Filler composition capable of reducing tire rolling resistance, low rolling resistance tire rubber material, preparation method thereof, and tire

Abstract

This application discloses a filler composition capable of reducing tire rolling resistance, a low-rolling-resistance tire rubber compound, a preparation method thereof, and a tire, belonging to the field of tire rubber technology. The filler composition capable of reducing tire rolling resistance described herein is composed of raw materials comprising white carbon black and a modified graphene oxide masterbatch. The modified graphene oxide masterbatch is produced by heat-treating a mixture of the graphene oxide masterbatch and a polysulfide compound. The chemical formula of the polysulfide compound is: #imgabs0#, where 2≤n≤5. On the one hand, the filler composition of the present application can combine silica and modified graphene oxide masterbatch based on adsorption to block the graphene oxide flakes, effectively promoting the dispersion of the combined filler in the rubber matrix; on the other hand, it can improve the compatibility of graphene oxide with the rubber matrix, and based on the fact that the modified graphene oxide can participate in the cross-linking reaction of the rubber, the interfacial bonding is significantly enhanced; thirdly, it can catalyze the silanization reaction of silica and the silane coupling agent, effectively improving the interfacial interaction between silica and the rubber matrix, thereby effectively enhancing the reinforcement effect of the combined filler and reducing the rolling resistance of the tread rubber through the synergistic effect of modified graphene oxide, silica and the silane coupling agent.

Description

Technical Field

[0001] The present invention belongs to the technical field of tire rubber, and in particular relates to a filler composition capable of reducing tire rolling resistance, a low rolling resistance tire rubber material, a preparation method thereof, and a tire. Background Art

[0002] The rolling resistance, wet skid resistance, and wear resistance of tread compounds each affect a tire's fuel efficiency, safety, and service life. Improving one property often reduces one or both of the others, creating a mutually dependent and interconnected relationship known as the "Magic Triangle." Research has shown that the addition of fillers improves the compound's tensile strength, aging resistance, and wear resistance to varying degrees, while significantly impacting the "Magic Triangle" of properties. This has made filler-modified tire compound performance a hot topic of research.

[0003] Due to the cost and high binding energy of graphene, it is difficult to realize the real application of graphene as a single filler in the preparation of tire rubber. The use of white carbon black and graphene oxide as a filler can reduce the amount of graphene used, save costs, and utilize the hybrid synergistic effect of the filler to improve the dispersion of graphene in the rubber matrix, which is an effective measure to prepare high-performance graphene tire rubber materials. However, due to the poor compatibility of graphene oxide with the rubber matrix, the interface bonding between graphene oxide and the rubber matrix is ​​poor, which limits the actual reinforcement effect. In order to improve the problem of poor compatibility between graphene oxide and the rubber matrix, the relevant field provides many graphene oxide modification methods. For example, J.Phys.D et al. non-covalently modified graphene oxide with sodium 12α-dihydroxy-5β-cholanoate to improve the compatibility of graphene oxide with the rubber matrix; Small et al. enhanced the interface bonding between rubber and graphene oxide by grafting 2-acrylamide on the surface of graphene oxide. In addition, how to improve the synergistic reinforcement effect of graphene and silica in tire rubber has always been a major challenge facing this field.

[0004] As mentioned above, common graphene modification methods generally involve complex chemical modification processes, there are problems such as the use of organic solvents, poor controllability, high difficulty in scale, and it is difficult to be actually applied to industrial products such as tires, and the dispersion effect is poor, the interface effect is weak, and the performance of the prepared rubber composite material is difficult to improve the dynamic service performance (low rolling resistance, high wet-slip resistance) of the rubber compound at the same time, tensile strength, aging resistance and wear resistance, and it is impossible to be applied to tire formulations. In addition, while graphene oxide is modified, the interaction between graphene and white carbon black must also be considered, so that synergistic reinforcement can be achieved by utilizing graphene oxide / white carbon black combination to fill tire rubber materials, and obtain tire rubber materials with low rolling resistance and high wet-slip resistance. Therefore, it is necessary to develop a modification method and filler composition based on graphene oxide to provide a new solution for preparing high-performance tire rubber materials with low rolling resistance. Summary of the Invention

[0005] The present application discloses a filler composition capable of reducing tire rolling resistance, a low rolling resistance tire rubber compound, a preparation method thereof, and a tire, aiming to solve the technical problems that the existing filler composed of white carbon black and graphene oxide has a poor actual reinforcement effect, and that the modification strategy for improving the compatibility of graphene oxide with the rubber matrix has poor controllability, causes great environmental pollution, and cannot simultaneously improve the tensile strength, aging resistance, and wear resistance of the rubber compound.

[0006] In order to achieve the above objectives, the technical solutions adopted in this application are:

[0007] The first aspect of the present application provides a filler composition capable of reducing tire rolling resistance, wherein the raw material composition of the filler composition comprises:

[0008] White carbon black; and a modified graphene oxide masterbatch, wherein the modified graphene oxide masterbatch is generated by mixing and heat treating the graphene oxide masterbatch and a polysulfide compound;

[0009] The chemical formula of the polysulfide compound is:

[0010]

[0011] Among them, 2≤n≤5.

[0012] In a preferred embodiment, the mass ratio of the white carbon black to the modified graphene oxide masterbatch is 100:(5-50).

[0013] In a preferred embodiment, when the graphene oxide masterbatch and the polysulfide compound are mixed and heat-treated, the mass ratio of the graphene oxide masterbatch to the polysulfide compound is 100:(0.05-1).

[0014] In a preferred embodiment, the graphene oxide masterbatch comprises natural rubber latex and graphene oxide compounded in the natural rubber latex;

[0015] The mass percentage concentration of the graphene oxide is 5-20wt%.

[0016] In a preferred embodiment, the heat treatment temperature is 80-170° C., and the heat treatment time is 1-8 minutes.

[0017] A second aspect of the present application provides a low rolling resistance tire rubber compound, wherein the raw material composition of the low rolling resistance tire rubber compound comprises:

[0018] Tire rubber base;

[0019] Silane coupling agent;

[0020] The filler composition according to any one of claims 1 to 3; and

[0021] Additives available for tire compounds.

[0022] In a preferred embodiment, the mass ratio of the tire rubber base material to the filler composition is 100:(40-70).

[0023] In a preferred embodiment, the additives available for the tire rubber compound include: an antioxidant, a resin, a dispersant, and a curing package.

[0024] The third aspect of the present application provides a method for preparing the low rolling resistance tire rubber material of the present application, the preparation method comprising the steps of:

[0025] According to the raw material composition of the tire rubber compound, the raw materials are mixed, kneaded and hot-pressed and vulcanized to obtain the low rolling resistance tire rubber compound.

[0026] A fourth aspect of the present application provides a tire containing the low rolling resistance tire rubber compound of the present application.

[0027] Compared with the prior art, the advantages or beneficial effects of the embodiments of the present application include at least:

[0028] The filler composition provided herein comprises a graphene oxide masterbatch grafted with a polysulfide compound represented by the chemical formula, and then used in combination with silica. Thanks to the modified graphene masterbatch, silica and graphene oxide masterbatch combine through adsorption, blocking the graphene oxide flakes, thereby inhibiting their self-agglomeration and effectively promoting the dispersion of the combined filler in the rubber matrix. Furthermore, the compatibility of graphene oxide with the rubber matrix is ​​improved, and the polysulfide compound grafted onto the graphene oxide can participate in the cross-linking reaction of the rubber, significantly enhancing the interfacial bonding between the graphene oxide and the rubber matrix. Thirdly, the amino functional groups grafted onto the surface of the modified graphene oxide catalyze the silanization reaction of silica with a silane coupling agent, effectively improving the interfacial interaction between silica and the rubber matrix. This, through the synergistic effect of the modified graphene oxide, silica, and silane coupling agent, effectively enhances the reinforcing effect of the combined filler and reduces the rolling resistance of the tread rubber. In addition, the modified graphene oxide masterbatch of the present application does not use organic solvents and the process is controllable, making it easy to produce on a large scale. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] To more clearly illustrate the technical solutions of the embodiments of this application, the following briefly introduces the drawings required for describing the embodiments. Obviously, the drawings described below are only some of the embodiments described in this application. For those skilled in the art, other drawings can be derived from these drawings without inventive effort.

[0030] Figure 1 The polysulfide compound S provided in the embodiment of the present application nIR spectrum of (n=2). DETAILED DESCRIPTION

[0031] The following will be combined with the accompanying drawings in the embodiments of this application to clearly and completely describe the technical solutions in the embodiments of this application. Obviously, the described embodiments are part of the embodiments of this application, not all of the embodiments. Based on the embodiments in this application, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of this application.

[0032] In the following description of this embodiment, the term "and / or" is used to describe the association relationship between associated objects, indicating that three relationships can exist. For example, A and / or B can represent: A exists alone, B exists alone, and A and B exist simultaneously. A and B can be singular or plural; the single symbol " / " means "or".

[0033] In the following description of this embodiment, the term "at least one" refers to one or more, and "plurality" refers to two or more. "At least one of the following" or similar expressions refers to any combination of these items, including any combination of single items or plural items. For example, "at least one of A, B or C", or "at least one of A, B and C" can mean any one of A, B, C, or A+B, or A+C, or B+C, or A+B+C, where A, B, and C can be single or multiple, respectively.

[0034] In the following description of this embodiment, the order of serial numbers does not mean the order of execution. Some or all steps can be executed in parallel or sequentially. The execution order of each process should be determined by its function and internal logic, and should not constitute any limitation on the implementation process of this embodiment.

[0035] In the following description of the present embodiment, the numerical range should be understood to also specifically disclose each intermediate value between the upper and lower limits of the range. Each smaller range between any stated value or intermediate value in the stated range and any other stated value or intermediate value in the stated range is also included in the present embodiment, and the upper and lower limits of the smaller ranges may be independently included or excluded in the range.

[0036] Unless otherwise indicated, the technical / scientific terms used in this embodiment have the same meanings as those generally understood by those skilled in the art. Although this application only describes preferred methods and materials, any similar or equivalent methods and materials may also be used in the implementation or testing of this application. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and / or materials related to the documents. In the event of any conflict with any incorporated document, the content of this specification shall prevail.

[0037] In a first aspect, the present invention provides a filler composition that can reduce tire rolling resistance. The filler composition of the present invention comprises:

[0038] White carbon black; and a modified graphene oxide masterbatch, wherein the modified graphene oxide masterbatch is generated by mixing and heat treating the graphene oxide masterbatch and a polysulfide compound;

[0039] The chemical formula of the polysulfide compound is:

[0040]

[0041] Among them, 2≤n≤5.

[0042] It should be noted that the examples of this application do not limit the specific sources and types of materials such as white carbon black and graphene oxide masterbatch, which can be obtained through commercial channels or synthesized in the laboratory. However, to facilitate the implementation of the above-mentioned technical solutions in this field, the examples of this application also provide a method for preparing a polysulfide compound, preferably comprising:

[0043] After the molten sulfur and vinyl monomer are stirred and reacted for 2 to 8 hours, monosubstituted aniline is added and stirred and reacted for 1 to 4 hours under the protection of inert gas. The reactants are then dissolved in tetrahydrofuran, the unreacted sulfur is filtered out, and the filtrate is poured into ethanol for precipitation to obtain a polysulfide compound.

[0044] It should be noted that the examples of the present application do not limit the materials, material ratios and related parameters involved in the preparation method. For example, the mass percentages of sulfur, vinyl monomer and mono-substituted aniline may preferably be (50-70%): (10-30%): (20-50%); the vinyl monomer may preferably be one or more of styrene and divinylbenzene; and the mono-substituted aniline may preferably be one or more of hydroxyaniline, methylaniline, 4-chloroaniline and m-phenylenediamine.

[0045] As a specific example: 5 g of sulfur was added to a three-necked flask equipped with a mechanical stirrer, heated to 119°C to melt it, and 5 g of hydroxyaniline was added under argon protection. The mixture was stirred and reacted for 2 h. After the reaction was completed, the reactant was dissolved in tetrahydrofuran and filtered to remove the unreacted sulfur. The filtered solution was then poured into ethanol to obtain a polysulfide compound S. n Its chemical formula is: Where n=2.

[0046] In order to test the successful synthesis of polysulfide compound S2, the present invention provides a spectrum of polysulfide compound S2, specifically: Figure 1 shown.

[0047] according to Figure 1 It can be seen that 3357~3459cm-1 The signal peak at 1607 cm comes from the NH of the amino group in the polysulfide compound; -1 The signal peak at 1463cm is attributed to the stretching vibration peak of CN; -1 The vibration peak of the aromatic ring is at 1015cm -1 The absorption peak of the CS bond is at 550cm -1 The absorption peak at is the SS bond, and the results show that the polysulfide compound was successfully prepared.

[0048] The filler composition provided herein comprises a graphene oxide masterbatch grafted with a polysulfide compound represented by the chemical formula, and then used in combination with silica. Thanks to the modified graphene masterbatch, silica and graphene oxide masterbatch combine through adsorption, blocking the graphene oxide flakes, thereby inhibiting their self-agglomeration and effectively promoting the dispersion of the combined filler in the rubber matrix. Furthermore, the compatibility of graphene oxide with the rubber matrix is ​​improved, and the polysulfide compound grafted onto the graphene oxide can participate in the cross-linking reaction of the rubber, significantly enhancing the interfacial bonding between the graphene oxide and the rubber matrix. Thirdly, the amino functional groups grafted onto the surface of the modified graphene oxide catalyze the silanization reaction of silica with a silane coupling agent, effectively improving the interfacial interaction between silica and the rubber matrix. This, through the synergistic effect of the modified graphene oxide, silica, and silane coupling agent, effectively enhances the reinforcing effect of the combined filler and reduces the rolling resistance of the tread rubber. In addition, the modified graphene oxide masterbatch of the present application does not use organic solvents and the process is controllable, making it easy to produce on a large scale.

[0049] In the embodiments of the present application, the mass ratio of the silica to the modified graphene oxide masterbatch can be preferably 100:(5-50), for example, (100:5), (100:10), (100:15), (100:20), (100:25), (100:30), (100:35), (100:40), (100:45), (100:50), or any ratio within the mass ratio range. In the embodiments of the present application, the composition of the filler in the tire rubber composition can be adjusted by using the mass ratio, and the synergistic effect of the modified graphene and silica can be utilized to achieve efficient reinforcement, low rolling resistance, and high wet skid resistance of the tire rubber. In particular, the hybridization of modified graphene and silica can inhibit mutual agglomeration and improve their dispersion in the rubber matrix. At the same time, the polysulfide compound and silane coupling agent grafted onto the graphene oxide provide covalent bonding for the interfaces between graphene, silica and rubber, respectively, and the amino groups grafted onto the graphene oxide can catalyze the silanization reaction, thereby significantly improving the dynamic properties of the tire rubber composition.

[0050] In the embodiment of the present application, when the graphene oxide masterbatch and the polysulfide compound are mixed and heat-treated, the mass ratio of the graphene oxide masterbatch to the polysulfide compound can be preferably 100:(0.05-1), such as (100:0.05), (100:0.1), (100:0.2), (100:0.3), (100:0.5), (100:0.8), (100:1) or any ratio within the mass ratio range. In the embodiment of the present application, the mass ratio can be used to enable the modified graphene oxide and silica to produce a synergistic effect to achieve efficient reinforcement, low rolling resistance and high wet skid resistance of the tire rubber. In particular, the polysulfide compound and the silane coupling agent grafted onto the graphene oxide provide covalent bonding at the interface between the graphene, silica and rubber, respectively, and the amino group grafted onto the graphene oxide can catalyze the silanization reaction, thereby significantly improving the dynamic performance of the tire rubber composition.

[0051] In an embodiment of the present application, the graphene oxide masterbatch comprises natural rubber latex and graphene oxide compounded in the natural rubber latex. The mass percentage concentration of the graphene oxide can preferably be 5-20wt%, such as 5wt%, 10wt%, 15wt%, 20wt%, or any ratio within the mass percentage concentration range. In this embodiment of the present application, by using the mass percentage concentration, a masterbatch can be prepared from graphene oxide to improve the dispersion of graphene oxide in the rubber matrix, while also providing a simple and easily scalable processing platform for thermal reduction treatment and polysulfide compound modification of graphene oxide. In short, by controlling the percentage concentration, a graphene oxide masterbatch with good dispersibility and easy modification can be prepared.

[0052] It should be noted that the present invention does not limit the preparation method of the graphene oxide masterbatch, and the synthesis can be carried out according to the steps disclosed in the art. To facilitate the implementation of the technical solution of this application in the art, this application provides an example preparation method of the graphene oxide masterbatch, which specifically includes:

[0053] The graphene oxide aqueous dispersion is added to the natural rubber latex and stirred to mix uniformly at a stirring rate of 100-500 r / min. A 2-8 wt% calcium chloride aqueous solution is sprayed at a spraying rate of 0.5-3 L / min. After spraying, the mixture is flocculated and dried to obtain a graphene oxide masterbatch. The amount of the graphene oxide aqueous dispersion added is calculated as 5-20 wt% of the mass percentage of the graphene oxide relative to the natural rubber latex.

[0054] As a specific example: the graphene oxide dispersion is ultrasonically treated (power of 70kw, time of 20min), and then the natural rubber latex NR is pumped into the ultrasonically treated graphene oxide dispersion at a stirring rate of 100r / min and stirred and mixed, and then an 8wt% calcium chloride aqueous solution is sprayed at a flow rate of 2L / min. The mixture of natural latex NR and graphene oxide is flocculated to obtain a brown slurry, and the brown slurry is pumped into a centrifuge at a speed of 1900r / min for 20min to obtain a blocky brown solid; the brown solid is dried at a temperature of 40°C for 36h to obtain a graphene oxide masterbatch GO / NR. Wherein, the mass percentage concentration of the graphene oxide relative to the natural latex NR is 10wt%.

[0055] The preparation process of modified graphene oxide masterbatch includes:

[0056] Polysulfide S n Add the graphene oxide masterbatch GO / NR into the internal mixer and mix with heat treatment to obtain modified graphene masterbatch S n -GO / NR. The mixed heat treatment temperature is 80-170°C, and the heat treatment time is 1-8 minutes. In an exemplary description, the heat treatment temperature is 80°C, and the time is 1 minute, 3 minutes, or 8 minutes; or the heat treatment temperature is 150°C, and the time is 1 minute, 3 minutes, or 8 minutes; or the heat treatment temperature is 170°C, and the time is 1 minute, 3 minutes, or 8 minutes.

[0057] In a second aspect, the present invention provides a low rolling resistance tire rubber compound. The raw material composition of the low rolling resistance tire rubber compound of the present invention comprises:

[0058] Tire rubber base;

[0059] Silane coupling agent;

[0060] The filler composition described herein above; and

[0061] Additives available for tire compounds.

[0062] It should be noted that the tire rubber base material can be various general tire rubbers in the art, and an example is described as a mixture of natural rubber and solution-polymerized styrene-butadiene rubber. The mass ratio of natural rubber to solution-polymerized styrene-butadiene rubber can preferably be (10-40):(60-90), such as (10:90), (20:80), (30:70), (40:60), etc. To obtain a tire rubber with excellent overall performance, solution-polymerized styrene-butadiene rubber / natural rubber is preferably 70 / 30. Of course, other general tire rubbers can also be used, and the present embodiment will not be described in detail here.

[0063] In the embodiment of the present application, the mass ratio of the tire rubber base material to the filler composition can be preferably 100:(40-70), for example, (100:40), (100:45), (100:50), (100:55), (100:60), (100:65), (100:70). Among them, the embodiment of the present application can prepare a tire rubber composition with practical performance by controlling the above mass ratio. By adjusting the amount and composition of the filler in the tire rubber composition, the modified graphene oxide and the white carbon black can produce a synergistic effect to achieve efficient reinforcement, low rolling resistance and high wet skid resistance of the tire rubber. In particular, the hybridization of modified graphene and silica can inhibit mutual agglomeration and improve their dispersion in the rubber matrix. At the same time, the polysulfide compound and silane coupling agent grafted onto the graphene oxide provide covalent bonding for the interfaces between graphene, silica and rubber, respectively, and the amino groups grafted onto the graphene oxide can catalyze the silanization reaction, thereby significantly improving the dynamic properties of the tire rubber composition.

[0064] In the present application embodiment, the available auxiliary agent of the tire rubber material refers to various auxiliary agents commonly used in tire rubber material, and can include antioxidant, resin, dispersant and curing bag etc.Wherein, the present application embodiment is not limited for the specific source and composition and consumption of antioxidant, resin, dispersant and curing bag.As an example description, antioxidant can be one or both of antioxidant RD, 6PPD, and the mass ratio of antioxidant to tire rubber base material is (1-3): 100;Dispersant can be dispersant TDAE (environmentally friendly aromatic oil / rubber filler oil), and the mass ratio of dispersant to tire rubber base material is (2-5): 100;Resin can be the common additive of tire rubber material, and can be one or more of phenolic resin, C5 resin, coumarone-indene resin, styrene resin, terpene resin, and the mass ratio of resin to tire rubber base material is (4-18): 100.Certainly, the present application embodiment is not limited for specific auxiliary agent type, auxiliary agent composition and consumption, and is based on the generality of this area.

[0065] In the embodiment of the present application, the material composition of the vulcanization package includes stearic acid, zinc oxide, accelerator and sulfur. Wherein, the accelerator can be preferably one or both of accelerator NS and accelerator DPG. The addition amount of the vulcanization package is (0.6-2.4): (1-4): (3.5-5.5): 100 according to the mass ratio of accelerator, stearic acid, zinc oxide and tire rubber base material. In addition, in order to improve the performance-enhancing effect of the filler composition of the present application on the tire rubber base material, the mass ratio of silane coupling agent to tire rubber base material is (3-8): 100. Of course, the specific source and model of the embodiment of the present application for the silane coupling agent are not limited, and can be various silane coupling agents known in the art.

[0066] In a third aspect, the embodiments of the present application further provide a method for preparing the low rolling resistance tire rubber compound of the present application, the method preferably comprising:

[0067] According to the raw material composition of the tire rubber compound, the raw materials are mixed, kneaded and hot-pressed and vulcanized to obtain the low rolling resistance tire rubber compound.

[0068] In a preferred embodiment, the filler composition, tire rubber base material, and silane coupling agent are first mixed in an internal mixer to form a rubber mix. The rubber mix is ​​then transferred to an open mixer and added with additives including, but not limited to, zinc oxide, stearic acid, accelerators, and sulfur. After standing for 24 hours, the low rolling resistance tire rubber mix is ​​prepared by hot press vulcanization. The mixing temperature is preferably 80-170°C and the mixing time is 1-8 minutes.

[0069] Fourthly, embodiments of the present application provide a tire containing the low rolling resistance tire compound of the present application. Given that the filler composition of the present application effectively enhances reinforcement and reduces the rolling resistance of the tread rubber, the tire of the present application exhibits excellent dynamic service performance, including low rolling resistance, low heat buildup, and wet skid resistance.

[0070] The technical solution of the present application will be further described below in conjunction with specific embodiments.

[0071] Example 1

[0072] This embodiment provides a filler composition S2-GO / NR-white carbon black, the raw material composition of which includes:

[0073] 100g of white carbon black; and

[0074] 30 g of modified graphene oxide masterbatch S2-GO / NR;

[0075] The preparation process of the filler composition S2-GO / NR-silica includes:

[0076] The graphene oxide masterbatch GO / NR prepared above and the polysulfide compound S2 were added into an internal mixer at a mass ratio of 100:0.5, mixed and heat-treated at 150°C for 3 minutes to obtain a modified graphene oxide masterbatch S2-GO / NR.

[0077] The modified graphene oxide masterbatch S2-GO / NR and white carbon black are stirred and mixed to obtain a filler composition S2-GO / NR-white carbon black.

[0078] Example 2

[0079] This embodiment provides a tire rubber material TYRE, the raw material composition of which is:

[0080] Natural rubber NR 30g, styrene-butadiene rubber SSBR 70g, antioxidant 6PPD 2g, RD 2g, silane coupling agent KH5505g, styrene resin 12g, dispersant TDAE 3g, stearic acid 4.5g, zinc oxide 2g, accelerator NS 1.8g, accelerator DPG 1.5g, sulfur 1.8g and S2-GO / NR-silica carbon black 40g;

[0081] The specific preparation process includes:

[0082] The natural rubber NR, styrene-butadiene rubber SSBR, S2-GO / NR-silica, silane coupling agent, resin, dispersant and antioxidant in the aforementioned parts by weight are added to an internal mixer and kneaded at 150° C. for 3 minutes to obtain a rubber mix; the rubber mix is ​​added to an open mixer, stearic acid, zinc oxide, an accelerator and sulfur are added at room temperature, and hot pressing vulcanization is performed to obtain a tire rubber compound TYRE-1.

[0083] Example 3

[0084] This embodiment provides a tire rubber compound TYRE-2, the raw material composition of which is:

[0085] Natural rubber NR 30g, styrene-butadiene rubber SSBR 70g, antioxidant 6PPD 2g, RD 2g, silane coupling agent KH5505g, styrene resin 12g, dispersant TDAE 3g, stearic acid 4.5g, zinc oxide 2g, accelerator NS 1.8g, accelerator DPG 1.5g, sulfur 1.8g and S2-GO / NR-silica carbon black 50g;

[0086] The specific preparation process includes:

[0087] The natural rubber NR, styrene-butadiene rubber SSBR, S2-GO / NR-silica, silane coupling agent, resin, dispersant and antioxidant in the aforementioned parts by weight are added to an internal mixer and kneaded at a temperature of 150° C. for 3 minutes to obtain a rubber mix; the rubber mix is ​​added to an open mixer, stearic acid, zinc oxide, an accelerator and sulfur are added at room temperature, and hot pressing vulcanization is performed to obtain a tire rubber compound TYRE-2.

[0088] Example 4

[0089] This embodiment provides a tire rubber compound TYRE-3, the raw material composition of which is:

[0090] Natural rubber NR 30g, styrene-butadiene rubber SSBR 70g, antioxidant 6PPD 2g, RD 2g, silane coupling agent KH5505g, styrene resin 12g, dispersant TDAE 3g, stearic acid 4.5g, zinc oxide 2g, accelerator NS 1.8g, accelerator DPG 1.5g, sulfur 1.8g and S2-GO / NR-silica carbon black 60g;

[0091] The specific preparation process includes:

[0092] The natural rubber NR, styrene-butadiene rubber SSBR, S2-GO / NR-silica, silane coupling agent, resin, dispersant and antioxidant in the aforementioned parts by weight are added to an internal mixer and kneaded at a temperature of 150° C. for 3 minutes to obtain a rubber mix; the rubber mix is ​​added to an open mixer, stearic acid, zinc oxide, an accelerator and sulfur are added at room temperature, and hot pressing vulcanization is performed to obtain a tire rubber compound TYRE-3.

[0093] Example 5

[0094] This embodiment provides a tire rubber compound TYRE-4, the raw material composition of which is:

[0095] Natural rubber NR 30g, styrene-butadiene rubber SSBR 70g, antioxidant 6PPD 2g, RD 2g, silane coupling agent KH5505g, styrene resin 12g, dispersant TDAE 3g, stearic acid 4.5g, zinc oxide 2g, accelerator NS 1.8g, accelerator DPG 1.5g, sulfur 1.8g and S2-GO / NR-silica carbon black 70g;

[0096] The specific preparation process includes:

[0097] The natural rubber NR, styrene-butadiene rubber SSBR, S2-GO / NR-silica, silane coupling agent, resin, dispersant and antioxidant in the aforementioned parts by weight are added to an internal mixer and kneaded at a temperature of 150° C. for 3 minutes to obtain a rubber mix; the rubber mix is ​​added to an open mixer, stearic acid, zinc oxide, an accelerator and sulfur are added at room temperature, and hot pressing vulcanization is performed to obtain a tire rubber compound TYRE-4.

[0098] The present application conducts static and dynamic performance tests on the tire rubber materials prepared in Examples 2-5. Among them, the tensile strength, elongation at break and 300% modulus of stress are measured according to the measurement standard of ISO37-2005, the test temperature is room temperature, and the tensile rate is 500 mm / min. The dynamic performance test conditions are: in tensile mode, temperature -100℃~100℃, heating rate 3℃ / min, frequency 1Hz, dynamic strain 0.5%, and tanδ at 0℃ is measured; temperature -10℃~100℃, heating rate 3℃ / min, frequency 10Hz, dynamic strain 5%, and tanδ at 60℃ is measured. The compression heat generation test conditions are: temperature 50℃, frequency 10Hz, and prestress 1MPa. The measurement results are shown in Table 1.

[0099] Table 1: Performance test results of tire rubber compounds in the examples

[0100] TYRE-1 TYRE-2 TYRE-3 TYRE-4 Tensile strength (MPa) 17.4 20.1 23.8 22.8 300% modulus (MPa) 8.4 10.2 13.4 12.6 Elongation at break (%) 451 467 478 470 0℃ tanδ (loss factor) 0.88 0.87 0.96 0.95 60℃ tanδ (loss factor) 0.147 0.133 0.084 0.102 Compression fatigue heat generation (℃) 22.1 20.5 15.6 18.5

[0101] As shown in Table 1, adding the filler composition can effectively improve wet skid resistance (increase in 0°C tanδ) and rolling resistance (decrease in 60°C tanδ), reduce compression heat generation, and improve dynamic service performance. Furthermore, the filler content of TYPE1-2 is too low to meet the mechanical performance requirements of the tread rubber. The filler content of TYPE4 is too high, and the interaction between the fillers exceeds the dispersing effect of the polysulfide compound, causing agglomeration. As a result, all performance is inferior to TYPE3. Overall, the performance of TYPE3 (Example 4) is the best.

[0102] In order to illustrate the actual effect of the filler composition of the present application, the present application uses Example 4 with the best filler addition amount screened as the experimental group, and provides Comparative Examples 1-3 for comparison. Among them:

[0103] The difference between Comparative Example 1 and Example 4 is that the added filler S2-GO / NR-silica is replaced by GO / NR-silica (graphene oxide and silica are mixed and heat-treated in a mass ratio of 50:100), and the other components and preparation process are the same as those in Example 4.

[0104] The difference between Comparative Example 2 and Example 4 is that the silane coupling agent KH550 is omitted, and the remaining components and preparation process are the same as those of Example 4.

[0105] The difference between Comparative Example 3 and Example 4 is that the added filler S2-GO / NR-white carbon black is replaced by S2-GO / NR (that is, the filler composition does not contain white carbon black), and the remaining components and preparation process are the same as Example 4.

[0106] The tire rubber compounds prepared in Comparative Examples 1-3 were subjected to performance tests, and the results are shown in Table 2.

[0107] Table 2: Performance test results of tire rubber compounds prepared in Example 4 and Comparative Examples 1-3

[0108] Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Tensile strength (MPa) 23.8 21.5 22.2 23.5 300% modulus (MPa) 13.4 11.4 15.2 6.3 Elongation at break (%) 478 453 404 895 0℃ tanδ (loss factor) 0.95 0.084 0.081 0.069 60℃ tanδ (loss factor) 0.084 0.107 0.105 0.021 Compression fatigue heat generation (℃) 15.6 18.8 19.7 10.4

[0109] As shown in Table 2, the combination of a polysulfide compound and a coupling agent in the present examples demonstrates improved wet skid resistance (higher tanδ at 0°C), lower rolling resistance (lower tanδ at 60°C), excellent dynamic service performance, and improved mechanical properties compared to Comparative Examples 1 and 2. Without the polysulfide compound (Comparative Example 1), the graphene is poorly dispersed, resulting in a weak reinforcing effect. The rubber exhibits higher compression heat generation and rolling resistance, leading to poor mechanical properties.

[0110] If the silane coupling agent is not added (Comparative Example 2), the agglomeration of the silica filler will be more serious, the compression heat generation and rolling resistance of the rubber compound will be too high, and the elongation at break will be too low, resulting in poor mechanical properties and dynamic service performance.

[0111] Without adding silica filler, although the compression fatigue heat generation and rolling resistance (60℃ tanδ) are the lowest, the modulus of the rubber compound is too low and does not meet the requirements of the tread rubber compound. In addition, the anti-skid performance (0℃ tanδ) is low and the dynamic service performance is poor.

[0112] The examples of the present application also studied the effects of mixing temperature and time on tire rubber properties. The specific mixing and time settings are shown in Table 3.

[0113] Table 3: Mixing temperature and time

[0114]

[0115] The present application tested the performance of tire rubber compounds prepared under different mixing conditions, and the results are shown in Table 4.

[0116] Table 4: Performance test results of tire rubber compounds prepared under different mixing conditions

[0117]

[0118] As shown in Table 4, the tensile strength, 300% modulus, and elongation at break of the rubber compound at 180°C are all lower than those at 80°C and 150°C. If the temperature is too high, the molecular chain of natural rubber will age and degrade, thereby affecting the tensile strength, modulus, and elongation at break of the sample. When the temperature is too low, the modification efficiency of the polysulfide compound is not high, and the dispersibility and interfacial effect of graphene oxide are not as good as at higher temperatures.

[0119] At 180°C, excessive heat treatment time causes the rubber molecular chains in the masterbatch to cleave, leading to significant degradation of various properties after 8 minutes of heat treatment. However, at 80°C, extended heat treatment time resulted in little change in the rubber compound prepared from the modified graphene oxide masterbatch, indicating that the reaction rate of polysulfide compounds is low at this temperature, making extended modification time ineffective. The "150°C heat treatment for 3 minutes" process used in Example 5 achieved the lowest compression fatigue heat generation, the lowest rolling resistance (tan@60°C), and the highest wet skid resistance (tan@0°C).

[0120] Therefore, in summary, the tread compound designed with the modified graphene oxide masterbatch obtained by heat treatment at 150°C for 3 min has better mechanical properties and dynamic service performance as well as lower fatigue temperature rise.

[0121] The present invention also studies the effect of the mass ratio of modified graphene oxide masterbatch and white carbon black in the filler composition on the performance of tire rubber. Specifically, Example 4 is used as the experimental group, and the modified graphene oxide masterbatch S in the filler composition is adjusted. n -GO / NR and silica mass ratio, and the properties of the obtained tire rubber compound were tested, and the results are shown in Table 5.

[0122] Table 5: Different silica and S n -Tire compound performance under GO / NR ratio

[0123] 100:5 100:10 100:20 100:30 100:40 100:50 100:55 Tensile strength (MPa) 15.2 15.6 23.2 22.8 15.9 15.4 14.4 300% modulus (MPa) 14.8 13.4 13.8 13.4 11.5 10.8 9.5 Elongation at break (%) 305 326 344 478 412 438 443 0℃ tanδ (loss factor) 0.92 0.94 0.93 0.95 0.94 0.82 0.76 60℃ tanδ (loss factor) 0.131 0.114 0.102 0.084 0.079 0.076 0.081 Compression fatigue heat generation (℃) 26.5 22.4 18.7 15.6 14.8 14.6 14.6

[0124] According to Table 5, as the proportion of silica in the filler composition increases, although the anti-skid ability of the rubber compound is better, the rolling resistance and compression heat generation performance are both higher. At the same time, the elongation at break of the rubber compound becomes shorter and the mechanical properties become worse.

[0125] As the proportion of modified graphene oxide masterbatch increases, although the compression fatigue heat generation and rolling resistance of the rubber are reduced, as the natural rubber content increases, the anti-skid ability and mechanical properties of the rubber deteriorate.

[0126] In summary, the modified graphene oxide masterbatch S in the filler composition n -The performance of the rubber compound is best when the mass ratio of GO / NR and silica is 100:30.

[0127] The various embodiments in this specification are described in a progressive manner. The same or similar parts between the various embodiments can be referenced to each other, and each embodiment focuses on the differences from other embodiments.

[0128] The above embodiments are only used to illustrate the technical solutions of the present application, rather than to limit the present application. Although the present application has been described in detail with reference to the aforementioned embodiments, a person skilled in the art should understand that the technical solutions described in the aforementioned embodiments can still be modified, or some or all of the technical features therein can be replaced by equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the present application.

Claims

1. A filler composition capable of reducing tire rolling resistance, characterized in that: The raw material composition includes: Silica; and A modified graphene oxide masterbatch, wherein the modified graphene oxide masterbatch is produced by mixing and heat-treating the graphene oxide masterbatch and a polysulfide compound; The chemical formula of the polysulfide compound is: Among them, 2≤n≤5.

2. The filler composition according to claim 1, characterized in that The mass ratio of the white carbon black to the modified graphene oxide masterbatch is 100:(5-50).

3. The filler composition according to claim 1, characterized in that When the graphene oxide masterbatch and the polysulfide compound are mixed and heat-treated, the mass ratio of the graphene oxide masterbatch to the polysulfide compound is 100:(0.05-1).

4. The filler composition according to claim 1, characterized in that The graphene oxide masterbatch comprises natural rubber latex and graphene oxide compounded in the natural rubber latex; The mass percentage concentration of the graphene oxide is 5-20wt%.

5. The filler composition according to claim 1, characterized in that The heat treatment temperature is 80-170° C., and the heat treatment time is 1-8 minutes.

6. A low rolling resistance tire rubber compound, characterized in that: The raw material composition includes: Tire rubber base; Silane coupling agent; The filler composition according to any one of claims 1 to 3; and Additives available for tire compounds.

7. The low rolling resistance tire rubber compound according to claim 6, characterized in that: The mass ratio of the tire rubber base material to the filler composition is 100:(40-70).

8. The low rolling resistance tire rubber compound according to claim 6, characterized in that: The additives available for the tire rubber compound include: antioxidant, resin, dispersant and vulcanization package.

9. A method for preparing a low rolling resistance tire rubber compound according to any one of claims 6 to 8, characterized in that the steps include: According to the raw material composition of the tire rubber compound, the raw materials are mixed, kneaded and hot-pressed and vulcanized in sequence to obtain the low rolling resistance tire rubber compound.

10. A tire, characterized in that: Contains the low rolling resistance tire rubber compound according to any one of claims 6 to 8.

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