High-resilience rubber material and preparation method thereof

Abstract

The invention discloses a high-resilience rubber material and a preparation method thereof, and belongs to the technical field of rubber preparation. The preparation method comprises the following steps: carrying out heat treatment on the raw natural rubber, mixing with the micro-nano spherical hollow powder, carrying out vacuum mixing, mixing the mixed product with the plasticizer and the processing aid, banburying, carrying out open milling on the banburying product, adding the vulcanizing agent, extruding, and finally vulcanizing. The micro-nano spherical hollow powder is introduced in the rubber production process, the targeted preparation method is designed, the high-resilience rubber material is obtained, the resilience performance of rubber is improved, and the preparation method is simple and suitable for industrial production.

Description

Technical Field

[0001] The present invention belongs to the technical field of rubber preparation, and particularly relates to a high resilience rubber material and a preparation method thereof. Background Art

[0002] In recent years, with the continuous growth of the global economy and the continuous improvement of people's living standards, the demand for rubber products has been increasing. Especially in emerging industries such as automobiles, electronics, and aerospace, the quality and performance requirements for rubber products are constantly improving, bringing new development opportunities for high resilience rubber. High resilience rubber is widely used in many fields such as industry, agriculture, national defense, transportation, machinery manufacturing, and daily life, and plays an important role especially in tire manufacturing, shoe-making, medical treatment, and sports equipment.

[0003] Currently, the main filler used in the production process of high resilience rubber is carbon black. This filler relies on a large amount of non-renewable resources such as petroleum and natural gas, and has high energy consumption, environmental pollution, and a high price during the production process. In the prior art, no other filler has been found that can achieve the high strength, high resilience, aging resistance, high temperature resistance, or low temperature resistance of rubber products. Summary of the Invention

[0004] The purpose of the present invention is to provide a high resilience rubber material and a preparation method thereof. By introducing micro-nano spherical hollow powder during the rubber production process and designing a targeted preparation method, a high resilience rubber material is obtained, improving the resilience performance of the rubber.

[0005] To achieve the above purposes, the present invention adopts the following specific technical solutions: In the first aspect, the present invention provides a preparation method of a high resilience rubber material, including the following steps: S1: Heat-treat the natural rubber raw rubber, mix it with micro-nano spherical hollow powder, and then conduct vacuum mixing. Utilize the vacuum effect and high-speed stirring to fully entangle and connect the rubber molecular chains with the micro-nano spherical hollow powder; S2: Mix the mixed product with a plasticizer and a processing aid and conduct internal mixing; S3: Open-mill the internally mixed product, add a vulcanizing agent, and extrude; S4: Vulcanize the product obtained in step S3 to obtain the high resilience rubber material.

[0006] Further, calculated based on 100 parts by weight of the natural rubber raw rubber, the micro-nano spherical hollow powder, plasticizer, processing aid, and vulcanizing agent are respectively 10 - 30 parts, 10 - 50 parts, 1 - 10 parts, and 1 - 5 parts.

[0007] Further, in step S1, the temperature of the heat treatment is 160 - 200 °C, and the time of the heat treatment is 1 - 2 h. The heat treatment within this temperature range is to reduce the rubber viscosity and simultaneously activate the molecular chain activity to fully entangle and connect with the surface of the powder and the pore wall structure inside. If the temperature is too low, the micro-nano spherical hollow powder cannot be fully mixed and the molecular chain activity cannot be improved; if the temperature is too high, the rubber is prone to decomposition.

[0008] Preferably, in step S1, the micro-nano spherical hollow powder has multiple closed small cavities inside, the overall porosity is 20 - 50%, the average particle size is 5 - 80 μm, the average surface pore diameter is between 2 - 5 μm, and the average diameter of the small cavities is 3 - 10 μm.

[0009] Preferably, the bulk density of the micro-nano spherical hollow powder is 0.1 - 0.8 g / cm 3 .

[0010] More preferably, the raw materials of the micro-nano spherical hollow powder include 40 - 50 parts by mass of silica, 40 - 50 parts by mass of alumina, and 5 - 10 parts by mass of calcium oxide.

[0011] Optionally, the plasticizer is one or more of paraffin oil, aromatic oil, naphthenic oil, or resin.

[0012] Optionally, the processing aid is one or more of stearic acid, antioxidant MMBI, active zinc oxide, dispersant RL, accelerator DM, accelerator TT, or accelerator S - 80.

[0013] Optionally, the vulcanizing agent is one or more of hydroquinone, bisphenol A, or bisphenol AF. Further, in step S2, the temperature of the internal mixer is 80 - 120 °C, and the time of the internal mixing is 3 - 10 min.

[0014] Further, in step S3, the temperature of the open mill is 30 - 60 °C, and the time of the open milling is 5 - 10 min. Further, the number of extrusions is 10 - 15 times. Further, in step S4, the temperature of the vulcanization is 150 - 190 °C, the time of the vulcanization is 30 - 90 min, and the pressure of the vulcanization is 8 - 10 MPa.

[0015] In the second aspect, the present invention also provides a high - resilience rubber material prepared by the described preparation method.

[0016] Compared with the prior art, the present invention introduces a micro-nano spherical hollow powder material. Due to its high strength and unique spherical hollow structure, the interfacial interaction with the raw rubber after heat treatment can slow down the slippage and deformation of rubber molecular chains, enhance the compressive performance and service life of the composite material, reduce plastic deformation during compression, enable it to better maintain its initial shape and performance, thereby improving the anti-compression deformation ability of the material and greatly enhancing the resilience of the rubber. At the same time, a strong link is formed with rubber molecular chains through the surface opening structure, improving the mechanical properties and aging resistance of the rubber. The preparation method of the present invention is simple and suitable for industrial production. Detailed Embodiments

[0017] The following will describe the implementation scheme of the present invention in detail in combination with specific embodiments. However, those skilled in the art will understand that the following embodiments are only used to illustrate the present invention and should not be regarded as limiting the scope of the present invention. For those not specified in the embodiments, they are carried out according to conventional conditions or conditions recommended by the manufacturer. For reagents or instruments not specified for the manufacturer, they are all conventional products that can be obtained through commercial purchase. Among them, the micro-nano spherical hollow powder is prepared according to the method of patent CN116422225B.

[0018] Example 1 A preparation method of a high resilience rubber material: Step 1: Weigh 100 g of natural rubber raw rubber and put it into a crucible, and then put it into a high-temperature furnace for heat treatment. The temperature is set at 170 °C, and the heat treatment time is 1 h. Then directly add the heat-treated rubber and 20 g of micro-nano spherical hollow powder into a vacuum high-speed mixer for mixing, and use the vacuum effect and high-speed stirring to fully wind and connect the rubber molecular chains with the micro-nano spherical hollow powder.

[0019] Among them, the micro-nano spherical hollow powder has multiple closed small cavities inside, the overall porosity is 42%, the average particle size is 26 μm, the average surface pore diameter is 1.4 μm, the average diameter of the small cavities is 3.7 μm, and the bulk density is 0.24 g / cm 3 .

[0020] Step 2: Put the product of Step 1, 20 g of paraffin oil and 5 g of stearic acid into a mixer for mixing in sequence. The mixing temperature is 100 °C, the rotor speed is 90 r / min, and the mixing time is 8 min.

[0021] Step 3: After the product of Step 2 is cooled, put it on a two-roll mill for rolling, add 5 g of hydroquinone, roll 15 times, the rolling temperature is 60 °C, and the rolling time is 10 min.

[0022] Step 4: Vulcanize the product of Step 3 in a flat vulcanizer. The vulcanization time is 60 min, the vulcanization temperature is 180 °C, and the vulcanization pressure is 10 MPa. After completion, the rubber product can be obtained, and its test performance is shown in Table 1.

[0023] Example 2 A preparation method of a high resilience rubber material: Step 1: Weigh 100 g of natural rubber raw rubber and put it into a crucible, then put it into a high-temperature furnace for heat treatment. The temperature is set at 180 °C, and the heat treatment time is 1.5 h. Then directly add the heat-treated rubber and 10 g of micro-nano spherical hollow powder into a vacuum high-speed mixer for mixing.

[0024] Among them, the micro-nano spherical hollow powder is the same as that in Example 1.

[0025] Step 2: Put the product of Step 1, 35 g of naphthenic oil and 10 g of stearic acid into a mixer in sequence for mixing. The mixing temperature is 90 °C, the rotor speed is 90 r / min, and the mixing time is 10 min.

[0026] Step 3: After the product of Step 2 is cooled, put it on a two-roll mill for milling, add 2 g of bisphenol A, extrude 10 times, the milling temperature is 40 °C, and the milling time is 5 min.

[0027] Step 4: Vulcanize the product of Step 3 in a flat vulcanizer. The vulcanization time is 80 min, the vulcanization temperature is 150 °C, and the vulcanization pressure is 8 MPa. After completion, the rubber product can be obtained, and its test performance is shown in Table 1.

[0028] Example 3 A preparation method of a high resilience rubber material: Step 1: Weigh 100 g of natural rubber raw rubber and put it into a crucible, then put it into a high-temperature furnace for heat treatment. The temperature is set at 160 °C, and the heat treatment time is 2 h. Then directly add the heat-treated rubber and 15 g of micro-nano spherical hollow powder into a vacuum high-speed mixer for mixing.

[0029] Among them, the micro-nano spherical hollow powder is the same as that in Example 1.

[0030] Step 2: Put the product of Step 1, 40 g of paraffin oil and 3 g of stearic acid into a mixer in sequence for mixing. The mixing temperature is 120 °C, the rotor speed is 90 r / min, and the mixing time is 3 min.

[0031] Step 3: After the product of Step 2 is cooled, put it on a two-roll mill for milling, add 3 g of bisphenol A, extrude 12 times, the milling temperature is 50 °C, and the milling time is 8 min.

[0032] Step 4: Vulcanize the product of Step 3 in a flat vulcanizer for 30 min at a vulcanization temperature of 160 °C and a vulcanization pressure of 9 MPa. After completion, the rubber product can be obtained, and its test performance is shown in Table 1.

[0033] Example 4 The difference from Example 1 is that the micro-nano spherical hollow powder has multiple closed small cavities inside, the overall porosity is 46%, the average particle size is 45 μm, the average surface pore diameter is 2.6 μm, the average diameter of the small cavities is 5.6 μm, and the bulk density is 0.46 g / cm 3 .

[0034] Its test performance is shown in Table 1.

[0035] Example 5 The difference from Example 1 is that the micro-nano spherical hollow powder has multiple closed small cavities inside, the overall porosity is 48%, the average particle size is 71 μm, the average surface pore diameter is 2.4 μm, the average diameter of the small cavities is 5.7 μm, and the bulk density is 0.59 g / cm 3 .

[0036] Its test performance is shown in Table 1.

[0037] Comparative Example 1 The difference from Example 1 is that no micro-nano spherical hollow powder is added. Its test performance is shown in Table 1.

[0038] Comparative Example 2 The difference from Example 1 is that the natural rubber raw rubber is not heat-treated. Its test performance is shown in Table 1.

[0039] Table 1 Comparison of the test performance of the rubber materials in Examples 1-5 and Comparative Examples 1-2 As can be seen from Table 1, for the rubber materials prepared in Examples 1-5, due to the introduction of the micro-nano spherical hollow powder material, the interfacial interaction with the heat-treated raw rubber can slow down the slip and deformation of the rubber molecular chains. Compared with Comparative Example 1, its resilience performance is significantly improved.

[0040] In Comparative Example 2, since the raw rubber was not heat-treated, the micro-nano spherical hollow powder could not be fully mixed and the molecular chain activity could not be improved, and its resilience performance was significantly inferior to that of Examples 1-5.

[0041] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that they can still modify the technical solutions described in the foregoing embodiments, or perform equivalent replacements on some or all of the technical features; and these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the various embodiments of the present invention.

[0042] In addition, those skilled in the art can understand that although some embodiments herein include certain features included in other embodiments rather than other features, the combination of the features of different embodiments means that it is within the scope of the present invention and forms different embodiments. For example, in the claims above, any one of the claimed embodiments can be used in any combination. The information disclosed in this background art section is only intended to deepen the understanding of the overall background art of the present invention, and should not be regarded as an admission or any form of suggestion that this information constitutes the prior art known to those skilled in the art.

Claims

1. A method for preparing a high resilience rubber material, characterized in that: The steps include: S1: heat-treating the raw natural rubber, mixing it with the micro-nano spherical hollow powder and then performing vacuum kneading; S2: mixing the mixed product with a plasticizer and a processing aid for internal kneading; S3: Open-milling the product after the internal mixing, adding a vulcanizing agent, and extruding; S4: The product obtained in step S3 is vulcanized to obtain the high resilience rubber material.

2. The preparation method according to claim 1, characterized in that: Based on 100 parts by weight of the raw natural rubber, the micro-nano spherical hollow powder, plasticizer, processing aid and vulcanizer are 10-30 parts, 10-50 parts, 1-10 parts and 1-5 parts respectively.

3. The preparation method according to claim 1, characterized in that: In step S1, the heat treatment temperature is 160-200° C., and the heat treatment time is 1-2 h.

4. The preparation method according to claim 1, characterized in that: In step S1, the micro-nano spherical hollow powder has a plurality of closed small cavities inside, an overall porosity of 20-50%, an average particle size of 5-80 μm, an average surface pore size of 2-5 μm, and an average diameter of the small cavities of 3-10 μm.

5. The preparation method according to claim 1 or 4, characterized in that: The bulk density of the micro-nano spherical hollow powder is 0.1-0.8 g / cm 3 .

6. The preparation method according to claim 1, characterized in that: The plasticizer is one or more of paraffin oil, aromatic oil, naphthenic oil or resin; And / or, the processing aid is one or more of stearic acid, antioxidant MMBI, active zinc oxide, dispersant RL, accelerator DM, accelerator TT or accelerator S-80; And / or, the vulcanizing agent is one or more of hydroquinone, bisphenol A or bisphenol AF.

7. The preparation method according to claim 1, characterized in that: In step S2, the banburying temperature is 80-120° C., and the banburying time is 3-10 min.

8. The preparation method according to claim 1, characterized in that: In step S3, the temperature of the open refining is 30-60°C, and the time of the open refining is 5-10 minutes; And / or, the pressing is performed 10-15 times.

9. The preparation method according to claim 1, characterized in that: In step S4, the vulcanization temperature is 150-190° C., the vulcanization time is 30-90 min, and the vulcanization pressure is 8-10 MPa.

10. A high resilience rubber material, characterized in that: The method is prepared by the method according to any one of claims 1 to 9.

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