Rubber material and application thereof, and water tire nozzle rubber and preparation method thereof

Abstract

The invention belongs to the technical field of high polymer materials, and particularly relates to a rubber material and application thereof, and a water tire nozzle rubber and a preparation method thereof. The rubber sizing material comprises 100 parts of main body rubber, 1-3 parts of asphalt, 0.5-1.5 parts of rosin, 10-40 parts of zinc oxide, 1-3 parts of stearic acid, 2-6 parts of an anti-aging agent, 2-6 parts of a softening agent, 40-80 parts of a reinforcing filler, 10-35 parts of a heat-resistant filler, 2-5 parts of an accelerant, 0.1-1 part of an anti-vulcanization reducing agent and 0.3-1 part of a vulcanizing agent. According to the rubber material provided by the invention, a formula is optimized, and a sulfide of the rubber material has the characteristics of high temperature resistance, aging resistance, high elasticity and high strength, so that the rubber material can give consideration to the properties of durability, high elasticity, aging resistance and high strength when being used as a bay nozzle rubber, and can better meet the long-term service requirement under a high-temperature working condition (150-170 DEG C).

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of high polymer materials, and particularly relates to a rubber compound and application thereof, and a bladder mouth sub-rubber and a preparation method thereof. BACKGROUND

[0002] Tires are core components of vehicles such as automobiles, engineering machinery, and rail transit, and the stability of the production process and the reliability of the finished product directly determine the driving safety, comfort, and service life of the vehicles. In the core process of tire vulcanization molding, the bladder (also known as a vulcanization capsule) is a key tooling component for realizing accurate shaping and uniform vulcanization of the tire inner cavity, and the bladder mouth sub-rubber is a core functional component for connecting the top end of the bladder to the gas / liquid passage joint of the vulcanization equipment, and is widely used in the vulcanization production scenes of various tires such as passenger radial tires, all-steel radial tires, engineering giant tires, and aviation special tires, and the performance thereof directly affects the stability of the vulcanization process, the overall service life of the bladder, and the quality consistency of the finished tire.

[0003] The service conditions of the bladder mouth sub-rubber have multiple severe characteristics: firstly, the component needs to be in direct contact with the gas / liquid joint of stainless steel for a long time, and in a high-temperature environment, an electrochemical corrosion microcell is easily formed at the metal-rubber interface, accompanied by mechanical friction caused by the operation of the equipment and physical impact caused by the plugging and unplugging of the joint, which easily causes problems such as debonding of the rubber-metal interface and wear of the rubber surface; secondly, various tire vulcanization processes need to be continuously carried out in a high-temperature environment of about 170 DEG C, and the vulcanization temperature of some special tires is even higher, and the continuous high temperature will accelerate the thermal oxidative aging of the rubber molecular chain, causing microstructure deterioration such as crosslinking bond rupture, molecular chain degradation, or excessive crosslinking, and macroscopically, the key performance degradation phenomena such as sharp rise of the elastic modulus, attenuation of the tensile strength, sharp drop of the elongation at break, abnormal increase of the hardness, deformation of the sealing surface, and cracking.

[0004] At present, the conventional bladder mouth sub-rubber in the industry is mostly made of ordinary butyl rubber or chlorinated butyl rubber system, and the high-temperature resistance and aging resistance thereof cannot match the long-term service requirement under high-temperature working conditions. SUMMARY

[0005] The application aims to provide a rubber compound and application thereof, and a bladder mouth sub-rubber and a preparation method thereof, and the vulcanizate of the rubber compound provided by the application has the characteristics of high-temperature resistance, aging resistance, high elasticity, and high strength, and as the bladder mouth sub-rubber, can have the properties of durability, high elasticity, aging resistance, and high strength, and can better match the long-term service requirement under high-temperature working conditions.

[0006] In order to achieve the above-mentioned purpose, the application provides the following technical scheme: The application provides a rubber compound, which comprises the following raw materials in mass fraction: The main rubber 100 parts, asphalt 1~3 parts, rosin 0.5~1.5 parts, zinc oxide 10~40 parts, stearic acid 1~3 parts, antioxidant 2~6 parts, softener 2~6 parts, reinforcing filler 40~80 parts, heat-resistant filler 10~35 parts, accelerator 2~5 parts, anti-reduction agent 0.1~1 parts, vulcanizing agent 0.3~1 parts;The main rubber includes natural rubber and chlorinated butyl rubber;The reinforcing filler includes one or more of carbon black, carbon fiber, carbon nanotube and graphene;The heat-resistant filler includes one or more of asbestos powder, clay and calcium carbonate.

[0007] Preferably, when the main rubber is natural rubber and chlorinated butyl rubber, the mass fraction of natural rubber in the rubber compound is 40~60 parts, and the mass fraction of chlorinated butyl rubber is 40~60 parts; The main rubber also includes one or more of butyl rubber, brominated butyl rubber, ethylene-propylene-diene rubber and chlorobutyl rubber;When the main rubber is natural rubber, chlorinated butyl rubber and ethylene-propylene-diene rubber, the mass fraction of the natural rubber in the rubber compound is 40~50 parts, the mass fraction of chlorinated butyl rubber is 20~40 parts, and the mass fraction of ethylene-propylene-diene rubber is 20~40 parts.

[0008] Preferably, the carbon black includes N330 carbon black and / or N660 carbon black.

[0009] Preferably, the antioxidant includes one or more of antioxidant RD, antioxidant 4020, antioxidant 4010NA, antioxidant MB, antioxidant MBZ, antioxidant NBC, antioxidant 2246, antioxidant 2246S, antioxidant 246, antioxidant SP, antioxidant 6DDP, antioxidant UOP588, antioxidant UOP788, antioxidant DD, antioxidant AW and antioxidant D.

[0010] Preferably, the softener includes one or more of aromatic oil, pine tar and dioctyl phthalate.

[0011] Preferably, the accelerator includes one or more of accelerator MBT, accelerator TMTD, accelerator NOBS and accelerator MBS.

[0012] Preferably, the vulcanizing agent includes sulfur and / or peroxide vulcanizing agent;The anti-reduction agent is anti-reduction agent WK-901.

[0013] The application provides the application of the rubber compound in the above technical solution in the bladder mouth sub-gum.

[0014] The application provides a bladder mouth sub-gum, which is prepared from the rubber compound in the above technical solution.

[0015] This invention provides a method for preparing the water-filled tire nozzle adhesive described in the above technical solution, comprising the following steps: The main rubber, asphalt, rosin, zinc oxide, stearic acid, heat-resistant filler, reinforcing filler, and softener are first mixed; then an antioxidant is added and a second mixing is carried out; finally, the mixture is discharged and cooled to obtain the mixed material. The intensively mixed material, accelerator, vulcanizing agent and anti-sulfurization reducing agent are mixed to obtain a compound material; The mixture is subjected to compression molding and vulcanization to obtain the water tire nozzle rubber.

[0016] This invention provides a rubber compound comprising the following raw materials in parts by weight: 100 parts of base rubber, 1-3 parts of asphalt, 0.5-1.5 parts of rosin, 10-40 parts of zinc oxide, 1-3 parts of stearic acid, 2-6 parts of antioxidant, 2-6 parts of softener, 40-80 parts of reinforcing filler, 10-35 parts of heat-resistant filler, 2-5 parts of accelerator, 0.1-1 part of anti-vulcanization reducing agent, and 0.3-1 part of vulcanizing agent; wherein the base rubber comprises natural rubber and chlorinated butyl rubber; wherein the reinforcing filler comprises one or more of carbon black, carbon fiber, carbon nanotubes, and graphene; and wherein the heat-resistant filler comprises one or more of asbestos powder, kaolin, and calcium carbonate. This invention uses a blend of natural rubber and chlorinated butyl rubber as the main rubber compound. The blend of natural rubber and chlorinated butyl rubber exhibits oil resistance, tear resistance, and resistance to heat and oxygen aging, improving the adhesive strength and physical properties of the rubber compound. This invention adds one or more of asbestos powder, kaolin, and calcium carbonate as heat-resistant fillers to the rubber compound. These fillers are uniformly incorporated into the rubber matrix, resulting in a highly heat-resistant cross-linked rubber after vulcanization. This invention also adds one or more of carbon black, carbon fiber, carbon nanotubes, and graphene as reinforcing fillers, providing high hardness, high elasticity, and flexural strength. This invention achieves these properties through the addition of heat-resistant materials. The addition of fillers and reinforcing fillers, through their compounding, improves the high-temperature resistance of rubber additives. The addition of asphalt and rosin improves the adhesive properties of the rubber compound. The addition of an anti-reversion agent improves the resistance to vulcanization reversion, slows down the breakage of rubber molecular chains, prevents over-vulcanization during high-temperature use, and increases the stability of the rubber compound. The vulcanization system of this invention uses 2-5 parts accelerator combined with 0.3-1 parts vulcanizing agent, employing a low-sulfur, high-accelerator system, which allows for rapid vulcanization during rubber vulcanization. The accelerator provides free sulfur at high temperatures, resulting in an increasing degree of vulcanization at high temperatures. In summary, the rubber compound provided by this invention, through optimized formulation, possesses characteristics of high-temperature resistance, aging resistance, high elasticity, and high strength. As a nozzle rubber for water-filled tires, it combines durability, high elasticity, aging resistance, and high strength, better meeting the long-term service requirements under high-temperature conditions (150-170℃).

[0017] This invention provides a method for preparing the water-filled tire nozzle glue described in the above technical solution. The preparation method provided by this invention is simple to operate, uses common raw materials, and is suitable for industrial application. Detailed Implementation

[0018] This invention provides a rubber compound comprising the following raw materials in parts by weight: The composition comprises 100 parts of base rubber, 1-3 parts of asphalt, 0.5-1.5 parts of rosin, 10-40 parts of zinc oxide, 1-3 parts of stearic acid, 2-6 parts of antioxidant, 2-6 parts of softener, 40-80 parts of reinforcing filler, 10-35 parts of heat-resistant filler, 2-5 parts of accelerator, 0.1-1 part of anti-sulfurization reducing agent, and 0.3-1 part of vulcanizing agent. The base rubber includes natural rubber and chlorinated butyl rubber. The reinforcing filler includes one or more of carbon black, carbon fiber, carbon nanotubes, and graphene. The heat-resistant filler includes one or more of asbestos powder, kaolin, and calcium carbonate.

[0019] In this invention, unless otherwise specified, all raw materials / components used in the preparation are commercially available products well known to those skilled in the art.

[0020] The rubber compound provided by this invention comprises 100 parts by weight of a main rubber. In this invention, the main rubber comprises natural rubber and chlorinated butyl rubber. The natural rubber can be No. 1 smoked sheet rubber. When the main rubber is natural rubber and chlorinated butyl rubber, the preferred weight percentage of natural rubber in the rubber compound is 40-60 parts, and in the examples, it can be 40, 45, 50, 55, or 60 parts; the preferred weight percentage of chlorinated butyl rubber is 40-60 parts, and in the examples, it can be 40, 45, 50, 55, or 60 parts. The main rubber in this invention, being a blend of natural rubber and chlorinated butyl rubber, can significantly improve the high heat resistance and high aging resistance of the rubber compound.

[0021] In this invention, the main rubber may further include one or more of butyl rubber, brominated butyl rubber, ethylene propylene diene monomer (EPDM) rubber, and chloroprene rubber, with EPDM rubber being used in the embodiments. When the main rubber is natural rubber, chlorinated butyl rubber, and EPDM rubber, the mass fraction of natural rubber in the rubber compound is preferably 40-50 parts, with 40 or 45 parts in the embodiments; the mass fraction of chlorinated butyl rubber is preferably 20-40 parts, with 20, 25, 30, 35, or 40 parts in the embodiments; and the mass fraction of EPDM rubber is preferably 20-40 parts, with 20, 25, 30, 35, or 40 parts in the embodiments. This invention uses a blend of natural rubber, chlorinated butyl rubber, and EPDM rubber. Through the synergistic effect of the three main rubbers, the heat resistance and aging resistance of the rubber compound can be further improved.

[0022] Based on the mass fraction of the main rubber, the rubber compound provided by this invention includes 1 to 3 parts of asphalt, which may be 1, 2, or 3 parts in the embodiments. The addition of asphalt in this invention improves the adhesive properties of the rubber compound.

[0023] Based on the mass fraction of the main rubber, the rubber compound provided by this invention includes 0.5 to 1.5 parts of rosin, which can be 0.5, 1, or 1.5 parts in the embodiments. The addition of rosin to the asphalt in this invention can further improve the adhesive properties of the rubber compound and enhance its overall performance.

[0024] Based on the mass fraction of the main rubber, the rubber compound provided by the present invention includes 10 to 40 parts of zinc oxide, which can be 10, 15, 20, 25, 30, 35 or 40 parts in the embodiments.

[0025] Based on the mass fraction of the main rubber, the rubber compound provided by the present invention includes 1 to 3 parts of stearic acid, which may be 1, 2 or 3 parts in the embodiments.

[0026] Based on the mass fraction of the main rubber, the rubber compound provided by the present invention includes 2 to 6 parts of antioxidant, which may be 2, 3, 4, 5, or 6 parts in the embodiments. In the present invention, the antioxidant preferably includes one or more of antioxidants RD, 4020, 4010NA, MB, MBZ, NBC, 2246, 2246S, 246, SP, 6DDP, UOP588, UOP788, DD, AW, and D.

[0027] Based on the mass fraction of the main rubber, the rubber compound provided by the present invention includes 2 to 6 parts of a softener, which may be 2, 3, 4, 5, or 6 parts in the embodiments. In the present invention, the softener preferably includes one or more of aromatic oil, pine tar, and dioctyl phthalate.

[0028] Based on the mass fraction of the main rubber, the rubber compound provided by this invention includes 40-80 parts of reinforcing filler, which can be 40, 45, 50, 55, or 60 parts in the embodiments. In this invention, the reinforcing filler includes one or more of carbon black, carbon fiber, carbon nanotubes, and graphene, and can be carbon black in the embodiments. In this invention, the carbon black preferably includes N330 carbon black and / or N660 carbon black, which can be N330 carbon black and N660 carbon black in the embodiments. In this invention, the mass fraction of N330 carbon black in the rubber compound is preferably 30-60 parts, which can be 30, 35, 40, 45, 50, 55, or 60 parts in the embodiments; the mass fraction of N660 carbon black is preferably 10-20 parts, which can be 10, 15, or 20 parts in the embodiments. This invention uses a blend of N330 carbon black and N660 carbon black as a reinforcing system, which can significantly improve the hardness, elasticity, and flexural strength of the rubber compound.

[0029] Based on the mass fraction of the main rubber, the rubber compound provided by this invention includes 10-35 parts of heat-resistant filler, which can be 10, 15, 20, 25, 30, or 35 parts in the embodiments. In this invention, the heat-resistant filler includes one or more of asbestos powder, kaolin, and calcium carbonate, preferably asbestos powder and kaolin. In this invention, the mass fraction of asbestos powder in the rubber compound is preferably 5-20 parts, which can be 5, 10, 15, or 20 parts in the embodiments; the mass fraction of kaolin is preferably 5-20 parts, which can be 5, 10, 15, or 20 parts in the embodiments. This invention uses a compound of asbestos powder and kaolin as a heat-resistant filler, which, in combination with the reinforcing filler, can significantly improve the hardness, elasticity, and flexural strength of the rubber compound while also considering heat resistance and aging performance.

[0030] Based on the mass fraction of the main rubber, the rubber compound provided by the present invention includes 2 to 5 parts of accelerator, which may be 2, 3, 4, or 5 parts in the embodiments. In the present invention, the accelerator preferably includes one or more of accelerator MBT, accelerator TMTD, accelerator NOBS, and accelerator MBS, and may be accelerator TMTD in the embodiments.

[0031] Based on the mass fraction of the main rubber, the rubber compound provided by this invention includes 0.1 to 1 part of an anti-vulcanization reversion agent, which can be 0.2, 0.3, 0.5, 0.7, 0.8, or 1 part in the embodiments. In this invention, the anti-vulcanization reversion agent can be anti-vulcanization reversion agent WK-901. The use of anti-vulcanization reversion agent WK-901 in this invention can further improve the anti-vulcanization reversion performance of the rubber compound and effectively prevent over-vulcanization during high-temperature use.

[0032] Based on the mass fraction of the main rubber, the rubber compound provided by the present invention includes 0.3 to 1 part of vulcanizing agent, which may be 0.5, 0.6, 0.8, or 1 part in the embodiments. In the present invention, the vulcanizing agent preferably includes sulfur and / or peroxide vulcanizing agent, which may be sulfur in the embodiments.

[0033] This invention provides the application of the rubber compound described above in the rubber compound for water tire nozzles.

[0034] This invention provides a water tire nozzle adhesive, which is made from the rubber compound described in the above technical solution.

[0035] This invention provides a method for preparing the water-filled tire nozzle adhesive described in the above technical solution, comprising the following steps: The main rubber, asphalt, rosin, zinc oxide, stearic acid, heat-resistant filler, reinforcing filler, and softener are first mixed; then an antioxidant is added and a second mixing is carried out; finally, the mixture is discharged and cooled to obtain the mixed material. The intensively mixed material, accelerator, vulcanizing agent and anti-sulfurization reducing agent are mixed to obtain a compound material; The mixture is subjected to compression molding and vulcanization to obtain the water tire nozzle rubber.

[0036] This invention involves a first internal mixer mixing of the main rubber, asphalt, rosin, zinc oxide, stearic acid, heat-resistant filler, reinforcing filler, and softener; followed by a second internal mixer mixing with an antioxidant; and finally, cooling the discharged material to obtain the mixed compound. In this invention, both the first and second internal mixer mixing are performed in an internal mixer. The preferred temperature for the first internal mixer mixing is 100-110°C, and the preferred time is 10-15 minutes. This invention does not have specific requirements for the time of the second internal mixer mixing, as long as the raw materials are mixed evenly. The discharged material is preferably cooled to room temperature.

[0037] After obtaining the internally mixed material, the present invention further mixes the internally mixed material, accelerator, vulcanizing agent, and anti-sulfurization reducing agent to obtain a compound. In the present invention, the mixing is carried out in a two-roll mill.

[0038] After obtaining the mixed rubber, the present invention subjectes the mixed material to compression molding and vulcanization to obtain the water tire nozzle rubber. In the present invention, the compression molding and vulcanization temperature is preferably 104~145℃, the compression molding and vulcanization time is preferably 20~30min, and the compression molding and vulcanization pressure is preferably 15~20MPa.

[0039] To further illustrate the present invention, the technical solutions provided by the present invention will be described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0040] Examples 1-8 and Comparative Examples 1-3 According to the formula in Table 1, weigh the raw materials, add the main rubber (natural rubber (No. 1 smoked sheet rubber), chlorinated butyl rubber, EPDM rubber), asphalt, rosin, zinc oxide, stearic acid, heat-resistant fillers (asbestos powder, kaolin), reinforcing fillers (N330 carbon black, N660 carbon black) and softener into a mixer and stir evenly. Heat to 110℃ and stir for 10 minutes. Then add antioxidants (2.5 parts of antioxidant RD and 1.5 parts of antioxidant 4010NA) and mix evenly. Then discharge and cool to room temperature and set aside for later use. Put the obtained cooled rubber compound into a two-roll mill for mixing. Add accelerator (TMTD), vulcanizing agent (sulfur), and anti-vulcanization reducing agent (WK-901) and mix evenly. Then use compression molding vulcanization at 145℃ for 20 minutes and a pressure of 20MPa to obtain the high-temperature resistant and aging-resistant water tire nozzle compound.

[0041] Table 1. Raw material formulations (parts by mass) for the examples and comparative examples.

[0042] Test case The test results of the high heat resistance and high aging resistance water-filled tire nozzle adhesives prepared in Examples 1-8 and Comparative Examples 1-3 are shown in Table 2. As can be seen from the results in Tables 1 and 2, the water-filled tire nozzles of the examples have good heat resistance and aging resistance, and excellent overall performance.

[0043] Table 2. Test results of water-filled tire nozzle adhesive in the examples and comparative examples.

[0044] As can be seen from the above embodiments, the rubber compound provided by the present invention adds high-temperature resistant fillers to improve the high-temperature resistance of the rubber; adds anti-vulcanization reducing agents to the rubber to slow down the breakage of rubber molecular chains as much as possible, thereby increasing the stability of the rubber; in addition, the vulcanization system is low in sulfur and high in accelerator, which makes the rubber vulcanize quickly, and the accelerator provides free sulfur at high temperature, so that the degree of vulcanization of the rubber at high temperature tends to increase; the water tire nozzle rubber of the present invention has the advantages of high temperature resistance and aging resistance, and can work effectively at high temperatures of 150~170℃.

[0045] Although the above embodiments have provided a detailed description of the present invention, they are only some embodiments of the present invention, and not all embodiments. Other embodiments can be obtained based on these embodiments without creative effort, and these embodiments all fall within the protection scope of the present invention.

Claims

1. A rubber compound, characterized in that, The preparation raw materials include the following mass fractions: The main rubber 100 parts, asphalt 1-3 parts, rosin 0.5-1.5 parts, zinc oxide 10-40 parts, stearic acid 1-3 parts, antioxidant 2-6 parts, softener 2-6 parts, reinforcing filler 40-80 parts, heat-resistant filler 10-35 parts, accelerator 2-5 parts, anti-reduction agent 0.1-1 parts, vulcanizing agent 0.3-1 parts; the main rubber includes natural rubber and chlorinated butyl rubber; the reinforcing filler includes one or more of carbon black, carbon fiber, carbon nanotube and graphene; the heat-resistant filler includes one or more of asbestos powder, clay and calcium carbonate.

2. Rubber mix according to claim 1, characterized in that When the main rubber is natural rubber and chlorinated butyl rubber, the mass fraction of natural rubber in the rubber compound is 40-60 parts, and the mass fraction of chlorinated butyl rubber is 40-60 parts; The main rubber also includes one or more of butyl rubber, brominated butyl rubber, ethylene-propylene-diene rubber and chlorobutyl rubber; when the main rubber is natural rubber, chlorinated butyl rubber and ethylene-propylene-diene rubber, the mass fraction of the natural rubber in the rubber compound is 40-50 parts, the mass fraction of chlorinated butyl rubber is 20-40 parts, and the mass fraction of ethylene-propylene-diene rubber is 20-40 parts.

3. The rubber mix according to claim 1, characterized in that The carbon black includes N330 carbon black and / or N660 carbon black.

4. The rubber mix according to claim 1, characterized in that The antioxidant includes one or more of antioxidant RD, antioxidant 4020, antioxidant 4010NA, antioxidant MB, antioxidant MBZ, antioxidant NBC, antioxidant 2246, antioxidant 2246S, antioxidant 246, antioxidant SP, antioxidant 6DDP, antioxidant UOP588, antioxidant UOP788, antioxidant DD, antioxidant AW and antioxidant D.

5. The rubber mix according to claim 1, characterized in that The softener includes one or more of aromatic hydrocarbon oil, pine tar and dioctyl phthalate.

6. The rubber mix according to claim 1, characterized in that The accelerator includes one or more of accelerator MBT, accelerator TMTD, accelerator NOBS and accelerator MBS.

7. The rubber mix according to claim 1, characterized in that The vulcanizing agent includes sulfur and / or peroxide vulcanizing agent; the anti-reduction agent is anti-reduction agent WK-901.

8. The rubber compound of any one of claims 1-7 for use in a bladder tip.

9. A bladder tip gasket characterized by, Prepared from the rubber compound of any one of claims 1-7.

10. The method of claim 9, wherein the method is characterized by, Including the following steps: Firstly, the main rubber, asphalt, rosin, zinc oxide, stearic acid, heat-resistant filler, reinforcing filler and softener are mixed in a first mixing process; then the antioxidant is added for a second mixing process, and finally the mixed material is discharged and cooled to obtain a mixed compound; The mixed compound, accelerator, vulcanizing agent and anti-reduction agent are mixed to obtain a mixed material; The mixed material is subjected to mold vulcanization to obtain the bladder tip.

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