hours; and / or, The product is post-processed after the reaction, including separation and removal of solvent and drying; preferably, the separation method is at least one of filtration, centrifugation, and sedimentation, preferably centrifugation; and / or, the drying method is at least one of vacuum drying, atmospheric pressure drying, microwave drying, spray drying, and freeze drying.

5. The application of a multidimensional filler as described in claim 1 or 2, or a multidimensional filler obtained by the preparation method as described in claim 3 or 4, in rubber composite materials.

6. A multidimensional filler rubber composite material, comprising the following components based on 100 parts by weight of rubber: 100 parts by weight of rubber; Multidimensional filler: 20-100 parts by weight; preferably 60-80 parts by weight; 0.2 to 15 parts by weight of silane coupling agent; preferably 1.2 to 8 parts by weight; Activator: 1-10 parts by weight; preferably 3-8 parts by weight; Plasticizer: 0.5 to 5 parts by weight; preferably 1 to 3 parts by weight; Anti-aging agent: 1-5 parts by weight; preferably 2-4 parts by weight; Accelerator: 1-8 parts by weight; preferably 2-6 parts by weight; Vulcanizing agent: 0.5 to 4 parts by weight; preferably 1 to 3 parts by weight. The multidimensional filler is the multidimensional filler according to claim 1 or 2, or the multidimensional filler obtained by the preparation method according to claim 3 or 4.

7. The multidimensional filler rubber composite material as described in claim 6, characterized in that: The rubber is at least one selected from solution-polymerized styrene-butadiene rubber, emulsion-polymerized styrene-butadiene rubber, nitrile rubber, acrylate rubber, polyurethane rubber, polyisoprene rubber, ethylene propylene rubber, chloroprene rubber, cis-butadiene rubber, butyl rubber, fluororubber, and natural rubber; and / or, The silane coupling agent is at least one of γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, bis-[γ-(triethoxysilyl)propyl]tetrasulfide, 3-(trimethoxysilyl)propyl methacrylate, (3-glycidoxy)trimethoxysilane, bis-[3-(triethoxysilyl)propyl]disulfide, and 3-mercaptopropylethoxybis(tetrazylpentaethoxysiloxane); and / or, The activator is at least one selected from zinc oxide, stearic acid, zinc fatty acid, lead oxide, magnesium oxide, and amines; the amine is at least one selected from ethylenediamine phosphate, propylenediamine phosphate, ammonium sulfate, and ammonium chloride; and / or, The plasticizer is at least one of petroleum-based plasticizers, fatty oil-based plasticizers, and pine oil-based plasticizers; preferably at least one of paraffin wax, aromatic oils, and naphthenic oils; and / or... The antioxidant is at least one of p-phenylenediamine, phenol, and organosulfur antioxidants; preferably at least one of antioxidant 4010NA, antioxidant 4020NA, and antioxidant RD; and / or The accelerator is at least one selected from sulfenamides, thiazoles, guanidines, thiurams, and thiocarbamates, preferably at least one selected from N-cyclohexyl-2-benzothiazole sulfenamide and diphenylguanidine; and / or, The vulcanizing agent is at least one of di-tert-butyl peroxide, sulfur, bis(2,5) vulcanizing agent, and dicumyl peroxide.

8. A method for preparing a multidimensional filler rubber composite material as described in claim 6 or 7, comprising the following steps: (1) Mix the components including the multidimensional filler, rubber, silane coupling agent, activator, plasticizer, and antioxidant to obtain mixture A; (2) After heat treatment, the mixture A obtained in step (1) is mixed with vulcanizing agent and accelerator to obtain mixture B; (3) The mixture B obtained in step (2) is vulcanized to obtain the multidimensional filler rubber composite material.

9. The method for preparing the multidimensional filler rubber composite material as described in claim 8, characterized in that: In step (1), The mixing method can be any of the mixing methods commonly used in rubber processing in the prior art, preferably mechanical mixing, more preferably mechanical mixing using at least one of a two-roll mill, a mixer, or a screw mixer; and / or, The mixing temperature is 20–60℃; and / or, The mixing time is 5–120 min, preferably 5–20 min; and / or, In step (2), The heat treatment temperature is 140–160°C; and / or, The heat treatment time is 5–10 min; and / or, The mixing temperature is 20–60℃; and / or, The mixing time is 2–30 min, preferably 5–10 min; and / or, In step (3), The vulcanization temperature is 120–170°C, preferably 140–160°C; and / or, The vulcanization pressure is 10-20 MPa, preferably 12-15 MPa.

10. The application of a multidimensional filler rubber composite material as described in claim 6 or 7 or a multidimensional filler rubber composite material obtained by the preparation method as described in claim 8 or 9 in tires, preferably in tread compound.

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