阅读说明：本技术 一种热处理的三嗪基石墨炔增强硫化橡胶及其制备方法和应用 (Heat-treated triazinyl graphdiyne reinforced vulcanized rubber and preparation method and application thereof ) 是由 孙翀 范春燕 阚晓楠 赵英杰 赵洪滢 隋晶 于广水 于 2021-10-13 设计创作，主要内容包括：本发明涉及一种热处理的三嗪基石墨炔增强硫化橡胶及其制备方法和应用,属于橡胶领域。所述三嗪基石墨炔增强硫化橡胶的组分包括热处理后三嗪基石墨炔、丁苯橡胶、防老剂、硬脂酸、氧化锌、炭黑、促进剂和硫黄。本发明结合了三嗪基石墨炔的优势及管式炉热处理的优势,可以显著降低丁苯橡胶的滚动阻力,加快橡胶硫化速度,提高硫化橡胶的交联密度,并提高炭黑在丁苯橡胶基体中的分散性,本发明在高力学性能、低滚动阻力轮胎用高性能橡胶复合材料开发领域具有潜在的应用价值。(The invention relates to heat-treated triazinyl graphite alkyne reinforced vulcanized rubber as well as a preparation method and application thereof, belonging to the field of rubber. The components of the triazinyl graphdiyne reinforced vulcanized rubber comprise heat-treated triazinyl graphdiyne, styrene-butadiene rubber, an anti-aging agent, stearic acid, zinc oxide, carbon black, an accelerator and sulfur. The invention combines the advantages of triazine-based graphite alkyne and the advantages of tubular furnace heat treatment, can obviously reduce the rolling resistance of styrene-butadiene rubber, quickens the vulcanization speed of rubber, improves the crosslinking density of vulcanized rubber, and improves the dispersibility of carbon black in a styrene-butadiene rubber matrix.)

1. The heat-treated triazinyl graphyne-reinforced vulcanized rubber is characterized in that the components of the triazinyl graphyne-reinforced vulcanized rubber comprise heat-treated triazinyl graphyne, styrene butadiene rubber, an anti-aging agent, stearic acid, zinc oxide, carbon black, an accelerator and sulfur.

2. The triazinyl graphdine-reinforced vulcanizate of claim 1, wherein the heat-treated triazinyl graphdine-reinforced vulcanizate comprises the following components in parts by weight:

3. the process for the preparation of the triazinyl-graphdine-reinforced vulcanizates according to claim 1 or 2, characterized in that it comprises the following steps:

step 1: carrying out heat treatment on the triazine-based graphdiyne by using a tube furnace, wherein the heat treatment conditions are as follows: n is a radical of₂Heating the mixture to 200 ℃ from room temperature in an atmosphere at a heating speed of 10 ℃/min;

step 2: adding styrene butadiene rubber into an open mill, wrapping rollers, adding the triazinyl graphite alkyne, zinc oxide, stearic acid, an anti-aging agent, carbon black, sulfur and an accelerator subjected to heat treatment in the step 1, pouring rubber for 3 times respectively from left to right after each feeding, cutting off and taking down the rubber material, adjusting the roller distance to 0.5mm, adding the rubber material, thinly passing, wrapping in a triangular bag, and thinly passing for 6 times to obtain a rubber mixed material;

and step 3: and vulcanizing and molding the obtained rubber mixed material to obtain the triazinyl graphite alkyne reinforced vulcanized rubber.

4. The method according to claim 3, wherein the accelerator in step 2 is N-tert-butyl-2-benzothiazolesulfenamide.

5. The method according to claim 3, wherein the antioxidant in step 2 is a 2,2, 4-trimethyl-1, 2-dihydroquinoline polymer.

6. The method according to claim 3, wherein the carbon black in the step 2 is N330.

7. The method according to claim 3, wherein the vulcanization temperature in step 3 is 160 ℃.

8. Use of the triazinyl-graphdiyne-reinforced vulcanizate of claim 1 or 2 in a low rolling resistance tire tread rubber.

9. Use of the triazinyl-graphite-alkyne-reinforced vulcanized rubber obtained by the preparation method according to any one of claims 3 to 7 in a tread rubber for a low rolling resistance tire.

Technical Field

The invention relates to heat-treated triazinyl graphite alkyne reinforced vulcanized rubber as well as a preparation method and application thereof, and belongs to the field of rubber.

Background

With the rapid increase of the global automobile holding capacity and the increasing dependence on petroleum energy, energy problems and environmental problems become more and more interesting. The energy conservation and emission reduction of the automobile are more and more emphasized in all countries around the world, and increasingly strict laws and regulations are established, for example, the rolling resistance grade standard of the 2 nd stage is executed in 2016 (11) months in European Union, and the rolling resistance coefficient is reduced by 1.5 N.KN compared with that of the l stage^-1The rolling resistance grade requirement is more and more strict; china also sets strict emission reduction standards for automobile fuel consumption, the fuel consumption standard of an automobile per 100km is reduced from 6.9L in 2015 to 5.0L in 2020, and the current sold passenger vehicles execute the national VI automobile emission standards. These measures prompt automobile manufacturers to improve the technical level of products or actively develop new more environment-friendly technologies, such as the technologies of hybrid electric vehicles, pure electric vehicles and hydrogen energy vehicles, so as to achieve the purposes of energy conservation and emission reduction.

The vehicle can be subjected to resistance in running, except for 80% of air resistance, the rest 20% is tire rolling resistance, and the increase of the rolling resistance can increase the emission of carbon dioxide gas, so that the environment protection is not facilitated. Research shows that the rolling resistance is reduced by 10%, and the fuel consumption of the passenger car can be reduced by 1% -2%. Therefore, in addition to technical innovation in the aspects of reducing the whole vehicle mass and the engine, automobile manufacturers also put forward strict technical requirements on the rolling resistance of tires, and the technical index requirements tend to be increased year by year.

The solution polymerized styrene butadiene rubber has better wet skid resistance, low rolling resistance and wear resistance, and has better application prospect in the field of tires. The dispersion form of the carbon black in the rubber matrix and the strength of the interaction between the carbon black and the rubber matrix have important influence on the performance of the rubber/carbon black composite material. As the primary particle diameter of the carbon black is about 10-100nm, the surface energy is higher, the stability is poorer, and agglomeration is easy to occur. Therefore, the carbon black nano particles have poor dispersibility in the rubber matrix, and further have a series of negative effects on the performances of the styrene butadiene rubber, such as increasing the rolling resistance and the stress at definite elongation, reducing the vulcanization speed and the like.

The styrene butadiene rubber filled with carbon black as a reinforcing agent has the following defects:

(1) poor dispersibility of carbon black in rubber matrix

(2) Influence on reduction of rolling resistance of styrene butadiene rubber

(3) The traditional filler and graphene can not enable the system to reach high crosslinking density

The graphoyne is composed of sp-and sp^2-The triazine-based graphdiyne is equivalent to conjugate connection of triazine rings by acetylene bonds, and then forms a polymer with a novel two-dimensional planar network structure. Therefore, the triazine-based graphdiyne has the characteristics of large conjugated system, wide surface space, good chemical stability and the like. After heating for a certain time, unreacted monomers, oligomers and the like in the product are removed, so that the triazine-based graphyne subjected to the heat treatment in the tube furnace has higher purity and fewer defects than untreated triazine-based graphyne.

Based on the above, in order to make up the defects of low vulcanization speed of the styrene-butadiene rubber, poor dispersibility of the carbon black in the rubber matrix and the like, the invention aims to mix the graphite alkyne with the solution-polymerized styrene-butadiene rubber filled with the carbon black, and aims to improve the vulcanization speed and the crosslinking degree of the styrene-butadiene rubber and improve the dispersibility of the carbon black so as to achieve the purposes of improving the mechanical property of the rubber material and reducing the rolling resistance.

Disclosure of Invention

Aiming at the problems, the invention provides a heat-treated triazine-based graphdiyne reinforced vulcanized rubber, and a preparation method and application thereof, wherein the rubber combines the advantages of triazine-based graphdiyne and the advantages of tubular furnace heat treatment, can obviously reduce the rolling resistance of styrene butadiene rubber, accelerate the vulcanization speed of rubber, improve the crosslinking density of vulcanized rubber, and improve the dispersibility of carbon black in a styrene butadiene rubber matrix. The technical scheme of the invention is as follows:

a heat-treated triazinyl graphdiyne reinforced vulcanized rubber is prepared from triazinyl graphdiyne (after heat treatment), butadiene styrene rubber, antiager, stearic acid, zinc oxide, carbon black, promoter and sulfur.

Further, the heat-treated triazine-based graphite alkyne reinforced vulcanized rubber comprises the following components in parts by weight:

furthermore, the preparation method of the heat-treated triazine-based graphyne reinforced vulcanized rubber comprises the following steps:

step 1: carrying out heat treatment on the triazine-based graphdiyne by using a tube furnace, wherein the heat treatment conditions are as follows: n is a radical of₂Heating the mixture to 200 ℃ from room temperature in an atmosphere at a heating speed of 10 ℃/min;

step 2: adding styrene butadiene rubber into an open mill, wrapping rollers, adding the triazinyl graphite alkyne, zinc oxide, stearic acid, an anti-aging agent, carbon black, sulfur and an accelerator subjected to heat treatment in the step 1, after all materials are eaten each time, cutting off and taking down the rubber material by 3 knives on the left and right, adjusting the roller distance to 0.5mm, adding the rubber material for thin passing, wrapping in a triangular bag, and thinly passing for 6 times to obtain a rubber mixed material;

and step 3: and vulcanizing and molding the obtained rubber mixed material to obtain the triazinyl graphite alkyne reinforced vulcanized rubber.

Preferably, the accelerator in step 2 is N-tert-butyl-2-benzothiazole sulfonamide (NS); the anti-aging agent is 2,2, 4-trimethyl-1, 2-dihydroquinoline polymer (RD); the carbon black is N330

Preferably, the vulcanization temperature in step 3 is 160 ℃.

The invention also comprises application of the heat-treated triazine-based graphite alkyne reinforced vulcanized rubber in low rolling resistance tire tread rubber.

Compared with the prior art, the invention has the following advantages:

in the invention, as the triazine group in the triazine-based graphdiyne and the sulfur form an intermediate ligand to participate in crosslinking, the vulcanization speed of the rubber composite material is accelerated, the balance torque is large, the crosslinking density is increased, and the stress at definite elongation of the triazine-based graphdiyne reinforced vulcanized rubber is higher than that of carbon black filled styrene-butadiene rubber and graphene oxide filled styrene-butadiene rubber. The triazine-based graphite alkyne is used as a flaky filler to be inserted into the carbon black aggregate, so that the Payne effect (the difference value of the storage modulus of vulcanized rubber under low strain and high strain) of the rubber composite material is obviously reduced, the dispersibility of the carbon black aggregate in a styrene butadiene rubber matrix is improved, and the improvement of the mechanical property of the filled vulcanized rubber is facilitated. The improvement of the triazine-based graphdine-reinforced vulcanized rubber and the crosslinking density thereof, and the improvement of the dispersibility of the carbon black, all reduce the hysteresis loss of the vulcanized rubber (which means that the rolling resistance is reduced). Therefore, the invention has potential application value in the field of development of high-performance rubber composite materials of high-mechanical-property low-rolling-resistance tires.

Drawings

FIG. 1 is a vulcanization curve diagram of a styrene-butadiene rubber composite material

FIG. 2 is a cross-linking density chart of a vulcanized styrene-butadiene rubber

FIG. 3 is a DSC graph of a heat treated mixture of triazinyl graphdine and sulfur

FIG. 4 is a stress-strain curve diagram of vulcanized styrene-butadiene rubber

FIG. 5 is a graph showing the relationship between storage modulus and strain of a vulcanized styrene-butadiene rubber

FIG. 6 is a graph showing the relationship between loss factor and strain of a vulcanized styrene-butadiene rubber

FIG. 7 is a graph showing the relationship between the loss factor and the temperature of the vulcanized styrene-butadiene rubber at-90-120 ℃ by temperature scanning

Detailed Description

The invention will be further described with reference to specific embodiments, and the advantages and features of the invention will be more apparent from the following description. The examples are illustrative only and do not limit the scope of the present invention in any way. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention, and that such changes and modifications may be made without departing from the spirit and scope of the invention.

Example 1: heat-treated triazinyl graphdiyne reinforced vulcanized rubber and preparation method thereof

The vulcanized rubber comprises the following components in parts by weight:

the preparation method of the triazine-based graphdiyne reinforced vulcanized rubber comprises the following steps:

step 1: carrying out heat treatment on the triazine-based graphdiyne by using a tube furnace, wherein the heat treatment conditions are as follows: n is a radical of₂Heating the mixture to 200 ℃ from room temperature in an atmosphere at a heating speed of 10 ℃/min;

step 2: adding styrene butadiene rubber into an open mill, wrapping rollers, adding the triazinyl graphite alkyne, zinc oxide, stearic acid, an anti-aging agent, carbon black, sulfur and an accelerator subjected to heat treatment in the step 1, after all materials are eaten each time, cutting off and taking down the rubber material by 3 knives on the left and right, adjusting the roller distance to 0.5mm, adding the rubber material for thin passing, wrapping in a triangular bag, and thinly passing for 6 times to obtain a rubber mixed material;

and step 3: and vulcanizing and molding the obtained mixed material, wherein the vulcanization stability is 160 ℃, and obtaining the triazinyl graphite alkyne reinforced vulcanized rubber.

Comparative example 1: the formula of the rubber composite material comprises the following components in parts by weight:

comparative example 2: the formula of the rubber composite material comprises the following components in parts by weight:

comparative example 3: the formula of the rubber composite material comprises the following components in parts by weight:

comparative example 4: the formula of the rubber composite material comprises the following components in parts by weight:

the accelerator is N-tertiary butyl-2-benzothiazole sulfonamide; the anti-aging agent is a 2,2, 4-trimethyl-1, 2-dihydroquinoline polymer; the carbon black is N330

The rubbers obtained in example 1 and comparative examples 1,2, 3, 4 were subjected to the following property tests: a vulcanization curve test, a strain scanning test, a swelling method cross-linking density test, a temperature scanning test, a tensile test and a scanning electron microscope image; wherein, fig. 1 is a vulcanization curve chart of the styrene butadiene rubber composite material, and it can be seen that the vulcanization speed of the embodiment is faster and the balance torque is higher. FIG. 2 is a graph showing the crosslink density of a vulcanized styrene-butadiene rubber, which is higher in the examples than in the comparative examples. FIG. 3 is a DSC of a mixture of heat-treated triazinyl graphdine and sulfur, showing that the heat-treated triazinyl graphdine reacts with sulfur at about 160 ℃ to produce an intermediate ligand. FIG. 4 is a stress-strain curve of a vulcanized styrene-butadiene rubber, and it can be seen that the stress at definite elongation of the example is significantly higher than that of the comparative example. FIG. 5 is a graph of the relationship between storage modulus and strain in dynamic mechanical properties, and it can be seen from FIG. 5 that the difference between storage modulus at low strain and storage modulus at high strain (i.e., Payne effect) is significantly reduced in the examples, which indicates that the dispersibility of carbon black in the rubber matrix is significantly improved in the examples. Fig. 6 is a graph of loss factor versus strain in dynamic mechanical properties, and it can be seen that the loss factor value is significantly reduced for each strain of the examples. FIG. 7 is a graph of the relationship between the loss factor and the temperature of the vulcanized styrene-butadiene rubber at-90 ℃ to 120 ℃ by temperature scanning, and it can be seen that the loss factor at 60 ℃ is obviously reduced and the rolling resistance of the embodiment is low.