CN115322463B - Low-heat-generation and anti-fatigue rubber composition and preparation method and application thereof - Google Patents
Low-heat-generation and anti-fatigue rubber composition and preparation method and application thereof Download PDFInfo
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- CN115322463B CN115322463B CN202211127965.8A CN202211127965A CN115322463B CN 115322463 B CN115322463 B CN 115322463B CN 202211127965 A CN202211127965 A CN 202211127965A CN 115322463 B CN115322463 B CN 115322463B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/26—Silicon- containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
Abstract
The invention relates to the technical field of preparation of air springs of vehicles, in particular to a low-heat-generation and anti-fatigue rubber composition for producing air springs, and a preparation method and application thereof. The rubber composition is prepared by mixing the following raw materials in parts by weight based on 100 parts by weight of rubber components: 100 portions of chloroprene rubber, 20 to 40 portions of carbon black, 5.0 to 30 portions of white carbon black, 1.0 to 5.0 portions of silane coupling agent, 5.0 to 20 portions of nano sheet silicate and 0 to 0.8 portion of organic sulfur donor. The air spring has lower heat generation and better anti-fatigue performance.
Description
Technical Field
The invention relates to the technical field of preparation of air springs of vehicles, in particular to a low-heat-generation and anti-fatigue rubber composition for producing air springs, and a preparation method and application thereof.
Background
Since the adoption of macpherson suspension by ford in 1950, macpherson suspension is widely used for automobile shock absorption by automobile factories due to good responsiveness and controllability, but when an automobile runs on an uneven road surface, the wheels are easy to steer automatically, and the stability is poor.
The adjustable air suspension is used for automobile shock absorption in 1984, the air spring has ideal nonlinear elastic characteristics, after the height adjusting device is additionally arranged, the height of an automobile body does not change along with increase and decrease of load, the spring stiffness can be designed to be lower, the riding comfort is good, but the air spring suspension is complex in structure, high in manufacturing cost and less in application range than a Macpherson suspension.
In recent years, new energy automobiles are to carry light hybrid power and plug-in hybrid power, and in the coming 2050 years, pure electric power and hydrogen energy become the main power of automobile energy, the driving comfort of automobiles is more and more concerned by consumers, and automobile engineers pay more attention to air springs.
In patent CN113429649A, a rubber composition for inner and outer layers of a commercial vehicle air spring leather bag and a preparation method thereof are introduced, wherein the rubber composition is provided in the patent, and the rubber composition is composed of a rubber composition a and a rubber composition B, wherein the rubber composition a is composed of the following raw materials in parts by weight: 100 parts of natural rubber, 52-56 parts of carbon black, 6.5-7.5 parts of an active agent, 4.5-7.5 parts of an anti-aging agent, 1.8-2.5 parts of protective wax, 0.7-1.0 part of an accelerator and 1.5-2 parts of sulfur; the rubber composition B is prepared from the following raw materials in parts by weight: 80-100 parts of chloroprene rubber, 10-20 parts of butadiene rubber, 20-25 parts of carbon black, 20-25 parts of white carbon black, 2-2.5 parts of silane coupling agent, 1-2 parts of stearic acid, 4.5-5.5 parts of zinc oxide, 3-4 parts of magnesium oxide, 5.5-6.5 parts of anti-aging agent, 1.8-2.5 parts of protective wax, 0.7-1.0 part of accelerator, 2-4 parts of homogenizing agent and 0.6-1.3 parts of sulfur. The rubber composition has excellent aging resistance and long service life. However, the rubber composition in the patent adopts a crude rubber system of natural rubber, butadiene rubber and chloroprene rubber, and the natural rubber and the butadiene rubber tend to influence the aging and fatigue properties.
A patent CN112358667A introduces a rubber composition, a preparation method and an application thereof, and the patent provides the rubber composition, the preparation method and the application thereof, and the rubber composition comprises the following components in parts by weight: 80-99 parts of mercaptan-regulated chloroprene rubber, 9-11 parts of a vulcanizing agent, 19-36 parts of a reinforcing agent, 15-25 parts of a softening agent, 3-5 parts of a primary anti-aging agent and 2-4 parts of an auxiliary anti-aging agent; the rubber composition is prepared by selecting mercaptan-regulated chloroprene rubber and matching a main anti-aging agent and an auxiliary anti-aging agent, so that the rubber composition has excellent mechanical property and wear resistance and also has excellent aging property within a specific addition range, and can meet the requirements of high reliability and long service life of long-term use of an air spring air bag of a passenger car. The patent relates to a rubber composition and a preparation method thereof, the rubber composition has excellent mechanical property, aging resistance and ozone resistance, and heat generation performance and fatigue resistance are not involved.
A magnetic-sensitive rubber composition for a rubber air spring and a preparation method thereof are introduced in patent CN111718521A, and the magnetic-sensitive rubber composition for the rubber air spring and the preparation method thereof are provided in the patent, wherein the magnetic-sensitive rubber composition comprises, by weight, 100 parts of matrix rubber, 2-8 parts of an active agent, 0-50 parts of carbon black, 0-20 parts of white carbon black, 0-4 parts of a silane coupling agent, 1-3 parts of an accelerator, 3-6 parts of an anti-aging agent, 1-2 parts of a vulcanizing agent, 200-600 parts of modified ferromagnetic particles and 1-10 parts of a self-repairing agent. Wherein the matrix rubber is composed of natural rubber, chloroprene rubber or hydrogenated nitrile rubber; the active agent consists of nano zinc oxide and stearic acid; the white carbon black is high-dispersion type precipitation white carbon black; the silane coupling agent is a liquid silane coupling agent Si-69; the accelerator is accelerator CBS; the anti-aging agent is the combination of anti-aging agent 6PPD and anti-aging agent RD; the vulcanizing agent is sulfur; the self-repairing agent is liquid nitrile rubber-phenolic resin. The magnetic-sensitive rubber composition has the tensile strength of more than 15MPa and the elongation at break of more than 400 percent. In this patent, the rubber composition is reinforced with modified ferromagnetic particles, and the improvement of the tensile strength at break and the elongation at break is considered, and the fatigue property is not considered.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a low-heat-generation and anti-fatigue rubber composition and a preparation method thereof, wherein the air spring of the vehicle has lower heat generation and better anti-fatigue performance.
In order to achieve the purpose, the invention adopts the following technical scheme:
the rubber composition is prepared by mixing the following raw materials in parts by weight based on 100 parts by weight of rubber components:
the Mooney viscosity ML (1 + 4) multiplied by 100 of the chloroprene rubber is 25-60; the carbon black has an iodine absorption value of 31-60mg/g and a CTAB adsorption specific surface area of 30-100m 2 (ii)/g; the nitrogen adsorption specific surface area (BET) of the white carbon black is 60-130m 2 (ii)/g; the silane coupling agent is Si747; the organic sulfur donor is alkylphenol disulfide, and the sulfur content in the organic sulfur donor is 20-40%.
The above alkylphenol disulfide has the following structural formula:
preferably, the rubber composition is prepared by mixing the following raw materials in parts by weight based on 100 parts by weight of rubber components:
preferably, the chloroprene rubber is DCR40A, mooney viscosity ML (1 + 4). Times.100 ℃ =43, a Japanese electrochemical product; the carbon black is selected from carbon black N660, a product of Hangzhou Zhongze Qingquan industry Co., ltd; white carbon black is selected from 1115MP with BET of 115m 2 (iv)/g, solvay chemical products; the inorganic filler is TNK, jiangsu Qi Xiang chemical products; the organic sulfur donor is selected from TB710, sulfur 27.4% and Shandong Yanggu Huatai chemical Co.
Preferably, the rubber composition further comprises the following raw materials: environment-friendly oil, stearic acid, an anti-aging agent 4020, an anti-aging agent 3100, microcrystalline wax SL-10345, magnesium oxide, zinc oxide, a promoter CZ and sulfur.
Preferably, the rubber component comprises, by weight, 100 parts of: 10-20 parts of environment-friendly oil, 1.0-3.0 parts of stearic acid, 3.0-5.0 parts of anti-aging agent 4022.0-4.0 parts of anti-aging agent 3100, 1.0-3.0 parts of microcrystalline wax SL-10345, 4.0-6.0 parts of magnesium oxide, 6.0-15 parts of zinc oxide, 0.5-1.5 parts of promoter CZ and 1.0-2.0 parts of sulfur.
Further, the invention also discloses a mixing method of the low-heat-generation and fatigue-resistant rubber composition, which comprises the following steps:
step 1, mixing, namely mixing by using an internal mixer, and adding chloroprene rubber into the internal mixer for mixing for 30-100 seconds; then lifting the top plug, adding all materials except the zinc oxide, the accelerant, the sulfur and the organic sulfur donor, then closing a charging door, pressing the top plug to keep 400-1200 seconds, keeping the rotating speed of a rotor of the internal mixer at 5-30 r/min, and discharging the rubber at 90-105 ℃;
step 2, mixing, namely mixing by using an internal mixer, adding all the mixture and the rest raw materials obtained in the first step of mixing into the internal mixer, closing a charging door, pressing a top bolt for 200-800 seconds, keeping the rotating speed of a rotor of the internal mixer at 5-30 r/min, and discharging rubber at 85-100 ℃; the final rubber composition was obtained.
Preferably, the step 1 of mixing is that the mixing time of the chloroprene rubber added into the internal mixer is 40 to 80 seconds, the holding time of the upper top bolt is 600 to 1000 seconds, and the rotating speed of the rotor of the internal mixer is 10 to 20 r/min; further preferably, the mixing time of adding the chloroprene rubber into the internal mixer is 50 to 70 seconds, the pressing-on top bolt holding time is 700 to 900 seconds, and the rotating speed of a rotor of the internal mixer is 10 to 15 r/min.
Preferably, the step 2 of mixing is carried out, a top bolt is pressed on the mixture and kept for 300 to 600 seconds, the rotating speed of a rotor of an internal mixer is 10 to 20 revolutions per minute, and the rubber discharge temperature is 90 to 100 ℃; further preferably, the top bolt is pressed for 400 to 550 seconds, the rotating speed of a rotor of the internal mixer is 10 to 15 r/min, and the rubber discharging temperature is 90 to 95 ℃.
The rubber composition obtained by the mixing method is used for preparing the air spring, so that the heat generation is lower, and the bending crack resistance is better.
Detailed Description
The reference proportions of the rubber compositions of the present invention, the formulations of the comparative examples and examples, and the experimental data are shown in Table 1.
TABLE 1
TABLE 1
1 Natural rubber, SVR3L, vietnam products
2 neoprene, DCR40A, mooney viscosity ML (1 + 4). Times.100 ℃ 43, japan electric chemical products
3 carbon Black N660, product of Hangzhou Zhongze Jiejingquan industries Ltd
4. White carbon black 1115MP, BET 115m2/g, solvay chemical product
5. Silane coupling agent A, si75, sulfur 15.3%, zhejiang metallocene rubber auxiliary products
6. Silane coupling agent B, si747, sulfur 3.4%, jiangsu Qi Xiang chemical products
7. Inorganic filler, TNK, jiangsu Qi Xiang chemical products
8. Organic sulfur donor, TB710, sulfur 27.4%, shandong Yanggu Huatai chemical Co., ltd
9. Other raw materials are all commercial industrial products; the other materials are environment-friendly oil/stearic acid/anti-aging agent 4020/anti-aging agent 3100/microcrystalline wax SL-10345/magnesium oxide/zinc oxide/accelerator CZ/sulfur: 15.0/2.0/4.0/3.0/2.0/5.0/10.0/1.0/1.5.
A method of compounding the rubber compositions described in the proportions, comparative examples and examples set forth in Table 1 above, which comprises the steps of:
step 1, mixing, namely mixing by using an internal mixer, and adding chloroprene rubber (or natural rubber) into the internal mixer for mixing for 50-70 seconds; then lifting the top bolt, adding all the materials except the zinc oxide, the accelerant, the sulfur and the organic sulfur donor (if any), then closing the charging door, pressing the top bolt for 700-900 seconds, keeping the rotating speed of a rotor of the internal mixer at 10-15 r/min, and discharging the rubber at 90-105 ℃.
Step 2, mixing, namely mixing by using an internal mixer, adding the mixture obtained by the first mixing and the rest raw materials into the internal mixer, closing a charging door, pressing a top bolt for 400-550 seconds, keeping the rotating speed of a rotor of the internal mixer at 10-15 r/min, and discharging rubber at 90-95 ℃; the final rubber composition was obtained.
Method for evaluating performance
The various performance tests in table 1 were performed according to the corresponding national standards.
Heat generation index
The larger the heat generation index, the lower the heat generation, see the formula (I)
Heat generation index = example resilience/reference resilience formula (one).
Index of resistance to inflexion and tear
The larger the flex crack resistance index is, the better the fatigue resistance is, see the formula (II)
Anti-inflexion vent index = inflexion vent of example/inflexion vent of reference example equation (two).
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention, including any reference to the above-mentioned embodiments. Various modifications to these embodiments will be readily apparent to those skilled in the art. The general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (12)
1. The rubber composition with low heat generation and fatigue resistance is characterized by being prepared by mixing the following raw materials in parts by weight based on 100 parts of rubber components:
chloroprene rubber 100 parts
20 to 40 portions of carbon black
5.0 to 30 portions of white carbon black
1.0 to 5.0 portions of silane coupling agent
5.0 to 20 portions of nano sheet silicate
0-0.8 parts of organic sulfur donor;
the Mooney viscosity ML (1 + 4) multiplied by 100 of the neoprene is 25-60; the carbon black has an iodine absorption value of 31-60mg/g and a CTAB adsorption specific surface area of 30-100m 2 (ii)/g; the nitrogen adsorption specific surface area (BET) of the white carbon black is 60-130m 2 (iv) g; the silane coupling agent is Si747; the organic sulfur donor is alkylphenol disulfide, and the sulfur content in the organic sulfur donor is 20-40%.
2. The low heat generation and fatigue resistance rubber composition according to claim 1, wherein the rubber composition is prepared by mixing the following raw materials in 100 parts by weight of rubber component:
100 portions of chloroprene rubber
30 to 35 portions of carbon black
10-20 parts of white carbon black
1.0 to 3.0 portions of silane coupling agent
10-15 parts of nano sheet silicate
0 to 0.8 portion of organic sulfur donor.
3. The rubber composition with low heat generation and fatigue resistance as claimed in claim 1, wherein the chloroprene rubber is selected from DCR40A, mooney viscosity ML (1 + 4) × 100 ℃=43, japan electrochemical products; the carbon black is selected from carbon black N660, a product of Hangzhou Zhongzhuiquan Kanghui Co Ltd; white carbon black is selected from 1115MP with BET of 115m 2 (iv) solvay chemical; the inorganic filler is TNK, jiangsu Qi Xiang chemical products; the organic sulfur donor is selected from TB710, sulfur 27.4% and Shandong Yanggu Huatai chemical Co.
4. A low heat build-up, fatigue resistant rubber composition as claimed in claim 1 further comprising the following raw materials: environment-friendly oil, stearic acid, an anti-aging agent 4020, an anti-aging agent 3100, microcrystalline wax SL-10345, magnesium oxide, zinc oxide, a promoter CZ and sulfur.
5. A low heat build-up, fatigue resistant rubber composition as claimed in claim 4 wherein based on 100 parts by weight of rubber component: 10-20 parts of environment-friendly oil, 1.0-3.0 parts of stearic acid, 3.0-5.0 parts of anti-aging agent 4020.0-4.0 parts of anti-aging agent 31002.0-4.0 parts of microcrystalline wax SL-10345.0-3.0 parts of magnesium oxide 4.0-6.0 parts of zinc oxide 6.0-15 parts of accelerator CZ0.5-1.5 parts of accelerator CZ and 1.0-2.0 parts of sulfur.
6. A method for compounding a low heat generation, fatigue resistant rubber composition according to any one of claims 1 to 5, comprising the steps of:
step 1, mixing, namely mixing by using an internal mixer, and adding chloroprene rubber into the internal mixer for mixing for 30-100 seconds; then lifting the top plug, adding all materials except the zinc oxide, the accelerant, the sulfur and the organic sulfur donor, then closing a charging door, pressing the top plug to keep 400-1200 seconds, keeping the rotating speed of a rotor of the internal mixer at 5-30 r/min, and discharging the rubber at 90-105 ℃;
step 2, mixing, namely mixing by using an internal mixer, adding all the mixture and the rest raw materials obtained in the first step of mixing into the internal mixer, closing a charging door, pressing a top bolt for 200-800 seconds, keeping the rotating speed of a rotor of the internal mixer at 5-30 r/min, and discharging rubber at 85-100 ℃; the final rubber composition was obtained.
7. The method of claim 6, wherein in the step 1, the mixing time of the chloroprene rubber added into the internal mixer is 40 to 80 seconds, the holding time of the upper ram is 600 to 1000 seconds, and the rotating speed of the rotor of the internal mixer is 10 to 20 revolutions per minute.
8. The method of claim 7, wherein the mixing time of the neoprene rubber added into the internal mixer is 50-70 seconds, the holding time of the upper top bolt is 700-900 seconds, and the rotating speed of the rotor of the internal mixer is 10-15 r/min.
9. The process as claimed in claim 6, wherein the 2 nd step of mixing is carried out by pressing a ram for 300-600 seconds, the rotor speed of the internal mixer is 10-20 rpm, and the temperature of rubber discharge is 90-100 ℃.
10. The method as claimed in claim 9, wherein the ram is pressed up for 400-550 seconds, the rotor speed of the internal mixer is 10-15 rpm, and the binder removal temperature is 90-95 ℃.
11. Use of the rubber composition according to any one of claims 1 to 5 for the production of an air spring.
12. An air spring having low heat generation and fatigue resistance, which is obtained by vulcanizing the rubber composition according to any one of claims 1 to 5.
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CN114015132B (en) * | 2021-12-07 | 2023-09-15 | 中国第一汽车股份有限公司 | Chloroprene rubber compound and preparation method and application thereof |
CN116656020A (en) * | 2023-06-09 | 2023-08-29 | 中策橡胶集团股份有限公司 | Anti-fatigue rubber composition, mixing method and application thereof in preparation of air spring |
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