阅读说明：本技术 一种高性能橡胶组合物及其制备方法 (High-performance rubber composition and preparation method thereof ) 是由 陈昶乐 齐美洲 于 2021-10-15 设计创作，主要内容包括：本发明提供了一种高性能橡胶组合物及其制备方法。本发明提供的高性能橡胶组合物,由包括以下质量份组分的原料制得：100份橡胶基体,1～4份有机二元羧酸,2～20份聚乙烯微米颗粒,1～2份硬脂酸,4～6份氧化锌,1～2份防老剂,0.5～1.5份促进剂,1～3份硫磺。本发明将橡胶基体、有机二元羧酸、聚乙烯微米颗粒、硬脂酸、氧化锌、防老剂、促进剂和硫磺以一定比例搭配制得高性能橡胶组合物,使硫化橡胶材料具有高拉伸强度、300％定伸应力和撕裂强度、较好的抗老化性能,同时具有较低的压缩生热以及损耗因子。(The invention provides a high-performance rubber composition and a preparation method thereof. The high-performance rubber composition provided by the invention is prepared from the following raw materials in parts by mass: 100 parts of rubber matrix, 1-4 parts of organic dicarboxylic acid, 2-20 parts of polyethylene microparticles, 1-2 parts of stearic acid, 4-6 parts of zinc oxide, 1-2 parts of anti-aging agent, 0.5-1.5 parts of accelerator and 1-3 parts of sulfur. According to the invention, a rubber matrix, organic dicarboxylic acid, polyethylene micro-particles, stearic acid, zinc oxide, an anti-aging agent, an accelerator and sulfur are matched according to a certain proportion to prepare the high-performance rubber composition, so that the vulcanized rubber material has high tensile strength, 300% stress at definite elongation and tear strength, better anti-aging performance, lower compression heat generation and loss factor.)

1. The high-performance rubber composition is characterized by being prepared from the following raw materials in parts by mass:

2. the rubber composition of claim 1, wherein the rubber matrix is selected from at least one of cis-polyisoprene rubber, cis-butadiene rubber and styrene-butadiene rubber.

3. The rubber composition according to claim 1, wherein the organic dicarboxylic acid is selected from the group consisting of C8-C18 organic dicarboxylic acids.

4. The rubber composition according to claim 1 or 3, wherein the organic dicarboxylic acid is at least one selected from suberic acid, azelaic acid, sebacic acid, dodecanedioic acid and hexadecanedioic acid.

5. The high performance rubber according to claim 1, wherein the polyethylene microparticles are low density polyethylene and/or linear low density polyethylene.

6. The rubber composition according to claim 1 or 5, wherein the polyethylene microparticles have a median particle diameter D50 of 50 to 300 μm.

7. The rubber composition according to claim 1, wherein the antioxidant is at least one selected from the group consisting of N-phenyl-N '-cyclohexyl-p-phenylenediamine, N-phenyl-N' -isopropyl-p-phenylenediamine, and microcrystalline wax;

the accelerator is at least one selected from 2-mercaptobenzothiazole, diphenylthiazole disulfide, N-cyclohexyl-2-benzothiazole sulfonamide and N-tertiary butyl-2-benzothiazole sulfonamide.

8. A method for producing the high-performance rubber composition according to any one of claims 1 to 7, comprising:

mixing a rubber matrix, organic dicarboxylic acid, an anti-aging agent, polyethylene micro-particles, stearic acid, zinc oxide, sulfur and an accelerator to obtain the high-performance rubber composition.

9. The method of claim 8, comprising the steps of:

a) mixing a rubber matrix, organic diacid carboxylic acid and an anti-aging agent to obtain mixed rubber 1;

b) mixing the mixed rubber 1 with polyethylene micron particles to obtain mixed rubber 2;

c) mixing the mixed rubber 2 with stearic acid and zinc oxide to obtain mixed rubber 3;

d) and (3) scouring the rubber compound 3 with sulfur and an accelerator to obtain the high-performance rubber composition.

10. The method according to claim 9, wherein in the step a), the mixing conditions are as follows: the temperature is 50-80 ℃, the rotating speed is 30-50 rpm, and the time is 2-5 min;

in the step b), the mixing conditions are as follows: the temperature is 110-125 ℃, the rotating speed is 20-30 rpm, and the time is 1-4 min;

in the step c), the mixing conditions are as follows: the temperature is 50-80 ℃, the rotating speed is 30-50 rpm, and the time is 3-8 min;

in the step d), the open milling conditions are as follows: the temperature is 40-70 ℃.

Technical Field

The invention belongs to the technical field of rubber materials, and particularly relates to a high-performance rubber composition and a preparation method thereof.

Background

The formula of the rubber product is a matching system of raw rubber and a matching agent, the rubber is used as raw rubber and can be divided into natural rubber and synthetic rubber according to the source, the natural rubber is a natural high molecular compound which is obtained from natural plants and takes isoprene as a main component, and the natural rubber is a rubber variety with the best comprehensive performance. The synthetic rubber is a high molecular compound which is formed by polymerizing different monomers under the action of an initiator and has various varieties. Among them, general-purpose rubbers such as styrene butadiene rubber, isoprene rubber, and butadiene rubber are main types of synthetic rubbers. Synthetic rubber is artificially synthesized by chemical means, the stability of batches is guaranteed, but the tensile strength is relatively insufficient, the ageing resistance is also poor, and the method has great challenges in completely replacing natural rubber when manufacturing tires and other rubber industrial products.

In order to improve the tensile property, 300% stress at definite elongation and aging property of rubber, the rubber is usually required to be subjected to formulation design, chemical modification, blending modification and the like. The formula design needs a large amount of experiments to find a good formula, and the effect is often not good. The chemical modification is used for modifying the main chain structure of rubber, such as epoxidation, anhydride grafting and the like of rubber with a main chain containing double bonds, a large amount of solvent is usually needed for dissolving the rubber, and the reaction temperature is high, so that the time and the labor are wasted. In comparison, blending modification is a simple and effective modification method, and the performance of the rubber can be improved by directly adding a small amount of modifier in the banburying process. However, it is difficult to modify the rubber to improve the tensile and aging properties of the rubber.

Disclosure of Invention

In view of the above, the present invention aims to provide a high performance rubber composition and a preparation method thereof. The high-performance rubber composition provided by the invention can effectively improve the tensile strength, 300% stress at definite elongation, tear strength and ageing resistance of a rubber material, and has lower compression heat generation and loss factor.

The invention provides a high-performance rubber composition which is prepared from the following raw materials in parts by mass:

preferably, the rubber matrix is selected from at least one of cis-polyisoprene rubber, cis-butadiene rubber and styrene-butadiene rubber.

Preferably, the organic dicarboxylic acid is selected from organic dicarboxylic acids of C8-C18.

Preferably, the organic dicarboxylic acid is at least one selected from suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, and hexadecanedioic acid.

Preferably, the polyethylene microparticles are low density polyethylene and/or linear low density polyethylene.

Preferably, the median diameter D50 of the polyethylene microparticles is 50-300 μm.

Preferably, the anti-aging agent is at least one selected from N-phenyl-N '-cyclohexyl-p-phenylenediamine, N-phenyl-N' -isopropyl-p-phenylenediamine and microcrystalline paraffin;

the accelerator is at least one selected from 2-mercaptobenzothiazole, diphenylthiazole disulfide, N-cyclohexyl-2-benzothiazole sulfonamide and N-tertiary butyl-2-benzothiazole sulfonamide.

The invention also provides a preparation method of the high-performance rubber composition in the technical scheme, which comprises the following steps:

mixing a rubber matrix, organic dicarboxylic acid, an anti-aging agent, polyethylene micro-particles, stearic acid, zinc oxide, sulfur and an accelerator to obtain the high-performance rubber composition.

Preferably, the method comprises the following steps:

a) mixing a rubber matrix, organic diacid carboxylic acid and an anti-aging agent to obtain mixed rubber 1;

b) mixing the mixed rubber 1 with polyethylene micron particles to obtain mixed rubber 2;

c) mixing the mixed rubber 2 with stearic acid and zinc oxide to obtain mixed rubber 3;

d) and (3) scouring the rubber compound 3 with sulfur and an accelerator to obtain the high-performance rubber composition.

Preferably, in the step a), the mixing conditions are as follows: the temperature is 50-80 ℃, the rotating speed is 30-50 rpm, and the time is 2-5 min;

in the step b), the mixing conditions are as follows: the temperature is 110-125 ℃, the rotating speed is 20-30 rpm, and the time is 1-4 min;

in the step c), the mixing conditions are as follows: the temperature is 50-80 ℃, the rotating speed is 30-50 rpm, and the time is 3-8 min;

in the step d), the open milling conditions are as follows: the temperature is 40-70 ℃.

The high-performance rubber composition provided by the invention is prepared by matching a rubber matrix, organic dicarboxylic acid, polyethylene microparticles, stearic acid, zinc oxide, an anti-aging agent, an accelerator and sulfur in a certain proportion, wherein the organic dicarboxylic acid reacts with the zinc oxide to form zinc dicarboxylate, so that the solubility of the zinc oxide in rubber is greatly increased; meanwhile, the polyethylene micron particles are rigid particles with micron structures, are specific polyethylene polymer particles, can be well mixed with rubber, and form a better two-phase structure with the interface of the rubber after high-temperature banburying; the two aspects of synergistic effect, and under the coordination of stearic acid, an anti-aging agent, an accelerator and sulfur, the vulcanized rubber material has high tensile strength, 300 percent stress at definite elongation, tear strength, better aging resistance, lower compression heat generation and loss factor.

Experimental results show that the high-performance rubber composition provided by the invention can enable the tensile strength of a vulcanized rubber material to be more than 26.5MPa, the 300% stress at definite elongation to be more than 2.40MPa, the tear strength to be more than 30MPa, the heat generated by compression to be less than or equal to 9.2 ℃, the absolute value of the change rate of the tensile strength after aging to be less than 15.9%, the absolute value of the change rate of the elongation at break after aging to be less than 15.2%, and the loss factor corresponding to Tg to be less than 2.4.

Detailed Description

The invention provides a high-performance rubber composition which is prepared from the following raw materials in parts by mass:

the high-performance rubber composition provided by the invention is prepared by matching a rubber matrix, organic dicarboxylic acid, polyethylene microparticles, stearic acid, zinc oxide, an anti-aging agent, an accelerator and sulfur in a certain proportion, wherein the organic dicarboxylic acid reacts with the zinc oxide to form zinc dicarboxylate, so that the solubility of the zinc oxide in rubber is greatly increased; meanwhile, the polyethylene micron particles are rigid particles with micron structures, are specific polyethylene polymer particles, can be well mixed with rubber, and form a better two-phase structure with the interface of the rubber after high-temperature banburying; the two aspects of synergistic effect, and under the coordination of stearic acid, an anti-aging agent, an accelerator and sulfur, the vulcanized rubber material has high tensile strength, 300 percent stress at definite elongation, tear strength, better aging resistance, lower compression heat generation and loss factor.

In the present invention, the rubber matrix is preferably at least one of cis-polyisoprene rubber, butadiene rubber and styrene-butadiene rubber. In the invention, the source of the rubber matrix is not particularly limited, and the rubber matrix is a commercial product sold in the market. In the present invention, the amount of the rubber base used in the raw materials for forming the high-performance rubber composition product is 100 parts by mass.

In the invention, the organic dicarboxylic acid is preferably C8-C18 organic dicarboxylic acid; more preferably, the organic dicarboxylic acid is at least one selected from suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, and hexadecanedioic acid; most preferred is dodecanedioic acid. In the research, the organic dicarboxylic acid can effectively improve the performance of rubber products, and if other organic dicarboxylic acids (such as malonic acid, succinic acid, glutaric acid, pimelic acid and the like) are used, the effect is poor, and particularly the tensile strength is poorer than that when the organic dicarboxylic acid is not used for modification. In the invention, the amount of the organic dicarboxylic acid is 1-4 parts based on 100 parts by mass of the rubber matrix; in some embodiments of the present invention, the organic dicarboxylic acid is used in an amount of 2 parts, 2.4 parts, or 4 parts.

According to the invention, the polyethylene micron particles are used as one of the additives, can be melted, plasticized and reprocessed after being heated, are easily fused with the rubber matrix, and form a better two-phase structure with the interface of the rubber after high-temperature banburying, so that the performances of the rubber such as tensile strength, 300% stress at definite elongation, tear strength, ageing resistance and the like can be improved; if other polymer particles such as polystyrene particles are used, the raw rubber is easily degraded by melt post-processing, and the mechanical properties are reduced. In the present invention, the polyethylene microparticles are preferably low density polyethylene and/or linear low density polyethylene; more preferably low density polyethylene or linear low density polyethylene; most preferably low density polyethylene. Polyethylene (PE), a thermoplastic resin obtained by polymerizing ethylene, is classified into High Density Polyethylene (HDPE), Low Density Polyethylene (LDPE) and Linear Low Density Polyethylene (LLDPE) according to a polymerization method, a high or low molecular weight and a difference in chain structure. Among them, low density polyethylene is also called high pressure polyethylene, which is the lightest variety of polyethylene resins; linear low density polyethylene resins, known as third generation polyethylenes, are molecular structures in which ethylene is copolymerized with a small amount of an alpha-olefin to form a linear ethylene backbone with very short comonomer branches. The invention adopts low density polyethylene and/or linear low density polyethylene, can be uniformly mixed in rubber at a lower temperature, and can not reduce the mechanical property of the rubber, if the high density polyethylene is adopted, the invention not only needs higher mixing temperature, but also is easy to reduce the mechanical property of the rubber.

In the invention, the median diameter D50 of the polyethylene microparticles is preferably 50-300 μm, and more preferably 50-100 μm. The granularity is controlled within the range, so that the requirement on crushing equipment is not high, the particles with the grain diameters are easy to obtain, the uniform mixing with rubber is facilitated, and the rubber performance is improved; if the particle size of the particles is too low, the requirement on crushing equipment is high, the energy consumption and the cost are high, and if the particle size of the particles is too high, the particles are not easy to be uniformly dispersed in rubber after being heated and melted. In some embodiments of the invention, the median particle diameter D50 is 100 μm or 300 μm. In the invention, the amount of the polyethylene micron particles is 2-20 parts by mass based on 100 parts by mass of the rubber matrix; in some embodiments of the invention, the polyethylene microparticles are used in an amount of 5 parts or 10 parts.

In the invention, stearic acid and zinc oxide are used as vulcanization activators of the material system, so that the vulcanization speed and the vulcanization efficiency are improved, the heat resistance and the aging resistance of the rubber can be improved, and if other oxides such as magnesium oxide and the like are adopted, the vulcanization time is long, the vulcanization degree is not high, and the performance of the rubber cannot be effectively improved; in addition, zinc oxide is adopted and reacts with organic dicarboxylic acid in the material system to form zinc dicarbamate, so that the solubility of the zinc oxide in rubber is greatly increased, and the performance of the rubber is favorably improved.

In the invention, the using amount of the zinc oxide is 4-6 parts by mass based on 100 parts by mass of the rubber matrix; in some embodiments of the invention, the zinc oxide is used in an amount of 4 parts, 5 parts, or 6 parts. Based on 100 parts by mass of the rubber matrix, the stearic acid is 1-2 parts; in some embodiments of the invention, the stearic acid is used in an amount of 1 part or 2 parts.

In the present invention, the antioxidant is preferably at least one of N-phenyl-N '-cyclohexyl-p-phenylenediamine, N-phenyl-N' -isopropyl-p-phenylenediamine, and microcrystalline wax. In the invention, the using amount of the anti-aging agent is 1-2 parts by mass based on 100 parts by mass of the rubber matrix; in some embodiments of the invention, the antioxidant is used in an amount of 1 part, 1.5 parts, or 2 parts.

In the present invention, the accelerator is preferably at least one of 2-mercaptobenzothiazole, diphenylpropylthiazole disulfide, N-cyclohexyl-2-benzothiazylsulfenamide and N-t-butyl-2-benzothiazylsulfenamide. In the invention, the amount of the accelerator is 0.5-1.5 parts by mass based on 100 parts by mass of the rubber matrix; in some embodiments of the invention, the accelerator is used in an amount of 0.7 parts or 1.5 parts.

In the present invention, the sulfur is preferably insoluble sulfur and/or sulfur powder, and more preferably insoluble sulfur. In the invention, the amount of the sulfur is 1-3 parts based on 100 parts by mass of the rubber matrix; in some embodiments of the invention, the sulfur is used in an amount of 1 part, 2.5 parts, or 3 parts.

The high-performance rubber composition provided by the invention is prepared by matching a rubber matrix, organic dicarboxylic acid, polyethylene microparticles, stearic acid, zinc oxide, an anti-aging agent, an accelerator and sulfur in a certain proportion, wherein the organic dicarboxylic acid reacts with the zinc oxide to form zinc dicarboxylate, so that the solubility of the zinc oxide in rubber is greatly increased; meanwhile, the polyethylene micron particles are rigid particles with micron structures, are specific polyethylene polymer particles, can be well mixed with rubber, and form a better two-phase structure with the interface of the rubber after high-temperature banburying; the two aspects of synergistic effect, and under the coordination of stearic acid, an anti-aging agent, an accelerator and sulfur, the vulcanized rubber material has high tensile strength, 300 percent stress at definite elongation, tear strength, better aging resistance, lower compression heat generation and loss factor.

The invention also provides a preparation method of the high-performance rubber composition in the technical scheme, which comprises the following steps:

mixing a rubber matrix, organic dicarboxylic acid, an anti-aging agent, polyethylene micro-particles, stearic acid, zinc oxide, sulfur and an accelerator to obtain the high-performance rubber composition.

The types and the amounts of the rubber matrix, the organic dicarboxylic acid, the anti-aging agent, the polyethylene micron particles, the stearic acid, the zinc oxide, the sulfur and the accelerator are all consistent with those in the technical scheme, and are not repeated herein.

In the present invention, the preparation method preferably specifically comprises the following steps:

a) mixing a rubber matrix, organic diacid carboxylic acid and an anti-aging agent to obtain mixed rubber 1;

b) mixing the mixed rubber 1 with polyethylene micron particles to obtain mixed rubber 2;

c) mixing the mixed rubber 2 with stearic acid and zinc oxide to obtain mixed rubber 3;

d) and (3) scouring the rubber compound 3 with sulfur and an accelerator to obtain the high-performance rubber composition.

With respect to step a):

the mixing is preferably carried out in an internal mixer. The mixing temperature is preferably 50-80 ℃, and in some embodiments of the invention, is 50 ℃ or 80 ℃. The mixing time is preferably 2-5 min, and in some embodiments of the invention, the mixing time is 4min or 5 min. The mixing speed is preferably 30-50 rpm, and in some embodiments of the invention, 30 rpm. Specifically, the temperature of the internal mixer is increased to a target temperature in advance, a target rotating speed is set, and then the materials are put into the internal mixer for mixing. After the above-mentioned mixing, discharging to obtain rubber compound 1.

With respect to step b):

the mixing is preferably carried out in an internal mixer. The mixing temperature is preferably 110-125 ℃, and in some embodiments of the invention, is 110 ℃ or 120 ℃. The mixing time is preferably 1-4 min, and in some embodiments of the invention, is 2min or 4 min. The mixing speed is preferably 20-30 rpm, and in some embodiments of the invention, 20rpm or 30 rpm. Specifically, after the mixing and discharging of the step a), the temperature of the internal mixer is raised to a target temperature, a target rotating speed is set, and the mixed rubber 1 obtained in the step a) and the polyethylene microparticles are put into the internal mixer for mixing. And (3) after the mixing, discharging and cooling to obtain the mixed rubber 2.

With respect to step c):

the mixing is preferably carried out in an internal mixer. The mixing temperature is preferably 50-80 ℃, and in some embodiments of the invention, is 50 ℃ or 80 ℃. The mixing time is preferably 3-8 min, and in some embodiments of the invention, 3 min. The mixing speed is preferably 30-50 rpm, and in some embodiments of the invention, 30rpm or 50 rpm. Specifically, after the mixing and discharging in the step b), the temperature of the internal mixer is raised to a target temperature, a target rotating speed is set, and the mixed rubber 2 obtained in the step b), stearic acid and zinc oxide are put into the internal mixer for mixing. After the mixing, discharging the rubber. After the rubber is discharged, preferably standing at room temperature; the room temperature can be 20-25 ℃; the parking time is preferably 12-24 hours, and more preferably 24 hours. After the above treatment, a rubber compound 3 was obtained.

With respect to step d):

the scouring is preferably performed in a scouring machine. The temperature of the scouring is preferably 40 to 70 ℃, and in some embodiments of the invention is 40 ℃ or 70 ℃. Specifically, the roll of the open mill is heated to the target temperature, the rubber compound C is added for open milling, and sulfur and an accelerator are added for open milling in the open milling process. Wherein the time for separately milling the rubber compound C is 2-5 min. And (3) during the process of adding the sulfur and the accelerator for co-refining, performing triangular bag formation for 8-20 times. After uniform opening, the film is taken out, and the film is placed at room temperature; the room temperature can be 20-25 ℃; the parking time is preferably 16-24 h. After the above treatment, a high-performance rubber composition is obtained.

The rubber composition provided by the invention is used as a rubber raw material for vulcanization, so that the tensile strength, 300% stress at definite elongation, tear strength and ageing resistance of the vulcanized rubber material are obviously improved, and the heat generation and loss factor under compression are obviously reduced. Wherein the vulcanization conditions are preferably: the vulcanization temperature is 135-145 ℃, the vulcanization pressure is 10-25 MPa, and the vulcanization time is t90 to (t90+5 min). In some embodiments of the invention, the vulcanization temperature is 135 ℃ or 145 ℃; the vulcanization pressure is 10MPa or 25 MPa; the vulcanization time was t90 or t90+5 min.

The preparation method provided by the invention belongs to doping modification, and chemical modification of rubber is not required, so that a large amount of solvents are avoided; the method has the advantages of simple process, low cost, no need of adding additional processing equipment and complicated steps, and important prospect in preparing high-performance rubber materials. In the preparation process, the organic dicarboxylic acid reacts with the zinc oxide to form zinc dicarboxylate, so that the solubility of the zinc oxide in rubber is greatly increased; meanwhile, the polyethylene micron particles are rigid particles with micron structures, are specific polyethylene polymer particles, can be well mixed with rubber, and form a better two-phase structure with the interface of the rubber after high-temperature banburying; the two aspects of synergistic effect, and under the coordination of stearic acid, an anti-aging agent, an accelerator and sulfur, the vulcanized rubber material has high tensile strength, 300 percent stress at definite elongation, tear strength, better aging resistance, lower compression heat generation and loss factor.

Experimental results show that the high-performance rubber composition provided by the invention can enable the tensile strength of a vulcanized rubber material to be more than 26.5MPa, the 300% stress at definite elongation to be more than 2.40MPa, the tear strength to be more than 30MPa, the heat generated by compression to be less than or equal to 9.2 ℃, the absolute value of the change rate of the tensile strength after aging to be less than 15.9%, the absolute value of the change rate of the elongation at break after aging to be less than 15.2%, and the loss factor corresponding to Tg to be less than 2.4.

For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.

Examples 1 to 3

S1, adding the rubber, the organic dicarboxylic acid and the anti-aging agent into an internal mixer with the temperature of 80 ℃ and the rotation speed of 30rpm, mixing for 5min, and discharging to obtain mixed rubber 1.

S2, raising the temperature of the internal mixer to 110 ℃, controlling the rotating speed to be 20rpm, adding the mixed rubber 1 and polyethylene particles with the median particle size D50 of 100 mu m, mixing for 2min, discharging and cooling to obtain mixed rubber 2.

S3, adding the mixed rubber 2, stearic acid and zinc oxide into an internal mixer with the temperature of 80 ℃ and the rotation speed of 50rpm, mixing for 5min, discharging rubber, standing at room temperature for 24h, and obtaining mixed rubber 3.

S4, after the mixed rubber 3 is milled on an open mill with the roll temperature of 40 ℃ for 2min, adding sulfur and an accelerator, performing triangular bag packing for 8 times, discharging after uniform milling, and standing the rubber sheet for 24h at room temperature to obtain the high-performance rubber composition.

The vulcanization molding conditions of the high-performance rubber composition are as follows: the vulcanization temperature is 135 ℃, the vulcanization pressure is 25MPa, and the vulcanization time is t90+5 min.

Comparative example 1

The procedure of example 1 was followed except that no organic dicarboxylic acid and no polyethylene microparticles were added.

Comparative example 2

The procedure of example 1 was followed except that no polyethylene microparticles were added.

The raw material formulas of examples 1 to 3 and comparative examples 1 to 2 are shown in Table 1:

TABLE 1 raw material formulas of examples 1 to 3 and comparative examples 1 to 2

The properties of the rubbers obtained in examples 1 to 3 and comparative examples 1 to 2 were measured, and the results are shown in Table 2.

In the test of compression heat generation, reference is made to GB/T1687.3-2016 vulcanized rubber, and part 3 of the measurement of temperature rise and fatigue resistance performance in a flexing test is as follows: the sample is a cylinder with a diameter of 17.80mm +/-0.15 mm and a height of 25.00mm +/-0.15 mm. Test reference for aging: GBT3512-2014 vulcanized rubber or thermoplastic rubber hot air accelerated aging and heat resistance test standard, 100 ℃ multiplied by 24 hours.

TABLE 2 Properties of rubbers obtained in examples 1 to 3 and comparative examples 1 to 2

Item	Comparative example 1	Comparative example 2	Example 1	Example 2	Example 3
						Positive vulcanization time t90(min)	30.2	28.5	25.0	26.3	24.2
Tensile Strength (MPa)	21.5	24.2	26.6	27.3	26.5
						Elongation at Break (%)	760	745	729	710	712
300% stress at definite elongation (MPa)	1.35	1.95	2.40	2.82	2.91
						Tear Strength (kN/m)	25.9	27.8	31.4	32.3	34.2
Heat generation by compression (. degree.C.)	9.5	9.2	7.1	7.5	8.2
						Tensile Strength Change after aging (%)	-22.5	-15.2	-15.9	-6.5	-12.3
Percentage change in elongation at break after aging (%)	-30.2	-11.2	-10.5	-15.2	-12.5
						Tg corresponding loss factor	2.89	2.53	2.38	2.17	2.05

As can be seen from the test results in Table 2, the rubbers obtained in examples 1 to 3 of the present invention have a tensile strength of 26.5MPa or more, a 300% stress at definite elongation of 2.40MPa or more, a tear strength of 31MPa or more, a heat generation under compression of < 8.5 ℃, an absolute value of a change in tensile strength after aging of 15.9% or less, an absolute value of a change in elongation at break after aging of 15.2% or less, and a loss factor corresponding to Tg of 2.4 or less. The tensile strength of the rubber obtained in the comparative examples 1-2 is below 24.5MPa, the 300% stress at definite elongation is below 1.95MPa, the tearing strength is below 28MPa, the heat generated by compression is not less than 9.2 ℃, the absolute value of the tensile strength change rate after aging is above 15.2%, the absolute value of the tensile elongation change rate after aging is above 11.2%, and the loss factor corresponding to Tg is above 2.5. The rubber provided by the invention obviously improves the tensile strength, 300% stress at definite elongation, tear strength and aging resistance of the material, and reduces the compression heat generation and loss factor.

Examples 4 to 6

S1, adding the rubber, the organic dicarboxylic acid and the anti-aging agent into an internal mixer with the temperature of 50 ℃ and the rotation speed of 30rpm, mixing for 4min, and discharging to obtain mixed rubber 1.

S2, raising the temperature of the internal mixer to 120 ℃, controlling the rotating speed to be 30rpm, adding the mixed rubber 1 and polyethylene particles with the median particle size D50 of 300 mu m, mixing for 4min, discharging and cooling to obtain mixed rubber 2.

S3, adding the mixed rubber 2, stearic acid and zinc oxide into an internal mixer with the temperature of 50 ℃ and the rotation speed of 30rpm, mixing for 3min, discharging rubber, standing at room temperature for 24h, and obtaining mixed rubber 3.

And S4, rolling the mixed rubber 3 on an open mill with the roll temperature of 70 ℃ for 5min, adding sulfur and an accelerator, performing triangular bag packing for 20 times, discharging after uniform rolling, and standing the rubber sheet at room temperature for 16h to obtain the high-performance rubber composition.

The vulcanization molding conditions of the high-performance rubber composition are as follows: the vulcanization temperature is 145 ℃, the vulcanization pressure is 10MPa, and the vulcanization time is t 90.

Comparative example 3

The procedure of example 4 was followed except that no organic dicarboxylic acid and no polyethylene microparticles were added.

Comparative example 4

The procedure of example 5 was followed except that no organic dicarboxylic acid was added.

The raw material formulas of examples 4 to 6 and comparative examples 3 to 4 are shown in Table 3:

TABLE 3 raw material formulas of examples 4 to 6 and comparative examples 3 to 4

The properties of the rubbers obtained in examples 4 to 6 and comparative examples 3 to 4 were measured, and the results are shown in Table 4.

TABLE 4 Properties of rubbers obtained in examples 4 to 6 and comparative examples 3 to 4

Item	Comparative example 3	Comparative example 4	Example 4	Example 5	Example 6
						Positive vulcanization time t90(min)	33.5	28.3	25.0	21.5	19.5
Tensile Strength (MPa)	23.5	25.2	27.8	28.1	27.2
						Elongation at Break (%)	745	770	725	735	710
300% stress at definite elongation (MPa)	1.68	1.82	2.59	2.75	2.83
						Tear Strength (kN/m)	24.2	28.6	30.2	32.5	36.7
Heat generation by compression (. degree.C.)	10.2	9.9	8.5	8.3	9.2
						Tensile Strength Change after aging (%)	-19.5	-10.2	-11.5	-6.3	-9.5
Percentage change in elongation at break after aging (%)	-20.2	-10.9	-10.0	-8.2	-11.2
						Tg corresponding loss factor	2.69	2.35	2.20	2.03	1.95

As can be seen from the test results in Table 4, the tensile strength of the rubber obtained in examples 4 to 6 of the present invention is 27MPa or more, the 300% stress at definite elongation is 2.59MPa or more, the tear strength is 30MPa or more, the heat generated by compression is 9.2 ℃ or less, the absolute value of the change rate of the tensile strength after aging is 11.5% or less, the absolute value of the change rate of the elongation at break after aging is 11.2% or less, and the loss factor corresponding to Tg is 2.2 or less. The tensile strength of the rubber obtained in the comparative examples 3-4 is below 25.2MPa, the 300% stress at definite elongation is below 1.82MPa, the tear strength is below 28.6MPa, the heat generated by compression is not less than 9.9 ℃, the absolute value of the tensile strength change rate after aging is above 10.2%, the absolute value of the tensile elongation change rate after aging is above 10.9%, and the loss factor corresponding to Tg is above 2.35. The rubber provided by the invention obviously improves the tensile strength, 300% stress at definite elongation, tear strength and aging resistance of the material, and reduces the compression heat generation and loss factor.

As can be seen from the above examples 1-6 and comparative examples 1-4, the addition of organic dicarboxylic acid and polyethylene microparticles in the invention, in combination with stearic acid, anti-aging agent, accelerator and sulfur, makes the vulcanized rubber material have high tensile strength, 300% stress at definite elongation and tear strength, better aging resistance, and lower heat generation under compression and loss factor.

The foregoing examples are provided to facilitate an understanding of the principles of the invention and their core concepts, including the best mode, and also to enable any person skilled in the art to practice the invention, including making and using any devices or systems and performing any incorporated methods. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention. The scope of the invention is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that approximate the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.