High-temperature-resistant rubber for automobile oil seal and preparation method of high-temperature-resistant rubber

Abstract

The invention relates to the technical field of rubber, and provides high-temperature-resistant rubber for an automobile oil seal and a preparation method of the high-temperature-resistant rubber. The high-temperature-resistant rubber for the automobile oil seal comprises the following raw material components in parts by weight: 80-90 parts of acrylate rubber, 45-55 parts of a wear-resistant filler, 2-3 parts of a vulcanizing agent, 1-2 parts of a vulcanization accelerator and 2-6 parts of an anti-aging agent, the wear-resistant filler comprises titanium phosphate and molybdenum disulfide. According to the technical scheme, the problem of poor wear resistance of the high-temperature-resistant rubber for the automobile oil seal in the prior art is solved.

Description

Technical Field

[0001] The invention relates to the technical field of rubber, and in particular to a high-temperature resistant rubber for automobile oil seal and a preparation method thereof. Background Art

[0002] During the operation of a car, oil seals, as key components, play a vital role in ensuring the normal operation of the engine, transmission and other systems. They are mainly used to prevent the leakage of working media such as lubricating oil, while preventing the invasion of external impurities to ensure that all components work in a well-lubricated and clean environment.

[0003] With the continuous development of the automobile industry, engine performance is constantly improving and operating temperatures are getting higher and higher. The performance of traditional oil seal materials will be significantly reduced in high temperature environments. For example, ordinary rubber oil seals are prone to aging, hardening, and brittleness at high temperatures, resulting in sealing failure, which in turn causes lubricating oil leakage, which not only affects the normal driving of the car, but may also cause damage to key components such as the engine, increasing maintenance costs and safety hazards.

[0004] Acrylic rubber is widely used in the field of automotive oil seals due to its good high temperature resistance, however, its wear resistance is insufficient. When the car is running, the oil seal frequently contacts and moves relative to the shaft and other parts. Long-term friction will gradually wear the surface of the oil seal. Once the wear is excessive, the sealing performance of the oil seal will be greatly reduced.

[0005] Therefore, the development of an acrylic rubber material with good wear resistance is of great significance to the field of automotive oil seals. It not only helps to improve the service life and reliability of automotive oil seals, reduce the number of automotive repairs and maintenance due to oil seal failures, but also further promotes the automotive industry to develop in the direction of high performance and long life. Summary of the invention

[0006] The invention provides a high temperature resistant rubber for automobile oil seal and a preparation method thereof, which solves the problem of poor wear resistance of the high temperature resistant rubber for automobile oil seal in the related art.

[0007] The technical solution of the present invention is as follows: The present invention provides a high temperature resistant rubber for automobile oil seals, wherein the raw materials include the following components in parts by weight: 80-90 parts of acrylic rubber, 45-55 parts of wear-resistant filler, 2-3 parts of vulcanizing agent, 1-2 parts of vulcanization accelerator, and 2-6 parts of antioxidant; The wear-resistant filler includes titanium phosphate and molybdenum disulfide.

[0008] As a further technical solution, the mass ratio of titanium phosphate to molybdenum disulfide is 2~3:7.

[0009] In the present invention, the wear resistance of the high temperature resistant rubber for automobile oil seal is further improved by adjusting the mass ratio of titanium phosphate to molybdenum disulfide to 2-3:7.

[0010] As a further technical solution, the molybdenum disulfide is a molybdenum disulfide composite material; The raw materials of the molybdenum disulfide composite material include molybdenum disulfide and hydroxymethylphenylphosphinic acid.

[0011] As a further technical solution, the preparation method of the molybdenum disulfide composite material comprises the following steps: Molybdenum disulfide and hydroxymethylphenylphosphinic acid are mixed and ball-milled to obtain a molybdenum disulfide composite material; During the ball milling, the rotation speed is 300-500 rpm and the time is 7-9 hours.

[0012] In the present invention, molybdenum disulfide is treated with hydroxymethylphenylphosphinic acid to obtain a molybdenum disulfide composite material, and the phosphinic acid groups in the hydroxymethylphenylphosphinic acid reduce the lipophilicity of molybdenum disulfide and improve the oil resistance of the rubber for high-temperature resistant automobile oil seals.

[0013] As a further technical solution, the mass ratio of molybdenum disulfide to hydroxymethylphenylphosphinic acid is 5-9:1.

[0014] In the present invention, the mass ratio of molybdenum disulfide to hydroxymethylphenylphosphinic acid is adjusted to 5-9:1, thereby further improving the oil resistance of the high-temperature resistant rubber for automobile oil seals.

[0015] As a further technical solution, the vulcanizing agent includes one of hexamethylenediamine carbamate, sulfur, and dicumyl peroxide; The vulcanization accelerator includes one of diphenylguanidine and di-o-tolylguanidine; The antioxidant includes one of antioxidant 445 and antioxidant RD.

[0016] In the present invention, the vulcanizing agent is selected from one of hexamethylenediamine carbamate, sulfur and diisopropylbenzene peroxide, which forms chemical bonds between rubber molecular chains during the vulcanization process, connects the acrylic rubber chains together, forms a three-dimensional network structure, and thus improves the performance of the rubber.

[0017] In the present invention, the vulcanization accelerator is selected from diphenylguanidine and di-o-tolylguanidine, which accelerates the vulcanization speed and reduces energy consumption and production cost.

[0018] In the present invention, the antioxidant is selected from antioxidant 445 and antioxidant RD, which inhibits the aging of the rubber and prolongs the service life of the rubber.

[0019] The present invention also proposes a method for preparing the high temperature resistant rubber for automobile oil seal, comprising the following steps: S1, mixing all components except the vulcanizing agent and the vulcanization accelerator for the first time to obtain a mixed product; S2, mixing the mixed product with a vulcanizing agent and a vulcanization accelerator and then performing a second roll milling to obtain a second mixed product; S3, vulcanizing the second kneaded product, and cooling to room temperature to obtain a high temperature resistant rubber for automobile oil seals.

[0020] As a further technical solution, the temperature of the first mixing is 50-70° C. and the time is 4-7 min.

[0021] As a further technical solution, the temperature of the second mixing is 40-55° C. and the time is 2-4 min.

[0022] As a further technical solution, the vulcanization includes one-stage vulcanization and two-stage vulcanization in sequence. During the one-stage vulcanization, the temperature is 175-185°C, the pressure is 9-13MPa, and the time is 8-10min; During the second stage vulcanization, the temperature is 175-180° C., the pressure is 8-12 MPa, and the time is 2-5 min.

[0023] The working principle and beneficial effects of the present invention are: In the present invention, wear-resistant fillers are selected from titanium phosphate and molybdenum disulfide. Both titanium phosphate and molybdenum disulfide have a multilayer structure. The two work synergistically to improve the wear resistance of the rubber for high-temperature resistant automotive oil seals, effectively extend the service life of the oil seals, reduce the replacement frequency, reduce maintenance costs, and better maintain the sealing performance, adapt to more complex and harsh working environments, and improve the overall reliability of the equipment. DETAILED DESCRIPTION

[0024] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0025] In the following examples and comparative examples, the acrylic rubber model is ACM AR71; the content of titanium phosphate is 99 wt %, and the particle size is 200 mesh; the content of molybdenum disulfide is 99 wt %, and the particle size is 100 mesh.

[0026] Example 1 A high temperature resistant rubber for automobile oil seals, the raw materials comprising the following components in parts by weight: 90 parts of acrylic rubber, 55 parts of wear-resistant filler, 3 parts of vulcanizing agent, 2 parts of vulcanization accelerator, and 6 parts of antioxidant; The wear-resistant filler includes titanium phosphate and molybdenum disulfide in a mass ratio of 5:7; The vulcanizing agent is sulfur; The vulcanization accelerator is di-o-tolylguanidine; The antioxidant is antioxidant RD; The method for preparing high temperature resistant rubber for automobile oil seal comprises the following steps: S1, mixing all components except the vulcanizing agent and the vulcanization accelerator for the first time to obtain a mixed product; S2, mixing the mixed product with a vulcanizing agent and a vulcanization accelerator and then performing a second roll milling to obtain a second mixed product; S3, vulcanizing the second mixed product, and cooling it to room temperature to obtain a high temperature resistant automobile oil seal rubber; The first mixing temperature is 70°C and the time is 4 minutes; The second mixing temperature is 55°C and the time is 2 minutes; The vulcanization process includes one-stage vulcanization and two-stage vulcanization. During the first stage vulcanization, the temperature is 185°C, the pressure is 13MPa, and the time is 8min. During the second stage vulcanization, the temperature is 180°C, the pressure is 12MPa, and the time is 2min.

[0027] Example 2 A high temperature resistant rubber for automobile oil seals, the raw materials comprising the following components in parts by weight: 80 parts of acrylic rubber, 45 parts of wear-resistant filler, 2 parts of vulcanizing agent, 1 part of vulcanization accelerator, and 2 parts of antioxidant; The wear-resistant filler includes titanium phosphate and molybdenum disulfide in a mass ratio of 1:10; The curing agent is dicumyl peroxide; The vulcanization accelerator is diphenylguanidine; The antioxidant is antioxidant 445; The method for preparing high temperature resistant rubber for automobile oil seal comprises the following steps: S1, mixing all components except the vulcanizing agent and the vulcanization accelerator for the first time to obtain a mixed product; S2, mixing the mixed product with a vulcanizing agent and a vulcanization accelerator and then performing a second roll milling to obtain a second mixed product; S3, vulcanizing the second mixed product, and cooling it to room temperature to obtain a high temperature resistant automobile oil seal rubber; The first mixing temperature is 50°C and the time is 7 minutes; The second mixing temperature is 40°C and the time is 4 minutes; The vulcanization process includes one-stage vulcanization and two-stage vulcanization. During the first stage vulcanization, the temperature is 175°C, the pressure is 9MPa, and the time is 10min. During the second stage vulcanization, the temperature is 175°C, the pressure is 8MPa, and the time is 5min.

[0028] Example 3 A high temperature resistant rubber for automobile oil seals, the raw materials comprising the following components in parts by weight: 85 parts of acrylic rubber, 50 parts of wear-resistant filler, 2.5 parts of vulcanizing agent, 1.5 parts of vulcanization accelerator, and 4 parts of antioxidant; The wear-resistant filler includes titanium phosphate and molybdenum disulfide in a mass ratio of 1:7; The curing agent is hexamethylenediamine carbamate; The vulcanization accelerator is diphenylguanidine; The antioxidant is antioxidant 445; The method for preparing high temperature resistant rubber for automobile oil seal comprises the following steps: S1, mixing all components except the vulcanizing agent and the vulcanization accelerator for the first time to obtain a mixed product; S2, mixing the mixed product with a vulcanizing agent and a vulcanization accelerator and then performing a second roll milling to obtain a second mixed product; S3, vulcanizing the second mixed product, and cooling it to room temperature to obtain a high temperature resistant automobile oil seal rubber; The first mixing temperature is 60°C and the time is 5 minutes; The second mixing temperature is 45°C and the time is 3 minutes; The vulcanization process includes one-stage vulcanization and two-stage vulcanization. During the first stage vulcanization, the temperature is 180°C, the pressure is 11MPa, and the time is 9 minutes. During the second stage vulcanization, the temperature is 177°C, the pressure is 11MPa, and the time is 3min.

[0029] Example 4 The only difference between this embodiment and embodiment 3 is that the mass ratio of titanium phosphate to molybdenum disulfide in this embodiment is 4:7.

[0030] Example 5 The only difference between this embodiment and embodiment 3 is that the mass ratio of titanium phosphate to molybdenum disulfide in this embodiment is 2:7.

[0031] Example 6 The only difference between this embodiment and embodiment 3 is that the mass ratio of titanium phosphate to molybdenum disulfide in this embodiment is 3:7.

[0032] Example 7 The difference between this embodiment and embodiment 5 is that this embodiment uses an equal amount of molybdenum disulfide composite material to replace molybdenum disulfide. The preparation method of the molybdenum disulfide composite material includes the following steps: Molybdenum disulfide and hydroxymethylphenylphosphinic acid are mixed and ball-milled to obtain a molybdenum disulfide composite material; The ball milling speed was 300 rpm and the time was 9 h; The mass ratio of molybdenum disulfide to hydroxymethylphenylphosphinic acid is 10:1.

[0033] Example 8 The only difference between this embodiment and embodiment 7 is that the mass ratio of molybdenum disulfide to hydroxymethylphenylphosphinic acid in this embodiment is 4:1.

[0034] Example 9 The only difference between this embodiment and embodiment 7 is that the mass ratio of molybdenum disulfide to hydroxymethylphenylphosphinic acid in this embodiment is 5:1.

[0035] Example 10 The only difference between this embodiment and embodiment 7 is that the mass ratio of molybdenum disulfide to hydroxymethylphenylphosphinic acid in this embodiment is 9:1.

[0036] Embodiment 11 The difference between this embodiment and embodiment 5 is that this embodiment uses an equal amount of molybdenum disulfide composite material to replace molybdenum disulfide. The preparation method of the molybdenum disulfide composite material includes the following steps: Molybdenum disulfide and hydroxymethylphenylphosphinic acid are mixed and ball-milled to obtain a molybdenum disulfide composite material; The ball milling speed was 500 rpm and the time was 7 h; The mass ratio of molybdenum disulfide to hydroxymethylphenylphosphinic acid is 4:1.

[0037] Comparative Example 1 The only difference between this comparative example and Example 2 is that the wear-resistant filler in this comparative example is molybdenum disulfide.

[0038] Comparative Example 2 The only difference between this comparative example and Example 2 is that the wear-resistant filler in this comparative example is titanium phosphate.

[0039] Comparative Example 3 The only difference between this comparative example and Example 2 is that no wear-resistant filler is added in this comparative example.

[0040] Experimental Example 1 The high temperature resistant rubber for automobile oil seals prepared in Examples 1 to 6 and Comparative Examples 1 to 3 were tested for relative volume wear according to the method specified in GB / T 9867-2008 "Determination of wear resistance of vulcanized rubber or thermoplastic rubber (rotating roller abrader method)". The test results are shown in Table 1.

[0041]

[0042] It can be seen from Table 1 that the relative volume wear of the high temperature resistant automobile oil seal rubber prepared in Examples 1 to 6 is between 0.58 cm 3 The following describes that titanium phosphate and molybdenum disulfide produce a synergistic effect to improve the wear resistance of the high temperature resistant automotive oil seal rubber.

[0043] Experimental Example 2 The high temperature resistant automobile oil seal rubbers prepared in Examples 5 and 7 to 11 were subjected to an oil resistance test experiment. The experimental method is as follows: the high temperature resistant automobile oil seal rubber samples were immersed in 903# standard test oil, and the immersion conditions were 150°C × 70h. The Shore hardness before immersion and the Shore hardness after immersion were tested respectively.

[0044] The test results are shown in Table 2.

[0045]

[0046] It can be seen from Table 2 that the changes before and after the oil immersion of the rubber for high temperature resistant automobile oil seals prepared in Examples 7 to 11 are less than that in Example 5, indicating that the molybdenum disulfide is treated with hydroxymethylphenylphosphinic acid to obtain a molybdenum disulfide composite material, which improves the oil resistance of the rubber for high temperature resistant automobile oil seals.

[0047] Experimental Example 3 The high temperature resistant automobile oil seal rubber prepared in Example 1 was tested for tensile strength before high temperature aging and tensile strength after high temperature aging according to the method specified in GB / T 3512-2014 "Hot air accelerated aging and heat resistance test for vulcanized rubber or thermoplastic rubber"; The high temperature aging condition is 150℃×70h. The test results are shown in Table 3.

[0048]

[0049] It can be seen from Table 3 that the rubber provided by the present invention has good high temperature resistance and can meet the needs in actual use.

[0050] The above are only preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. A high temperature resistant rubber for automobile oil seal, characterized in that: The raw materials include the following components in parts by weight: 80-90 parts of acrylic rubber, 45-55 parts of wear-resistant filler, 2-3 parts of vulcanizing agent, 1-2 parts of vulcanization accelerator, and 2-6 parts of antioxidant; The wear-resistant filler includes titanium phosphate and molybdenum disulfide.

2. The high temperature resistant rubber for automobile oil seal according to claim 1, characterized in that: The mass ratio of the titanium phosphate to molybdenum disulfide is 2-3:

7.

3. The high temperature resistant rubber for automobile oil seal according to claim 1, characterized in that: The molybdenum disulfide is a molybdenum disulfide composite material; The raw materials of the molybdenum disulfide composite material include molybdenum disulfide and hydroxymethylphenylphosphinic acid.

4. The high temperature resistant rubber for automobile oil seal according to claim 3, characterized in that: The preparation method of the molybdenum disulfide composite material comprises the following steps: Molybdenum disulfide and hydroxymethylphenylphosphinic acid are mixed and ball-milled to obtain a molybdenum disulfide composite material; During the ball milling, the rotation speed is 300-500 rpm and the time is 7-9 hours.

5. The high temperature resistant rubber for automobile oil seal according to claim 4, characterized in that: The mass ratio of the molybdenum disulfide to hydroxymethylphenylphosphinic acid is 5-9:

1.

6. The high temperature resistant rubber for automobile oil seal according to claim 1, characterized in that: The vulcanizing agent includes one of hexamethylenediamine carbamate, sulfur, and dicumyl peroxide; The vulcanization accelerator includes one of diphenylguanidine and di-o-tolylguanidine; The antioxidant includes one of antioxidant 445 and antioxidant RD.

7. The method for preparing a high temperature resistant rubber for automobile oil seal according to any one of claims 1 to 6, characterized in that: The following steps are involved: S1, mixing all components except the vulcanizing agent and the vulcanization accelerator for the first time to obtain a mixed product; S2, mixing the mixed product with a vulcanizing agent and a vulcanization accelerator and then performing a second roll milling to obtain a second mixed product; S3, vulcanizing the second kneaded product, and cooling to room temperature to obtain a high temperature resistant rubber for automobile oil seals.

8. The method for preparing a high temperature resistant rubber for automobile oil seal according to claim 7, characterized in that: The first mixing is performed at a temperature of 50-70° C. and for a time of 4-7 minutes.

9. The method for preparing a high temperature resistant rubber for automobile oil seal according to claim 7, characterized in that: The second mixing is performed at a temperature of 40-55° C. and for a time of 2-4 min.

10. The method for preparing a high temperature resistant rubber for automobile oil seal according to claim 7, characterized in that: The vulcanization includes a first stage vulcanization and a second stage vulcanization, wherein the first stage vulcanization is performed at a temperature of 175-185°C, a pressure of 9-13 MPa, and a time of 8-10 min; During the second stage vulcanization, the temperature is 175-180° C., the pressure is 8-12 MPa, and the time is 2-5 min.

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