CN109401331B - Energy-absorbing high-temperature vulcanized silicone rubber and preparation method thereof - Google Patents

Energy-absorbing high-temperature vulcanized silicone rubber and preparation method thereof Download PDF

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CN109401331B
CN109401331B CN201811202951.1A CN201811202951A CN109401331B CN 109401331 B CN109401331 B CN 109401331B CN 201811202951 A CN201811202951 A CN 201811202951A CN 109401331 B CN109401331 B CN 109401331B
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silicone rubber
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pyroboric acid
agent
temperature
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CN109401331A (en
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何波兵
张东升
蒋楠
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Chengdu Zongheng Innovation Technology Co.,Ltd.
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Chengdu Weishang Technology Co ltd
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Abstract

The invention discloses energy-absorbing high-temperature vulcanized silicone rubber which is characterized by comprising the following components in percentage by weight: 80-120 parts of methyl vinyl silicone rubber, 0-110 parts of reinforcing filler, 0.1-3 parts of vulcanizing agent, 0.5-15 parts of structure control agent, 0.1-10 parts of anti-tearing agent and 2-50 parts of pyroboric acid modified polydimethylsiloxane. The invention also discloses a specific preparation method. The pyroboric acid modified hydroxyl-terminated polysiloxane and the high-temperature vulcanized silicone rubber are compounded, so that the pyroboric acid modified hydroxyl-terminated polysiloxane and the high-temperature vulcanized silicone rubber have good compatibility, the advantages of the pyroboric acid modified hydroxyl-terminated polysiloxane and the high-temperature vulcanized silicone rubber can be integrated, the shortages of the pyroboric acid modified hydroxyl-terminated polysiloxane and the high-temperature vulcanized silicone rubber can be made up, and the energy-absorbing composite material which can recover to the initial form after impact and has the impact resistance can be obtained.

Description

Energy-absorbing high-temperature vulcanized silicone rubber and preparation method thereof
Technical Field
The invention belongs to the technical field of polymer composite materials, and relates to a preparation method of a modified polysiloxane/high-temperature vulcanized silicone rubber composite material
Background
Pyroboric acid modified polysiloxane is a gel-like material having a shear hardening effect. Under the action of low speed, the material shows the property of viscous fluid, is easy to deform and even has the same slow flow as the fluid; but under the action of high speed, the material immediately shows extremely high strength, maintains the original shape and firmly resists the impact of external force, thereby playing the roles of buffering and absorbing energy. The material has stable physical and chemical properties and excellent shock resistance. However, since the resin is deformed and cannot be recovered when it is subjected to impact, it is not generally used as it is, and it is necessary to use it in combination with other base materials.
The high-temperature vulcanized silicone rubber is prepared by adding reinforcing filler and other various additives into high-molecular-weight (generally 40-80 ten thousand molecular weight) polyorganosiloxane (namely raw rubber), adopting organic peroxide as a vulcanizing agent, performing pressure molding (mould pressing, extrusion and calendaring) or injection molding, and crosslinking at high temperature to obtain the rubber. The high-temperature vulcanized silicone rubber has excellent performances of good high and low temperature resistance, weather resistance, ozone resistance, elasticity and the like, but the impact resistance performance of the high-temperature vulcanized silicone rubber is general and needs to be improved.
Disclosure of Invention
The invention aims to solve the problems in the prior art, and provides high-temperature vulcanized silicone rubber with impact resistance and a preparation method thereof.
The technical scheme of the invention is as follows:
an energy-absorbing high-temperature vulcanized silicone rubber (non-foaming) comprises the following components in percentage by weight: 80-120 parts of methyl vinyl silicone rubber, 0-110 parts of reinforcing filler, 0.1-3 parts of vulcanizing agent, 0.5-15 parts of structure control agent, 0.1-10 parts of anti-tearing agent and 2-50 parts of pyroboric acid modified polydimethylsiloxane.
Further, the energy-absorbing high-temperature vulcanized silicone rubber comprises the following components in percentage by weight: 100 parts of methyl vinyl silicone rubber, 0-100 parts of reinforcing filler, 0.5-1 part of vulcanizing agent, 1-10 parts of structure control agent, 0.2-5 parts of anti-tearing agent and 5-45 parts of pyroboric acid modified polydimethylsiloxane.
Preferably, the energy-absorbing high-temperature vulcanized silicone rubber comprises the following components in percentage by weight: 100 parts of methyl vinyl silicone rubber, 2 parts of reinforcing filler, 0.5 part of vulcanizing agent, 1 part of structure control agent, 1 part of anti-tearing agent and 18.4 parts of pyroboric acid modified polydimethylsiloxane. 100 parts of methyl vinyl silicone rubber, 10 parts of reinforcing filler, 0.5 part of vulcanizing agent, 1 part of structure control agent, 0.5 part of anti-tearing agent and 12.4 parts of pyroboric acid modified polydimethylsiloxane.
Preferably, the reinforcing filler comprises at least one of fumed silica, precipitated silica, organic montmorillonite, titanium dioxide, kaolin and calcium carbonate; the vulcanizing agent comprises at least one of di-tert-butyl peroxide (DTBP), dicumyl peroxide (DCP) and 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane (DBPMH); the structure control agent is at least one of phenyl silanediol, hexamethyldisilazane, low-molecular-weight hydroxyl-terminated polydimethylsiloxane and cyclic silazane; the anti-tearing agent is polyvinyl silicone oil; the molecular weight of the simethicone is 2-10 ten thousand; the mass ratio of the pyroboric acid to the dimethyl silicone oil is 0.1-10 percent; the pyroboric acid modified polydimethylsiloxane is prepared by reacting dimethyl silicone oil and pyroboric acid in a vacuum kneader at the temperature of 120-160 ℃ for 3-6 hours.
The preparation method of the energy-absorbing high-temperature vulcanized silicone rubber comprises the following steps:
(1) respectively adding the methyl vinyl silicone rubber, the reinforcing filler, the vulcanizing agent, the structure control agent and the anti-tearing agent into an internal mixer for internal mixing for 10 minutes at normal temperature, adding the pyroboric acid modified polydimethylsiloxane, and performing internal mixing for 20-30 minutes at normal temperature;
(2) putting the mixture obtained in the step (1) into a mold, and vulcanizing for 15min-20min on a flat vulcanizing machine with the pressure of 10MPa and the temperature of 155-170 ℃;
(3) and (3) carrying out over vulcanization on the high-temperature vulcanized silicone rubber obtained in the step (2) in an oven at 200 ℃ for 1-4h to obtain the energy-absorbing high-temperature vulcanized silicone rubber.
An energy-absorbing high-temperature vulcanized silicone rubber (foam) comprises the following components in percentage by weight: 100 parts of methyl vinyl silicone rubber, 0-100 parts of reinforcing filler, 0.5-1 part of vulcanizing agent, 1-10 parts of structure control agent, 0.2-5 parts of anti-tearing agent, 5-45 parts of pyroboric acid modified polydimethylsiloxane and 1-4 parts of foaming agent.
Preferably, the high-temperature-capable vulcanized silicone rubber is characterized by comprising the following components in percentage by weight: 100 parts of methyl vinyl silicone rubber, 2 parts of reinforcing filler, 0.5 part of vulcanizing agent, 1 part of structure control agent, 1 part of anti-tearing agent, 18.4 parts of pyroboric acid modified polydimethylsiloxane and 4 parts of foaming agent;
the anti-tear agent can also comprise 100 parts of methyl vinyl silicone rubber, 10 parts of reinforcing filler, 0.5 part of vulcanizing agent, 1 part of structure control agent, 0.5 part of anti-tear agent, 12.8 parts of pyroboric acid modified polydimethylsiloxane and 4 parts of foaming agent.
Preferably, the reinforcing filler comprises at least one of fumed silica, precipitated silica, organic montmorillonite, titanium dioxide, kaolin and calcium carbonate; the vulcanizing agent comprises at least one of di-tert-butyl peroxide (DTBP), dicumyl peroxide (DCP) and 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane (DBPMH); the structure control agent is at least one of phenyl silanediol, hexamethyldisilazane, low-molecular-weight hydroxyl-terminated polydimethylsiloxane and cyclic silazane; the anti-tearing agent is polyvinyl silicone oil; the molecular weight of the simethicone is 2-10 ten thousand; the mass ratio of the pyroboric acid to the dimethyl silicone oil is 0.1-10 percent; reacting dimethyl silicone oil and pyroboric acid in a vacuum kneader at the temperature of 120-160 ℃ for 3-6 hours to obtain pyroboric acid modified polydimethylsiloxane; the foaming agent is a microsphere foaming agent, and the foaming temperature is less than or equal to the vulcanization temperature of a vulcanizing agent.
The preparation method of the energy-absorbing high-temperature vulcanized silicone rubber comprises the following steps:
(1) respectively adding the methyl vinyl silicone rubber, the reinforcing filler, the vulcanizing agent, the structure control agent and the anti-tearing agent into an internal mixer for internal mixing for 10 minutes at normal temperature, then adding the foaming agent for internal mixing for 10 minutes, then adding the pyroboric acid modified polydimethylsiloxane for internal mixing for 20-30 minutes at normal temperature;
(2) putting the mixture obtained in the step (1) into a mold, and vulcanizing for 15min-20min on a flat vulcanizing machine with the pressure of 10MPa and the temperature of 155-170 ℃;
(3) and (3) carrying out over vulcanization on the high-temperature vulcanized silicone rubber obtained in the step (2) in an oven at 200 ℃ for 1-4h to obtain the foaming energy-absorbing high-temperature vulcanized silicone rubber.
Preferably, the molecular weight of the methyl vinyl silicone rubber is 40-80 ten thousand, and the mole fraction of vinyl chain units is 0.03-0.24%.
Has the advantages that:
the pyroboric acid modified hydroxyl-terminated polysiloxane and the high-temperature vulcanized silicone rubber are compounded, so that the pyroboric acid modified hydroxyl-terminated polysiloxane and the high-temperature vulcanized silicone rubber have good compatibility, the advantages of the pyroboric acid modified hydroxyl-terminated polysiloxane and the high-temperature vulcanized silicone rubber can be integrated, the shortages of the pyroboric acid modified hydroxyl-terminated polysiloxane and the high-temperature vulcanized silicone rubber can be made up, and the energy-absorbing composite material which can recover to the initial form after impact and has the impact resistance can be obtained.
The modified polysiloxane/high-temperature vulcanized silicone rubber composite material has the advantages that the pyroboric acid modified polysiloxane and the high-temperature vulcanized silicone rubber are compounded, and when the prepared modified polysiloxane/high-temperature vulcanized silicone rubber composite material is sheared or impacted, the pyroboric acid modified polysiloxane distributed in a disperse phase in the material absorbs and dissipates part of energy through the shearing and hardening action, so that the impact performance of the high-temperature vulcanized silicone rubber is enhanced; after impact, the non-destructive deformation can be restored. The preparation process is simple and convenient to operate, is suitable for industrial production, and the composite material can replace the traditional silicon rubber product and is used for sealing, damping, buffering and other environments.
The energy-absorbing high-temperature vulcanized silicone rubber comprises two types of foaming and non-foaming, wherein the foaming and the non-foaming can improve the impact resistance of the high-temperature vulcanized silicone rubber, but the application ranges of the foaming and the non-foaming are different, and the non-foaming energy-absorbing high-temperature vulcanized silicone rubber is relatively hard and is mainly used in the field with larger impact energy; the foaming energy-absorbing high-temperature vulcanized silicone rubber has better buffering performance due to the foaming body, and is mainly applied to the field with smaller impact energy and higher energy absorption rate.
The specific implementation mode is as follows:
the following examples and experimental examples are intended to illustrate the present invention, but are not intended to limit the scope of the present invention. The present invention will be further described with reference to the following examples and experimental examples
Example 1
Step 1: weighing 50g of 50000mPa & s dimethyl silicone oil, adding 1g of pyroboric acid, and reacting in a vacuum kneader at 130 ℃ for 3 hours to obtain pyroboric acid modified polydimethylsiloxane;
step 2: weighing 50g of methyl vinyl silicone rubber, placing the methyl vinyl silicone rubber into an internal mixer, sequentially adding 1g of fumed silica, 0.5g of hexamethyldisilazane, 0.5g of polyvinyl silicone oil and 0.25g of dicumyl peroxide, mixing for 10 minutes, adding 9.2g of the pyroboric acid modified polydimethylsiloxane in the step 1, and mixing for 30 minutes;
step 3, putting the mixture obtained in the step 2 into a mold, and vulcanizing for 15min under the pressure of 10MPa and the temperature of 170 ℃;
and 4, step 4: and (4) carrying out over vulcanization on the high-temperature vulcanized silicone rubber obtained in the step (3) in an oven at 200 ℃ for 4 hours to obtain the energy-absorbing high-temperature vulcanized silicone rubber.
Comparative example 1
Step 1: weighing 50g of methyl vinyl silicone rubber, putting the methyl vinyl silicone rubber into an internal mixer, adding 1g of fumed silica, 0.5g of hexamethyldisilazane, 0.5g of polyvinyl silicone oil, 0.25g of dicumyl peroxide and 9.2g of dimethyl silicone oil in sequence, and refining for 30 minutes;
step 2, putting the mixture obtained in the step 1 into a mold, and vulcanizing for 15min on a flat vulcanizing machine with the pressure of 10MPa and the temperature of 170 ℃;
and step 3: and (3) carrying out over vulcanization on the high-temperature vulcanized silicone rubber obtained in the step (2) in an oven at 200 ℃ for 4h to obtain the high-temperature vulcanized silicone rubber.
Comparative example 1 and comparative example 1:
adopting a drop hammer impact experiment to test the impact resistance of a sample, wherein the test conditions are as follows: impact energy of 10 joules, velocity of 3.162m/s, hardness, density, impact acceleration, energy absorption of the test samples, test results for example 1 and comparative example 1 are given in the following table:
sample (I) Comparative example 1 Example 1
Hardness (Shao A) 33.5 26.6
Density (g/cm)3) 1.132 1.056
Maximum impact acceleration (g) 406 280
Energy absorption rate 15.1％ 41.5％
As can be seen from the data in the table, compared with the common silicon rubber, the energy absorption rate of the energy-absorbing high-temperature vulcanized silicon rubber is improved by 174%, which shows that the impact resistance of the energy-absorbing high-temperature vulcanized silicon rubber is obviously improved.
Example 2
Step 1: weighing 50g of 50000mPa & s dimethyl silicone oil, adding 2g of pyroboric acid, and reacting in a vacuum kneader at 130 ℃ for 3 hours to obtain pyroboric acid modified polydimethylsiloxane;
step 2: weighing 50g of methyl vinyl silicone rubber, placing the methyl vinyl silicone rubber into an internal mixer, sequentially adding 5g of fumed silica, 0.5g of hexamethyldisilazane, 0.25g of polyvinyl silicone oil and 0.25g of dicumyl peroxide, mixing for 10 minutes, adding 6.4g of the pyroboric acid modified polydimethylsiloxane in the step 1, and mixing for 30 minutes;
step 3, putting the mixture obtained in the step 2 into a mold, and vulcanizing for 15min under the pressure of 10MPa and the temperature of 170 ℃;
and 4, step 4: and (4) carrying out over vulcanization on the high-temperature vulcanized silicone rubber obtained in the step (3) in an oven at 200 ℃ for 1h to obtain the energy-absorbing high-temperature vulcanized silicone rubber.
Comparative example 2
Step 1: weighing 50g of methyl vinyl silicone rubber, putting the methyl vinyl silicone rubber into an internal mixer, adding 5g of gas phase method silicon dioxide, 0.5g of hexamethyldisilazane, 0.25g of polyvinyl silicone oil, 0.25g of dicumyl peroxide and 6.4g of dimethyl silicone oil in sequence, and refining for 30 minutes;
step 2, putting the mixture obtained in the step 1 into a mold, and vulcanizing for 15min on a flat vulcanizing machine with the pressure of 10MPa and the temperature of 170 ℃;
and step 3: and (3) carrying out over vulcanization on the high-temperature vulcanized silicone rubber obtained in the step (2) in an oven at 200 ℃ for 1h to obtain the high-temperature vulcanized silicone rubber.
Comparative example 2 and comparative example 2
Adopting a drop hammer impact experiment to test the impact resistance of a sample, wherein the test conditions are as follows: impact energy of 10 joules, velocity of 3.162m/s, hardness, density, impact acceleration, energy absorption of the test samples, test results for example 2 and comparative example 2 are given in the following table:
sample (I) Comparative example 2 Example 2
Hardness (Shao A) 35.5 28
Density (g/cm)3) 1.145 1.086
Maximum impact acceleration (g) 430 289
Energy absorption rate 17.1％ 38.5％
As can be seen from the data in the table, compared with the common silicon rubber, the energy absorption rate of the energy-absorbing high-temperature vulcanized silicon rubber is improved by 125 percent, which shows that the impact resistance of the energy-absorbing high-temperature vulcanized silicon rubber is obviously improved.
Example 3
Step 1: weighing 50g of 50000mPa & s silicone oil, adding 1g of pyroboric acid, and reacting in a vacuum kneader at 130 ℃ for 3 hours to obtain pyroboric acid modified polydimethylsiloxane;
step 2: weighing 50g of methyl vinyl silicone rubber, placing the methyl vinyl silicone rubber into an internal mixer, sequentially adding 1g of fumed silica, 0.5g of hexamethyldisilazane, 0.5g of polyvinyl silicone oil and 0.25g of dicumyl peroxide, carrying out internal mixing for 10 minutes, adding 2g of microsphere foaming agent, carrying out internal mixing for 10 minutes, adding 9.5g of pyroboric acid modified polydimethylsiloxane in the step 1, and carrying out internal mixing for 30 minutes;
step 3, putting the mixture obtained in the step 2 into a mold, and vulcanizing for 15min under the pressure of 10MPa and the temperature of 170 ℃;
and 4, step 4: and (4) carrying out over vulcanization on the high-temperature vulcanized silicone rubber obtained in the step (3) in an oven at 200 ℃ for 4 hours to obtain the energy-absorbing foaming high-temperature vulcanized silicone rubber.
Comparative example 3
Step 1: weighing 50g of methyl vinyl silicone rubber, putting the methyl vinyl silicone rubber into an internal mixer, sequentially adding 1g of fumed silica, 0.5g of hexamethyldisilazane, 0.5g of polyvinyl silicone oil, 0.25g of dicumyl peroxide and 9.5g of dimethyl silicone oil, carrying out internal mixing for 10 minutes, adding 2g of microsphere foaming agent, and carrying out internal mixing for 20 minutes;
step 2, putting the mixture obtained in the step 1 into a mold, and vulcanizing for 15min on a flat vulcanizing machine with the pressure of 10MPa and the temperature of 170 ℃;
and step 3: and (3) carrying out over vulcanization on the high-temperature vulcanized silicone rubber obtained in the step (2) in an oven at 200 ℃ for 4h to obtain the foamed high-temperature vulcanized silicone rubber.
Comparative example 3 and comparative example 3
Adopting a drop hammer impact experiment to test the impact resistance of a sample, wherein the test conditions are as follows: impact energy of 10 joules, velocity of 2.449m/s, hardness, density, impact acceleration, energy absorption of the test samples, test results for example 3 and comparative example 3 are given in the following table:
sample (I) Comparative example 3 Example 3
Hardness (Shao A) 30 23.5
Density (g/cm)3) 0.702 0.623
Maximum impact acceleration (g) 370 252
Energy absorption rate 16.3％ 50.2％
As can be seen from the data in the table, compared with the common foamed silicone rubber, the energy absorption rate of the energy-absorbing foamed high-temperature vulcanized silicone rubber is improved by 207%, which shows that the impact resistance of the energy-absorbing foamed high-temperature vulcanized silicone rubber is obviously improved.
Example 4
Step 1: weighing 50g of 50000mPa & s silicone oil, adding 2g of pyroboric acid, and reacting in a vacuum kneader at 130 ℃ for 3 hours to obtain pyroboric acid modified polydimethylsiloxane;
step 2: weighing 50g of methyl vinyl silicone rubber, placing the methyl vinyl silicone rubber into an internal mixer, sequentially adding 5g of fumed silica, 0.5g of hexamethyldisilazane, 0.25g of polyvinyl silicone oil and 0.25g of dicumyl peroxide, carrying out internal mixing for 10 minutes, adding 2g of microsphere foaming agent, carrying out internal mixing for 10 minutes, adding 6.4g of pyroboric acid modified polydimethylsiloxane in the step 1, and carrying out internal mixing for 30 minutes;
step 3, putting the mixture obtained in the step 2 into a mold, and vulcanizing for 15min under the pressure of 10MPa and the temperature of 170 ℃;
and 4, step 4: and (4) carrying out over vulcanization on the high-temperature vulcanized silicone rubber obtained in the step (3) in an oven at 200 ℃ for 1h to obtain the energy-absorbing foaming high-temperature vulcanized silicone rubber.
Comparative example 4
Step 1: weighing 50g of methyl vinyl silicone rubber, putting the methyl vinyl silicone rubber into an internal mixer, sequentially adding 5g of fumed silica, 0.5g of hexamethyldisilazane, 0.25g of polyvinyl silicone oil, 0.25g of dicumyl peroxide and 6.4g of dimethyl silicone oil, carrying out internal mixing for 10 minutes, adding 2g of microsphere foaming agent, and carrying out internal mixing for 20 minutes;
step 2, putting the mixture obtained in the step 1 into a mold, and vulcanizing for 15min on a flat vulcanizing machine with the pressure of 10MPa and the temperature of 170 ℃;
and step 3: and (3) carrying out over vulcanization on the high-temperature vulcanized silicone rubber obtained in the step (1) in an oven at 200 ℃ for 1h to obtain the foamed high-temperature vulcanized silicone rubber.
Comparative example 4 and comparative example 4
Adopting a drop hammer impact experiment to test the impact resistance of a sample, wherein the test conditions are as follows: impact energy of 10 joules, velocity of 2.449m/s, hardness, density, impact acceleration, energy absorption of the test samples, test results for example 4 and comparative example 4 are given in the following table:
sample (I) Comparative example 4 Example 4
Hardness (Shao A) 31 25
Density (g/cm)3) 0.772 0.683
Maximum impact acceleration (g) 390 276
Energy absorption rate 20.3％ 46.5％
As can be seen from the data in the table, compared with the common foamed silicone rubber, the energy absorption rate of the energy-absorbing foamed high-temperature vulcanized silicone rubber is improved by 129%, which shows that the impact resistance of the energy-absorbing foamed high-temperature vulcanized silicone rubber is obviously improved.

Claims (9)

1. An energy-absorbing high-temperature vulcanized silicone rubber is characterized by comprising the following components in percentage by weight: 80-120 parts of methyl vinyl silicone rubber, 0-110 parts of reinforcing filler, 0.1-3 parts of vulcanizing agent, 0.5-15 parts of structure control agent, 0.1-10 parts of anti-tearing agent and 2-50 parts of pyroboric acid modified polydimethylsiloxane; the molecular weight of the simethicone is 2-10 ten thousand; the mass ratio of the pyroboric acid to the dimethyl silicone oil is 0.1-10 percent; the pyroboric acid modified polydimethylsiloxane is prepared by reacting dimethyl silicone oil with pyroboric acid in a vacuum kneader at the temperature of 120-160 ℃ for 3-6 hours; the molecular weight of the methyl vinyl silicone rubber is 40-80 ten thousand, and the mole fraction of vinyl chain units is 0.03-0.24%;
the preparation method of the energy-absorbing high-temperature vulcanized silicone rubber comprises the following steps:
(1) respectively adding the methyl vinyl silicone rubber, the reinforcing filler, the vulcanizing agent, the structure control agent and the anti-tearing agent into an internal mixer for internal mixing for 10 minutes at normal temperature, adding the pyroboric acid modified polydimethylsiloxane, and performing internal mixing for 20-30 minutes at normal temperature;
(2) putting the mixture obtained in the step (1) into a mold, and vulcanizing for 15min-20min on a flat vulcanizing machine with the pressure of 10MPa and the temperature of 155-170 ℃;
(3) and (3) carrying out over vulcanization on the high-temperature vulcanized silicone rubber obtained in the step (2) in an oven at 200 ℃ for 1-4h to obtain the energy-absorbing high-temperature vulcanized silicone rubber.
2. The energy-absorbing high-temperature vulcanized silicone rubber according to claim 1, wherein the energy-absorbing high-temperature vulcanized silicone rubber comprises the following components in parts by weight: 100 parts of methyl vinyl silicone rubber, 0-100 parts of reinforcing filler, 0.5-1 part of vulcanizing agent, 1-10 parts of structure control agent, 0.2-5 parts of anti-tearing agent and 5-45 parts of pyroboric acid modified polydimethylsiloxane; the molecular weight of the simethicone is 2-10 ten thousand; the mass ratio of the pyroboric acid to the dimethyl silicone oil is 0.1-10 percent; the pyroboric acid modified polydimethylsiloxane is prepared by reacting dimethyl silicone oil with pyroboric acid in a vacuum kneader at the temperature of 120-160 ℃ for 3-6 hours; the molecular weight of the methyl vinyl silicone rubber is 40-80 ten thousand, and the mole fraction of vinyl chain units is 0.03-0.24%.
3. The energy-absorbing high-temperature vulcanized silicone rubber according to claim 1, wherein the energy-absorbing high-temperature vulcanized silicone rubber comprises the following components in parts by weight: 100 parts of methyl vinyl silicone rubber, 2 parts of reinforcing filler, 0.5 part of vulcanizing agent, 1 part of structure control agent, 1 part of anti-tearing agent and 18.4 parts of pyroboric acid modified polydimethylsiloxane; the molecular weight of the simethicone is 2-10 ten thousand; the mass ratio of the pyroboric acid to the dimethyl silicone oil is 0.1-10 percent; the pyroboric acid modified polydimethylsiloxane is prepared by reacting dimethyl silicone oil with pyroboric acid in a vacuum kneader at the temperature of 120-160 ℃ for 3-6 hours; the molecular weight of the methyl vinyl silicone rubber is 40-80 ten thousand, and the mole fraction of vinyl chain units is 0.03-0.24%.
4. The energy-absorbing high-temperature vulcanized silicone rubber according to claim 1, wherein the energy-absorbing high-temperature vulcanized silicone rubber comprises the following components in parts by weight: 100 parts of methyl vinyl silicone rubber, 10 parts of reinforcing filler, 0.5 part of vulcanizing agent, 1 part of structure control agent, 0.5 part of anti-tearing agent and 12.4 parts of pyroboric acid modified polydimethylsiloxane; the molecular weight of the simethicone is 2-10 ten thousand; the mass ratio of the pyroboric acid to the dimethyl silicone oil is 0.1-10 percent; the pyroboric acid modified polydimethylsiloxane is prepared by reacting dimethyl silicone oil with pyroboric acid in a vacuum kneader at the temperature of 120-160 ℃ for 3-6 hours; the molecular weight of the methyl vinyl silicone rubber is 40-80 ten thousand, and the mole fraction of vinyl chain units is 0.03-0.24%.
5. Energy-absorbing high-temperature vulcanized silicone rubber according to any one of claims 1 to 4, wherein: the reinforcing filler comprises at least one of fumed silica, precipitated silica, organic montmorillonite, titanium dioxide, kaolin and calcium carbonate; the vulcanizing agent comprises at least one of di-tert-butyl peroxide, dicumyl peroxide and 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane; the structure control agent is at least one of phenyl silanediol, hexamethyldisilazane, low-molecular-weight hydroxyl-terminated polydimethylsiloxane and cyclic silazane; the anti-tearing agent is polyvinyl silicone oil.
6. An energy-absorbing high-temperature vulcanized silicone rubber is characterized by comprising the following components in percentage by weight: 100 parts of methyl vinyl silicone rubber, 0-100 parts of reinforcing filler, 0.5-1 part of vulcanizing agent, 1-10 parts of structure control agent, 0.2-5 parts of anti-tearing agent, 5-45 parts of pyroboric acid modified polydimethylsiloxane and 1-4 parts of foaming agent; the molecular weight of the methyl vinyl silicone rubber is 40-80 ten thousand, and the mole fraction of vinyl chain units is 0.03-0.24%; the molecular weight of the simethicone is 2-10 ten thousand; the mass ratio of the pyroboric acid to the dimethyl silicone oil is 0.1-10 percent; reacting dimethyl silicone oil and pyroboric acid in a vacuum kneader at the temperature of 120-160 ℃ for 3-6 hours to obtain pyroboric acid modified polydimethylsiloxane;
the preparation method of the energy-absorbing high-temperature vulcanized silicone rubber comprises the following steps:
(1) respectively adding the methyl vinyl silicone rubber, the reinforcing filler, the vulcanizing agent, the structure control agent and the anti-tearing agent into an internal mixer for internal mixing for 10 minutes at normal temperature, then adding the foaming agent for internal mixing for 10 minutes, then adding the pyroboric acid modified polydimethylsiloxane for internal mixing for 20-30 minutes at normal temperature;
(2) putting the mixture obtained in the step (1) into a mold, and vulcanizing for 15min-20min on a flat vulcanizing machine with the pressure of 10MPa and the temperature of 155-170 ℃;
(3) and (3) carrying out over vulcanization on the high-temperature vulcanized silicone rubber obtained in the step (2) in an oven at 200 ℃ for 1-4h to obtain the foaming energy-absorbing high-temperature vulcanized silicone rubber.
7. The energy-absorbing high-temperature vulcanized silicone rubber according to claim 6, wherein the energy-absorbing high-temperature vulcanized silicone rubber comprises the following components in parts by weight: 100 parts of methyl vinyl silicone rubber, 2 parts of reinforcing filler, 0.5 part of vulcanizing agent, 1 part of structure control agent, 1 part of anti-tearing agent, 18.4 parts of pyroboric acid modified polydimethylsiloxane and 4 parts of foaming agent; the molecular weight of the simethicone is 2-10 ten thousand; the mass ratio of the pyroboric acid to the dimethyl silicone oil is 0.1-10 percent; and reacting the dimethyl silicone oil and the pyroboric acid in a vacuum kneader at the temperature of 120-160 ℃ for 3-6 hours to obtain the pyroboric acid modified polydimethylsiloxane.
8. The energy-absorbing high-temperature vulcanized silicone rubber according to claim 6, wherein the energy-absorbing high-temperature vulcanized silicone rubber comprises the following components in parts by weight: 100 parts of methyl vinyl silicone rubber, 10 parts of reinforcing filler, 0.5 part of vulcanizing agent, 1 part of structure control agent, 0.5 part of anti-tearing agent, 12.8 parts of pyroboric acid modified polydimethylsiloxane and 4 parts of foaming agent; the molecular weight of the simethicone is 2-10 ten thousand; the mass ratio of the pyroboric acid to the dimethyl silicone oil is 0.1-10 percent; and reacting the dimethyl silicone oil and the pyroboric acid in a vacuum kneader at the temperature of 120-160 ℃ for 3-6 hours to obtain the pyroboric acid modified polydimethylsiloxane.
9. The energy-absorbing high temperature vulcanized silicone rubber of claim 6, wherein: the reinforcing filler comprises at least one of fumed silica, precipitated silica, organic montmorillonite, titanium dioxide, kaolin and calcium carbonate; the vulcanizing agent comprises at least one of di-tert-butyl peroxide, dicumyl peroxide and 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane; the structure control agent is at least one of phenyl silanediol, hexamethyldisilazane, low-molecular-weight hydroxyl-terminated polydimethylsiloxane and cyclic silazane; the anti-tearing agent is polyvinyl silicone oil; the molecular weight of the simethicone is 2-10 ten thousand; the mass ratio of the pyroboric acid to the dimethyl silicone oil is 0.1-10 percent; reacting dimethyl silicone oil and pyroboric acid in a vacuum kneader at the temperature of 120-160 ℃ for 3-6 hours to obtain pyroboric acid modified polydimethylsiloxane; the foaming agent is a microsphere foaming agent, and the foaming temperature is less than or equal to the vulcanization temperature of a vulcanizing agent.
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