CN116496551A - A kind of rubber composition with high modulus and preparation method thereof - Google Patents

Abstract

The invention discloses a rubber composition with high stretching stress and a preparation method thereof, and relates to the field of rubber materials. According to the invention, the rubber composition prepared by adding additives such as rubber, filler, activating agent, anti-aging agent, sulfur, accelerator and auxiliary agent has high stretching stress, and the obtained rubber composition has excellent wear resistance, strong adhesive force with metal plates/steel wires and excellent resistance to denaturation under the action of external force. In addition, the preparation raw materials are added according to different addition sequences, and the rubber composition with high stretching stress is obtained by combining a specific rubber preparation process, so that the preparation process is simple and adjustable, and compared with the prior art, the preparation method disclosed by the invention is more in accordance with the requirements of environmental protection, has the advantages of strong universality and suitability for large-scale production, and can be widely applied to rubber thick products such as mine tires, truck radial tires and the like.

Description

A kind of rubber composition with high modulus and preparation method thereof

technical field

The invention relates to the field of rubber materials, C08L7/00, in particular to a rubber composition with high modulus stress and a preparation method thereof.

Background technique

Thick rubber products such as mine tires and radial truck tires are mainly prepared from natural rubber. During the processing of natural rubber/isoprene rubber at high temperature for a long time, it is often accompanied by the occurrence of vulcanization reversion, which makes the torque and crosslink density gradually decrease with time, and finally leads to the mechanical properties of the tire (especially is the modulus of elongation) and decrease in life. In order to solve the above problems, it is desired to improve the vulcanization reversion of natural rubber/isoprene rubber (that is, reduce the reversion rate of rubber) by adding some new environmentally friendly rubber additives, thereby improving the vulcanization of vulcanized rubber. Stage modulus (including 100% modulus and 300% modulus).

Chinese patent application CN113429646A discloses a high-tear high modulus rubber containing sacrificial bonds and its preparation method and application. The raw materials include isoprene rubber or natural rubber, epoxidized natural rubber, talcum powder, zinc oxide, hard Fatty acid, naphthenic oil, accelerator, sulfur, use the good cross-linking effect of epoxy group in epoxidized natural rubber and talcum powder to form reversible sacrificial bonds in the rubber cross-linked network, with high rubber modulus, The tear strength is high, but its 100% modulus stress is up to 1.06MPa, and its 300% modulus stress is up to 2.22MPa, which needs to be further improved. Chinese patent application CN113861519A discloses a material for improving tire belt adhesion and a preparation method thereof, wherein, 1,3-bis(citraconimide methyl)benzene (PK900) and other biscitraconimide additives It can greatly increase the modulus of the tire belt layer, and at the same time improve the bonding force between the rubber and the steel cord, but its high modulus is relatively weak. The modulus of vulcanizate reflects the ability of its network structure to resist deformation under external force. Improving the modulus stress within an appropriate range is not only beneficial to improving the wear resistance of the rubber, but also beneficial to improving the adhesion between the rubber and the metal plate/steel cord. Therefore, it is desirable to provide a rubber composition capable of increasing the modulus at a higher level.

Contents of the invention

In order to solve the above problems, the first aspect of the present invention provides a rubber composition with high modulus stress. The raw materials for its preparation include: rubber, filler, activator, anti-aging agent, sulfur, accelerator, metal organic compound, and auxiliary agent.

Preferably, in parts by mass, its preparation raw materials include: 100 parts of rubber, 20-100 parts of filler, 2-17 parts of activator, 0.5-5 parts of anti-aging agent, 0.5-10 parts of sulfur, 0.1-8 parts of accelerator, 0-3 parts of metal organic matter, 0.5-10 parts of additives.

In some preferred embodiments, the rubber is selected from natural rubber, chlorinated butyl rubber, brominated butyl rubber, isoprene rubber, styrene-butadiene rubber, butadiene rubber, nitrile rubber, EPDM At least one of rubber and butyl rubber; preferably natural rubber and/or isoprene rubber; more preferably natural rubber.

In some preferred embodiments, the filler is selected from at least one of carbon black, white carbon black, clay, barite powder, talc powder, calcium carbonate powder, kaolin, mica powder; preferably carbon black and/or Silica.

Preferably, the iodine absorption value of the carbon black is 80-130g/kg, and the DBP value is 72-125cm3/100g;

Further preferably, the iodine absorption value of the carbon black is 120g/kg, and the DBP value is 125cm3/100g.

Further preferably, the carbon black has an iodine absorption value of 82 g/kg and a DBP value of 102 cm3/100 g.

Still further preferably, the filler is a mixture of carbon black and white carbon black, and the mass ratio of carbon black to white carbon black is (3-5):1; preferably 4.5:1.

Preferably, the specific surface area of the white carbon black is 150-185m2/g, and the tap density is 200-230g/L; preferably, the specific surface area is 172m2/g, and the tap density is 210g/L.

In some preferred embodiments, the activator is selected from at least one of zinc oxide, lead oxide, magnesium oxide, triethanolamine, stearic acid, zinc stearate; preferably zinc oxide and/or stearic acid .

In some preferred embodiments, when the activator is zinc oxide and stearic acid, the mass ratio of zinc oxide and stearic acid is (1-6): (0-2.5); preferably (2-4) : (1.5-2.5); more preferably 3.5:2.

In some preferred embodiments, the antioxidant is selected from at least one of phenolic antioxidants, ketamine antioxidants, benzimidazole antioxidants, p-phenylenediamine antioxidants, and thiourea antioxidants ; Preferably ketone amine anti-aging agent and p-phenylenediamine anti-aging agent.

In some preferred embodiments, the mass ratio of the ketoneamine antioxidant and p-phenylenediamine antioxidant is (0.8-2): (0.7-3); preferably (1-1.5): (1- 2).

In some preferred embodiments, the ketamine-based anti-aging agent is selected from at least one of anti-aging agent RD, anti-aging agent AW, anti-aging agent AM/anti-aging agent BLE; preferably anti-aging agent RD.

In some preferred embodiments, the p-phenylenediamine antiaging agent is at least one selected from Antiaging Agent 4010, Antiaging Agent 4020, Antiaging Agent 4010NA, and Antiaging Agent H; preferably Antiaging Agent 4020.

In some preferred embodiments, the sulfur is selected from at least one of oil-extended insoluble sulfur, sulfur predispersion, powder sulfur, colloidal sulfur, sedimentation sulfur, and surface-treated sulfur; preferably oil-extended insoluble sulfur and/or Sulfur predispersion.

In some preferred embodiments, the accelerator is selected from thiazoles, thiurams, sulfenamides, guanidines, dithiocarbamates, aldehyde amines, xanthates, thioureas At least one of the class; preferably a sulfenamide accelerator.

In some preferred embodiments, the sulfenamide accelerator is selected from at least one of accelerator CBS, accelerator DBS, accelerator NS, accelerator OTOS, accelerator NOBS; preferably accelerator CBS and/or or Accelerator DBS.

In some preferred embodiments, the metal organic compound is selected from at least one of cobalt stearate, cobalt decanoate, cobalt naphthenate, cobalt neodecanoate, cobalt boroacylate, and cobalt neodecanoate borate; preferably At least one of cobalt stearate, cobalt naphthenate, cobalt neodecanoate and cobalt boroacylate; more preferably cobalt neodecanoate.

In some preferred embodiments, the molecular structure of the auxiliary agent is shown in the following formula:

Wherein, R1-R5 are the same or different, selected from hydrogen, C1-10 alkyl, C3-10 alkenyl, C1-10 alkoxy, C1-10 haloalkyl, C2-10 haloalkenyl, hydroxyl, carboxyl, Amino, nitro, hydrogen, C1-10 alkyl, C2-10 alkenyl, C1-10 alkoxy, C1-10 haloalkyl, C2-10 haloalkenyl, hydroxyl, carboxyl, amino, nitro Vinyl substituted by one or more groups of hydrogen, C1-10 alkyl, C2-10 alkenyl, C1-10 alkoxy, C1-10 haloalkyl, C2-10 haloalkenyl, hydroxyl, Substituted by one or more of carboxyl, amino, nitro Among them, at least one substituent is hydrogen, C1-10 alkyl, C1-10 alkenyl, C1-10 alkoxy, C1-10 haloalkyl, C1-10 haloalkenyl, hydroxyl, carboxyl, amino, Vinyl substituted by one or more groups in nitro, or by hydrogen, C1-10 alkyl, C1-10 alkenyl, C1-10 alkoxy, C1-10 haloalkyl, C1-10 halo Substituted by one or more of alkenyl, hydroxyl, carboxyl, amino, nitro

R6-R10 are the same or different, selected from hydrogen, C1-10 alkyl, C3-10 alkenyl, C1-10 alkoxy, C1-10 haloalkyl, C2-10 haloalkenyl, hydroxyl, carboxyl, amino, Nitro, one of hydrogen, C1-10 alkyl, C2-10 alkenyl, C1-10 alkoxy, C1-10 haloalkyl, C2-10 haloalkenyl, hydroxyl, carboxyl, amino, nitro or vinyl substituted by multiple groups, by hydrogen, C1-10 alkyl, C2-10 alkenyl, C1-10 alkoxy, C1-10 haloalkyl, C2-10 haloalkenyl, hydroxyl, carboxyl, Substituted by one or more of amino and nitro groups Among them, at least one substituent is hydrogen, C1-10 alkyl, C1-10 alkenyl, C1-10 alkoxy, C1-10 haloalkyl, C1-10 haloalkenyl, hydroxyl, carboxyl, amino, Vinyl substituted by one or more groups in nitro, or by hydrogen, C1-10 alkyl, C1-10 alkenyl, C1-10 alkoxy, C1-10 haloalkyl, C1-10 halo Substituted by one or more of alkenyl, hydroxyl, carboxyl, amino, nitro

Preferably, the molecular structure of the vulcanization aid is as follows:

Wherein, R2-R9 is as defined above, and X is selected from hydrogen, C1-10 alkyl, C2-10 alkenyl, C1-10 alkoxy, C1-10 haloalkyl, C2-10 haloalkenyl, hydroxyl, carboxyl, At least one of amino group and nitro group.

Preferably, X is methyl.

Further preferably, the auxiliary agent is bis(2-citraconimidephenyl) disulfide.

The bis(2-citraconimide phenyl) disulfide is independently developed by the applicant, and its molecular structure is as follows:

In some preferred embodiments, the melting point of the bis(2-citraconimidephenyl) disulfide is 188-194°C, the ash content is 0.07%, and the heating loss is 0.13%.

In some preferred embodiments, the preparation method of the bis(2-citraconimide phenyl) disulfide is:

In an autoclave, mix benzothiazole and sodium hydroxide aqueous solution, raise the temperature and pressurize, and stir to obtain the first intermediate; then add industrial hydrochloric acid to proceed, then drop the industrial hydrogen peroxide after cooling down, keep warm, react, filter and dry to obtain the second intermediate Intermediate; finally, mix the second intermediate with acetic acid dropwise, add citrate anhydride to keep warm and stir, add toluenesulfonic acid to raise the temperature and reflux for reaction, then recover the first three, add ethanol and cool the system, and filter and dry the material to obtain the product. For specific parameters, please refer to 2021114041308.

In the present invention, through additives, especially adding bis(2-citraconimide phenyl) disulfide, synergistically acting with raw materials such as metal organics, as sulfur in the normal vulcanization stage, the crosslinking density of the rubber material is improved, Increase the proportion of polysulfide bonds in the rubber during the over-vulcanization stage; at the same time, it can significantly reduce the reversion rate of the rubber during the over-vulcanization stage, and the conjugated disulfide bond generated by the modification of the natural rubber/isoprene rubber main chain during the over-vulcanization stage The double Diels-Alder reaction of ene and triene can compensate the polysulfide cross-linking bond and carbon-carbon cross-linking bond at the same time, and greatly improve the modulus stress of vulcanizate. The inventors unexpectedly found that when the amount of additives added is 1.28 parts, the R30 of the obtained rubber composition is only 5.12%, and the 100% modulus is as high as 4.3 MPa, and the 300% modulus is as high as 17.3 MPa.

In some preferred embodiments, according to product performance requirements, the raw materials for the preparation of the rubber composition with high modulus stress may also include other additives, such as coupling agent, protective wax, flame retardant, anti-scorch agent, oil.

A second aspect of the present invention has a method for preparing a rubber composition with high modulus, comprising:

(1) One-stage mixing: after banburying the rubber in an internal mixer, add activators, additives, and fillers, then mix, then continue to add fillers, anti-aging agents, mix, and park after degluing;

(2) Two-stage mixing: pass the mixture obtained in (1) on an open mill, add sulfur, accelerators and metal organic substances, roll up, pack, and produce tablets.

Preferably, include:

(1) One-stage mixing: at 100-150°C, banbury the rubber in an internal mixer for 30-80s, then add activators, additives and fillers and mix for 30-60s, then continue to add the remaining fillers and anti-aging agents Mix for 2-10 minutes, and park for 12-48 hours after debinding;

(2) Two-stage mixing: at 25-80°C, pass the second-stage compound rubber on the open mill for 2-5 times, add sulfur, accelerators and metal organics, roll and pack for 2-6 times, and then release sheet to obtain the rubber composition with high modulus.

Preferably, the rotor speed of the internal mixer described in step (1) is 40-70r/min; preferably 45-60r/min; more preferably;

The filler described in step (1) is added in two times, and the mass parts of the first and second additions are equal.

The rotor speed of the mill described in step (2) is 40～70r/min; preferably 45～60r/min; more preferably;

In the step (2), the speed ratio of the front and rear rolls of the thin pass on the mill is adjusted to 1: (0.8-2); preferably 1:1.2.

Compared with the prior art, the present invention has the following beneficial effects:

(1) In the present invention, by adding additives such as rubber, filler, activator, anti-aging agent, sulfur, accelerator, auxiliary agent, the rubber composition prepared has high modulus, and the rubber composition obtained has excellent wear resistance Consumption performance, strong adhesion with metal plate/steel cord, and excellent resistance to denaturation under external force.

(2) By adding bis(2-citraconimide phenyl) disulfide, the present invention can improve the vulcanization reversion of rubber on the one hand; on the other hand, it can greatly improve the modulus of vulcanized rubber and enhance the external force The ability to resist deformation under action.

(3) In the present invention, the rubber composition with high modulus stress is obtained by adding the preparation raw materials according to different addition sequences, combined with a specific rubber preparation process, the preparation process is simple and adjustable, and compared with the prior art, this The invention is more in line with the requirements of green environmental protection, has the advantages of strong universality and is suitable for large-scale production, and can be widely used in thick rubber products such as mine tires and truck radial tires.

Description of drawings

The DSC spectrum of Fig. 1 bis (2-citraconimide phenyl) disulfide

Figure 2 The infrared spectrum of bis(2-citraconimide phenyl) disulfide

Detailed ways

Example 1

1. A rubber composition with high modulus stress. In terms of parts by mass, its preparation raw materials include: 100 parts of rubber, 50 parts of filler, 5.5 parts of activator, 2 parts of anti-aging agent, 2 parts of sulfur, and 1.2 parts of accelerator , 1 part of auxiliary agent.

Described rubber is natural rubber (natural rubber NR, Vietnam SVR-3L company).

The filler is carbon black.

The iodine absorption value of the carbon black is 120g/kg, and the DBP value is 125cm3/100g (Suzhou Baohua Carbon Black Co., Ltd., carbon black N234).

The activator is zinc oxide and stearic acid.

The mass ratio of zinc oxide and stearic acid is 3.5:2.

The anti-aging agent is a ketamine anti-aging agent and a p-phenylenediamine anti-aging agent.

The mass ratio of the ketamine anti-aging agent to the p-phenylenediamine anti-aging agent is 1:1.

The ketone-amine anti-aging agent is anti-aging agent RD.

The p-phenylenediamine anti-aging agent is anti-aging agent 4020.

The sulfur is a sulfur predispersion, specifically predispersion S-80.

The accelerator is a sulfenamide accelerator; the accelerator CBS is a sulfenamide accelerator.

The auxiliary agent is bis(2-citraconimide phenyl) disulfide.

The bis(2-citraconimide phenyl) disulfide is independently developed by the applicant, and its molecular structure is as follows:

The melting point of the bis(2-citraconimidephenyl) disulfide is 188-194°C, the ash content is 0.07%, and the heating loss is 0.13%.

The preparation method of described two (2-citraconimide phenyl) disulfides is:

In an autoclave, mix benzothiazole and sodium hydroxide aqueous solution, raise the temperature and pressurize, and stir to obtain the first intermediate; then add industrial hydrochloric acid to proceed, then drop the industrial hydrogen peroxide after cooling down, keep warm, react, filter and dry to obtain the second intermediate Intermediate; finally, mix the second intermediate with acetic acid dropwise, add citrate anhydride to keep warm and stir, add toluenesulfonic acid to raise the temperature and reflux for reaction, then recover the first three, add ethanol and cool the system, and filter and dry the material to obtain the product. For specific parameters, please refer to Example 1 in 2021114041308.

2. A method for preparing a rubber composition with high modulus, comprising:

(1) One-stage mixing: at 130°C, mix the rubber in an internal mixer for 60s, then add activators, additives, and fillers and mix for 40s, then continue to add the remaining fillers and anti-aging agents and mix for 3 minutes, then remove the rubber After parking for 12 hours;

(2) Second-stage mixing: at 25°C, the cooling water is fully turned on, and the second-stage compound rubber is thinly passed on the open mill for 3 times, adding sulfur, accelerators and metal organics, cutting the left and right knives 3 times, and making triangles Wrap 5 times, thin pass 3 times, pack 3 times, and then release the film.

The rotor speed of internal mixer described in step (1) is 45r/min.

The filler described in step (1) is added in two times, and the mass parts of the first and second additions are equal.

The rotor speed of the mill described in step (2) is 45r/min.

In the step (2), the speed ratio of the front and rear rolls of the thin pass on the mill is adjusted to 1:1.2.

Example 2

1. A rubber composition with high modulus, the difference from Example 1 is:

The preparation raw materials include: 1.28 parts of vulcanization aids.

2. A preparation method of a rubber composition with high modulus, same as in Example 1.

Comparative example 1

1. A rubber composition with high modulus, the difference from Example 1 is:

No additives are included in the preparation raw materials.

2. A preparation method of a rubber composition with high modulus, same as in Example 1.

Comparative example 2

1. A rubber composition with high modulus, the difference from Example 1 is:

The auxiliary agent is PK900.

2. A preparation method of a rubber composition with high modulus, same as in Example 1.

Table 1 shows the raw materials for preparing the rubber composition with high modulus in Example 1-2 and Comparative Example 1-2.

Table 1 Embodiment 1-2, comparative example 1-2 have the rubber composition object preparation raw material of high modulus stress

Example 3

1. A rubber composition with high modulus, the difference from Example 1 is:

In terms of parts by mass, its preparation raw materials include: 100 parts of rubber, 55 parts of filler, 8 parts of activator, 3.5 parts of anti-aging agent, 4.5 parts of sulfur, 1 part of accelerator, 1.2 parts of metal organic matter, and 1.28 parts of auxiliary agent.

The fillers are carbon black and white carbon black.

The iodine absorption value of the carbon black is 82g/kg, and the DBP value is 102cm3/100g (Jiangsu Ruiba New Material Technology Co., Ltd., carbon black N330).

The mass ratio of carbon black and white carbon black is 4.5:1.

The specific surface area of the white carbon black is 172m2/g, and the tap density is 210g/L (white carbon black VN3).

The metal organic compound is cobalt neodecanoate.

The activator is zinc oxide.

The mass ratio of the ketamine antioxidant and p-phenylenediamine antioxidant is 1.5:2.

The sulfur is insoluble sulfur, specifically oil-extended insoluble sulfur with an oil-extended content of 10%.

Said sulfenamide accelerator is accelerator DBS.

2. A preparation method of a rubber composition with high modulus, same as in Example 1.

Example 4

1, a kind of rubber composition with high modulus, the difference with embodiment 3 is:

The preparation raw materials include: 2.57 parts of auxiliary agents.

2. A preparation method of a rubber composition with high modulus, same as in Example 1.

Example 5

1, a kind of rubber composition with high modulus, the difference with embodiment 3 is:

The preparation raw materials include: 3.85 parts of auxiliary agents.

2. A preparation method of a rubber composition with high modulus, same as in Example 1.

Example 6

1, a kind of rubber composition with high modulus, the difference with embodiment 3 is:

The preparation raw materials include: 5.13 parts of auxiliary agents.

2. A preparation method of a rubber composition with high modulus, same as in Example 1.

Comparative example 3

1, a kind of rubber composition with high modulus, the difference with embodiment 3 is:

The raw materials for its preparation do not include additives.

2. A preparation method of a rubber composition with high modulus, same as in Example 1.

Comparative example 4

1, a kind of rubber composition with high modulus, the difference with embodiment 3 is:

The preparation raw materials include: 1 part of auxiliary agent.

The auxiliary agent is PK900.

2. A preparation method of a rubber composition with high modulus, same as in Example 1.

Comparative example 5

1, a kind of rubber composition with high modulus, the difference with embodiment 3 is:

The preparation raw materials include: 2 parts of auxiliary agent.

The auxiliary agent is PK900.

2. A preparation method of a rubber composition with high modulus, same as in Example 1.

Comparative example 6

1. A rubber composition with high modulus, the difference from Example 1 is:

The preparation raw materials include: 3 parts of auxiliary agents.

The auxiliary agent is PK900.

2. A preparation method of a rubber composition with high modulus, same as in Example 1.

Comparative example 7

1. A rubber composition with high modulus, the difference from Example 1 is:

The preparation raw materials include: 4 parts of auxiliary agents.

The auxiliary agent is PK900.

2. A preparation method of a rubber composition with high modulus, same as in Example 1.

Table 2 shows the raw materials for the preparation of rubber compositions with high modulus in Examples 3-6 and Comparative Examples 3-7.

Raw materials for the preparation of rubber composites with high modulus in Table 2 Examples 3-6 and Comparative Examples 3-7

Performance Testing

1. DSC test: See Figure 1 for specific results.

2. Infrared test: See Figure 2 for specific results.

Vulcanization characteristics: According to the standard GB/T16584-1996, the test is carried out with a rotorless rheometer, the test temperature is 150°C, and the test time is 60 minutes. The vulcanization reversion rate of the rubber compound is calculated by the following formula (1):

In the formula, Rt represents the reversion rate at time t (unit: minute), and MH, ML and Mt represent the maximum torque, minimum torque and torque at time t (unit: minute) respectively.

2. 100% modulus and 300% modulus: each rubber composition was vulcanized at 150° C. for 30 minutes, and stood for 16 hours after vulcanization to be tested. Electronic tensile testing machine is used to test according to GB/T 528-2009.

The specific test results are shown in Table 1 and Table 2.

It can be clearly seen from the test results of Table 1 and Table 2 that, compared with the rubber compositions corresponding to Comparative Examples 1-7, no matter the parts or moles of PK900 and bis(2-citraconimide phenyl) disulfide (mol) When the amount is the same, the rubber compositions of Examples 1-6 all have higher 100% modulus and 300% modulus, which shows that two (2-citraconimide phenyl) disulfide The compounds not only participate in the vulcanization reaction, but also provide better anti-reversion performance.

Claims (10)

1. A rubber composition with high stretching stress is characterized in that the preparation raw materials comprise: rubber, filler, activator, anti-aging agent, sulfur, accelerator, metal organic matter and auxiliary agent.

2. The rubber composition with high stretching stress according to claim 1, wherein the preparation raw materials comprise, by mass: 100 parts of rubber, 20-100 parts of filler, 2-17 parts of activating agent, 0.5-5 parts of anti-aging agent, 0.5-10 parts of sulfur, 0.1-8 parts of accelerator, 0-3 parts of metal organic matter and 0.5-10 parts of auxiliary agent.

3. A rubber composition with high elongation stress according to claim 1 or 2, wherein the molecular structure of the auxiliary agent is represented by the following formula:

wherein R is ¹ -R ⁵ Identical or different, selected from hydrogen, C _1-10 Alkyl, C _3-10 Alkenyl, C _1-10 Alkoxy, C _1-10 Haloalkyl, C _2-10 Haloalkenyl, hydroxy, carboxy, amino, nitro, substituted with hydrogen, C _1-10 Alkyl, C _2-10 Alkenyl, C _1-10 Alkoxy, C _1-10 Haloalkyl, C _2-10 Vinyl substituted by one or more of halogen alkenyl, hydroxy, carboxyl, amino, nitro, hydrogen, C _1-10 Alkyl, C _2-10 Alkenyl, C _1-10 Alkoxy, C _1-10 Haloalkyl, C _2-10 Substituted with one or more of haloalkenyl, hydroxy, carboxyl, amino, nitroWherein at least one substituent is hydrogen, C _1-10 Alkyl, C _1-10 Alkenyl, C _1-10 Alkoxy, C _1-10 Haloalkyl, C _1-10 Vinyl substituted by one or more of haloalkenyl, hydroxy, carboxyl, amino, nitro, or by hydrogen, C _1-10 Alkyl, C _1-10 Alkenyl, C _1-10 Alkoxy, C _1-10 Haloalkyl, C _1-10 Halo alkenyl, hydroxy, carboxyl, amino, nitro>

R ⁶ -R ¹⁰ Identical or different, selected from hydrogen, C _1-10 Alkyl, C _3-10 Alkenyl, C _1-10 Alkoxy, C _1-10 Haloalkyl, C _2-10 Haloalkenyl, hydroxy, carboxyAmino, nitro, hydrogen, C _1-10 Alkyl, C _2-10 Alkenyl, C _1-10 Alkoxy, C _1-10 Haloalkyl, C _2-10 Vinyl substituted by one or more of halogen alkenyl, hydroxy, carboxyl, amino, nitro, hydrogen, C _1-10 Alkyl, C _2-10 Alkenyl, C _1-10 Alkoxy, C _1-10 Haloalkyl, C _2-10 Substituted with one or more of haloalkenyl, hydroxy, carboxyl, amino, nitroWherein at least one substituent is hydrogen, C _1-10 Alkyl, C _1-10 Alkenyl, C _1-10 Alkoxy, C _1-10 Haloalkyl, C _1-10 Vinyl substituted by one or more of haloalkenyl, hydroxy, carboxyl, amino, nitro, or by hydrogen, C _1-10 Alkyl, C _1-10 Alkenyl, C _1-10 Alkoxy, C _1-10 Haloalkyl, C _1-10 Halo alkenyl, hydroxy, carboxyl, amino, nitro>

4. A rubber composition having a high tensile stress according to claim 3, wherein the molecular structure of said auxiliary agent is of the formula:

wherein R is ² -R ⁹ As defined above, X is selected from at least one of hydrogen, C1-10 alkyl, C2-10 alkenyl, C1-10 alkoxy, C1-10 haloalkyl, C2-10 haloalkenyl, hydroxy, carboxy, amino, nitro.

5. The rubber composition with high stretching stress according to claim 1 or 2, wherein the rubber is at least one selected from the group consisting of natural rubber, chlorinated butyl rubber, brominated butyl rubber, isoprene rubber, styrene-butadiene rubber, nitrile rubber, ethylene propylene diene monomer rubber and butyl rubber.

6. The rubber composition having a high stretching stress according to claim 5, wherein the filler is at least one selected from the group consisting of carbon black, white carbon black, clay, barite powder, talc, calcium carbonate powder, kaolin, and mica powder.

7. The rubber composition having a high stretching stress according to claim 6, wherein the antioxidant is at least one selected from the group consisting of phenolic antioxidants, ketoamine antioxidants, benzimidazole antioxidants, p-phenylenediamine antioxidants and thiourea antioxidants.

8. The rubber composition having a high stretching stress according to claim 7, wherein the sulfur is at least one selected from the group consisting of oil-filled insoluble sulfur, sulfur pre-dispersion, powdered sulfur, colloidal sulfur, precipitated sulfur, surface treated sulfur;

the accelerator is at least one selected from thiazoles, thiurams, sulfenamides, guanidine, dithiocarbamates, aldamines, xanthates and thioureas.

9. The rubber composition of claim 8, wherein said metal organic is at least one selected from the group consisting of cobalt stearate, cobalt decanoate, cobalt naphthenate, cobalt neodecanoate, cobalt boronoate, and cobalt neodecanoate borate.

10. A process for the preparation of a rubber composition having a high tensile stress according to any one of claims 1 to 9, comprising:

(1) And (3) mixing: mixing rubber in an internal mixer, adding an activating agent, an auxiliary agent and a filler, mixing, continuously adding the filler and an anti-aging agent, mixing, discharging rubber and standing;

(2) Two-stage mixing: and (3) thinning the mixture obtained in the step (1) on an open mill, adding sulfur, an accelerator and metal organic matters, rolling, packaging and discharging tablets.