Hindered phenol AO-1010 / nitrile rubber composite damping material and preparation method thereof

Abstract

The invention discloses a hindered phenol AO-1010 / nitrile rubber composite damping material and a preparation method thereof. The hindered phenol AO-1010 / nitrile rubber composite damping material comprises a nitrile rubber matrix, zinc oxide, stearic acid, sulfur, carbon black, an anti-aging agent 4020, an accelerant DM, an accelerant TMTD and hindered phenol AO-1010. According to the invention, hindered phenol AO-1010 is adopted to form hydrogen-bond interaction on a nitrile rubber matrix to improve the damping performance of nitrile rubber, and fracture and recovery of hydrogen bonds can greatly improve the friction resistance of molecular chain activity of nitrile rubber, so that the movement of molecular chains is hindered, the friction heating effect between molecules is improved, and the damping performance is better; a proper amount of carbon black is added into the rubber blend, and the carbon black is used as a rubber reinforcing agent, so that the mechanical property of the rubber can be greatly improved, the carbon black has a relatively strong adsorption effect on molten hindered phenol AO-1010, and the compatibility between the hindered phenol AO-1010 and a rubber matrix is indirectly improved; therefore, the rubber can still keep good mechanical properties while having good damping performance.

Description

Technical Field

[0001] The invention relates to the technical field of polymer materials, and in particular to a hindered phenol AO-1010 / nitrile rubber composite damping material and a preparation method thereof. Background Art

[0002] As a polymer material, rubber damping material is widely used in the vibration reduction design of high-speed trains and engine suspensions due to its good elasticity, durability and economy. The severe vibrations generated by the key parts of high-speed trains and automobile engines during operation not only affect the riding comfort, but also shorten the service life of high-speed train parts. Adding rubber damping vibration reduction materials to these key parts is currently regarded as an extremely effective solution.

[0003] Nitrile rubber (NBR) is a random polymer obtained by emulsion polymerization with butadiene and acrylonitrile as basic units. The polar nitrile groups and unsaturated double bonds in its molecular structure make it oil-resistant and wear-resistant, and it also has excellent heat resistance and chemical medium stability. To improve the damping performance of nitrile rubber, the acrylonitrile content, vulcanization system, and reinforcing filling system of nitrile rubber are usually changed, or copolymerization and blending are used. Among them, although copolymerization modification can effectively regulate the damping temperature range and maintain the mechanical properties of the material, its reaction conditions are harsh, the production process is complex, and the cost is high, which limits the application of this method. The use of plasticizers can enhance the damping performance of the material, but excessive plasticizers often reduce the tensile strength and hardness of the material. Filler modification can also make the material brittle and reduce its fatigue resistance and ductility.

[0004] Therefore, the prior art still needs to be improved and enhanced. Summary of the invention

[0005] In view of the above-mentioned deficiencies in the prior art, the object of the present invention is to provide a hindered phenol AO-1010 / nitrile rubber composite damping material and a preparation method thereof, aiming to solve the problems in the prior art that the production process of nitrile rubber damping is complicated, the amount of plasticizer used is difficult to control, which often reduces the tensile strength and hardness of the material, and filler modification also causes the material to become brittle and reduces its fatigue resistance and ductility.

[0006] In order to achieve the above object, the present invention adopts the following technical solutions: In the first aspect, a hindered phenol AO-1010 / nitrile rubber composite damping material includes a nitrile rubber matrix, zinc oxide, stearic acid, sulfur, carbon black, antioxidant 4020, accelerator DM, accelerator TMTD and hindered phenol AO-1010; wherein the above raw materials are divided into the following parts by mass: 100 parts of nitrile rubber matrix, 4-7 parts of zinc oxide, 1-2 parts of stearic acid, 1-2 parts of sulfur, 35-45 parts of carbon black, 1-2 parts of antioxidant 4020, 1-2 parts of accelerator DM, 0.15-0.25 parts of accelerator TMTD, and 10-20 parts of hindered phenol AO-1010.

[0007] Furthermore, the hindered phenol AO-1010 forms a hydrogen bond with the nitrile rubber matrix to form a composite material body.

[0008] In a second aspect, a method for preparing a hindered phenol AO-1010 / nitrile rubber composite damping material comprises: Step 1, at 20-30° C., uniformly plasticate the nitrile rubber matrix on an open mill for 5-10 minutes, and after 3-6 thin passes, stand for 12-16 minutes for standby use, then sequentially add the plasticated nitrile rubber matrix, sulfur, hindered phenol AO-1010, zinc oxide, stearic acid, antioxidant 4020, carbon black, accelerator DM, accelerator TMTD and hindered phenol AO-1010 to the open mill and mix for 20-30 minutes to ensure more uniform blending, after all the compounding agents and rubber materials are evenly mixed, pack the mixed rubber into a triangle bag, and stand for 24 hours for standby use; Step 2, plasticize the rubber compound obtained in step 1 again for 3-5 minutes, and thin out the rubber compound after it is plasticized evenly, and vulcanize the rubber compound for 8-15 minutes using a flat plate vulcanizer with a high temperature mold to obtain a vulcanized hindered phenol / nitrile rubber damping rubber material.

[0009] Furthermore, during mixing in step 1, the nitrile rubber matrix, sulfur, hindered phenol AO-1010, zinc oxide, stearic acid, antioxidant 4020, carbon black and the mixed accelerator should be added to the mixing mill in this order.

[0010] Furthermore, during vulcanization in step 2, the mixed rubber should be mixed at a temperature of 155-165° C. and a pressure of 8-15 MPa.

[0011] The technical solution adopted by the present invention has the following beneficial effects: The present invention firstly adopts the hydrogen bonding effect formed by hindered phenol AO-1010 on the nitrile rubber matrix to improve the damping performance of the nitrile rubber. The breaking and recovery of the hydrogen bonds will greatly increase the friction resistance of the nitrile rubber molecular chain activity, so that the movement of the molecular chain is hindered, and the friction heat increase effect between molecules is increased. In each frequency band, the loss factor is higher than that of the nitrile rubber matrix, and the damping performance is better.

[0012] The present invention also adds a proper amount of carbon black to the rubber blend. Carbon black, as a rubber reinforcing agent, can greatly improve the mechanical properties of the rubber. At the same time, carbon black has a large specific surface area and has a strong adsorption effect on the molten hindered phenol AO-1010, which reduces the agglomeration of the hindered phenol AO-1010 in the rubber matrix and indirectly improves the compatibility between the hindered phenol AO-1010 and the rubber matrix, so that the rubber can maintain good mechanical properties while having good damping performance. BRIEF DESCRIPTION OF THE DRAWINGS

[0013] Figure 1 The dynamic loss factor-frequency spectrum of the vulcanized rubber with different usage of hindered phenol AO-1010 prepared in the specific embodiment of the present invention; Figure 2 A graph showing the tensile strength of vulcanized rubber using different amounts of hindered phenol AO-1010 prepared in accordance with a specific embodiment of the present invention; Figure 3 This is a graph of tensile breaking rate of vulcanized rubber with different usage of hindered phenol AO-1010 prepared in a specific embodiment of the present invention; Figure 4 This is the molecular model of AO-1010 / NBR composite material. DETAILED DESCRIPTION

[0014] In order to make the purpose, technical solution and effect of the present invention clearer and more specific, the present invention is further described in detail with reference to the accompanying drawings and examples. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0015] A hindered phenol AO-1010 / nitrile rubber composite damping material, the molecular model of the hindered phenol AO-1010 / nitrile rubber composite damping material is as follows Figure 4 As shown, the composite material is composed of the following raw materials in parts by weight: 100 parts of nitrile rubber matrix, 5 parts of zinc oxide, 2 parts of stearic acid, 1.5 parts of sulfur, 40 parts of carbon black, 2 parts of antioxidant 4020, 2 parts of accelerator DM, 0.25 parts of accelerator TMTD, and 10-20 parts of hindered phenol AO-1010.

[0016] The specific preparation steps are as follows: (1) Mixing Under the condition of 20 to 30 ℃, the nitrile rubber matrix is ​​uniformly plasticized on the mixing mill for 5-10 minutes, and after 3-6 thin passes, it is allowed to stand for 12-16 minutes for use. Subsequently, the plasticized nitrile rubber matrix, sulfur, hindered phenol AO-1010, zinc oxide, stearic acid, antioxidant 4020, carbon black and the mixed accelerator are sequentially added to the mixing mill and mixed for 20-30 minutes to ensure a more uniform blending. After all the compounding agents and rubber materials are evenly mixed, the mixed rubber is packed in a triangle bag and allowed to stand for 24 hours for use.

[0017] (2) Vulcanization The rubber mix obtained in step (1) is plasticized again for 3-5 minutes. After the rubber mix is ​​plasticized uniformly, a thin sheet is cut out. The rubber mix is ​​vulcanized for 8-15 minutes using a plate vulcanizer at a temperature of 155-165° C. and a pressure of 8-15 MPa using a high-temperature mold to obtain a vulcanized hindered phenol / nitrile rubber damping rubber material.

[0018] Furthermore, the brand of the nitrile rubber matrix is ​​N220S, the carbon black model is N330, and the remaining materials are all commercially available chemically pure reagents.

[0019] The features and performance of the present application are further described below in conjunction with the embodiments.

[0020] Example 1 Under the condition of 20 to 30° C., 100 parts of nitrile rubber matrix are uniformly plasticized for 5-10 minutes on an open mill, and after 3-6 thin passes, they are allowed to stand for 12-16 minutes for use. Subsequently, the plasticized 100 parts of nitrile rubber matrix, 1.5 parts of sulfur, 5 parts of zinc oxide, 2 parts of stearic acid, 2 parts of antioxidant 4020, 40 parts of carbon black, and the mixed 2 parts of DM accelerator and 0.25 parts of TMTD accelerator are sequentially added to the open mill and mixed for 20-30 minutes. After all the compounding agents and rubber materials are uniformly mixed, the mixed rubber is packaged in a triangle and allowed to stand for 24 hours for use. After standing for 24 hours, the mixed rubber is plasticized again for 3-5 minutes, and after the mixed rubber is uniformly plasticized, a thin pass is made into a sheet, and a flat plate vulcanizer is used to vulcanize the mixed rubber with a high-temperature mold for 8-15 minutes at a temperature of 160° C. and a pressure of 10 MPa to obtain a vulcanized nitrile rubber damping rubber material.

[0021] The vulcanized rubber is first cut and trimmed, and then put into a rubber punching machine to make the test specimens required for the test, and then the DMA damping performance test and rubber tensile test are carried out respectively.

[0022] Furthermore, the tensile properties were tested on dumbbell-shaped 1A type NBR specimens according to GB 528-2009 standard, with a specimen thickness of 2 mm, a tensile test setting speed of 500 ± 5 mm / min, a calibration distance of 25 mm, a given elongation of 300%, and a test temperature of 25 ± 1 °C.

[0023] Furthermore, the dynamic mechanical analyzer (DMA) selected the film stretching mode, constant temperature frequency sweep, temperature of 25°C, frequency of 0.1-200 Hz, and strain amplitude of 15 μm.

[0024] Example 2 Under the condition of 20 to 30 ℃, 100 parts of nitrile rubber matrix are uniformly plasticized on an open mill for 5-10 minutes, and after 3-6 thin passes, they are allowed to stand for 12-16 minutes for use. Subsequently, 100 parts of the plasticized nitrile rubber matrix, 1.5 parts of sulfur, 10 parts of hindered phenol AO-1010, 5 parts of zinc oxide, 2 parts of stearic acid, 2 parts of antioxidant 4020, 40 parts of carbon black and the mixed 2 parts of DM accelerator and 0.25 parts of TMTD accelerator are sequentially added into the open mill and mixed for 20-30 minutes. After all the compounding agents and rubber materials are evenly mixed, the mixed rubber is packed in a triangle bag and allowed to stand for 24 hours for use. After standing for 24 hours, the rubber mix was plasticized again for 3-5 minutes. After the rubber mix was plasticized evenly, a thin sheet was cut out. The rubber mix was vulcanized for 8-15 minutes using a flat plate vulcanizer at a temperature of 160°C and a pressure of 10 MPa using a high-temperature mold to obtain a vulcanized nitrile rubber damping rubber material.

[0025] The vulcanized rubber is first cut and trimmed, and then put into a rubber punching machine to make the test specimens required for the test, and then DMA damping performance test, rubber tensile and tearing test are carried out respectively.

[0026] Furthermore, the tensile properties were tested on dumbbell-shaped 1A type NBR specimens according to GB 528-2009 standard, with a specimen thickness of 2 mm, a tensile test setting speed of 500 ± 5 mm / min, a calibration distance of 25 mm, a given elongation of 300%, and a test temperature of 25 ± 1 °C.

[0027] Furthermore, the tearing performance test was conducted on a right-angle NBR specimen according to GB 529-2008 standard, the specimen thickness was 2 mm, the tensile test speed was set at 500±5 mm / min, and the test temperature was 25±1°C.

[0028] Furthermore, the dynamic mechanical analyzer (DMA) selected the film stretching mode, constant temperature frequency sweep, temperature of 25°C, frequency of 0.1-200 Hz, and strain amplitude of 15 μm.

[0029] Example 3 Under the condition of 20 to 30 ℃, 100 parts of nitrile rubber matrix are uniformly plasticized on an open mill for 5-10 minutes, and after 3-6 thin passes, they are allowed to stand for 12-16 minutes for use. Subsequently, 100 parts of the plasticized nitrile rubber matrix, 1.5 parts of sulfur, 20 parts of hindered phenol AO-1010, 5 parts of zinc oxide, 2 parts of stearic acid, 2 parts of antioxidant 4020, 40 parts of carbon black and the mixed 2 parts of DM accelerator and 0.25 parts of TMTD accelerator are sequentially added into the open mill and mixed for 20-30 minutes. After all the compounding agents and rubber materials are evenly mixed, the mixed rubber is packed in a triangle bag and allowed to stand for 24 hours for use. After standing for 24 hours, the rubber mix was plasticized again for 3-5 minutes. After the rubber mix was plasticized evenly, a thin sheet was cut out. The rubber mix was vulcanized for 8-15 minutes using a flat plate vulcanizer at a temperature of 160°C and a pressure of 10 MPa using a high-temperature mold to obtain a vulcanized nitrile rubber damping rubber material.

[0030] The vulcanized rubber is first cut and trimmed, and then put into a rubber punching machine to make the test specimens required for the test, and then DMA damping performance test, rubber tensile and tearing test are carried out respectively.

[0031] Furthermore, the tensile properties were tested on dumbbell-shaped 1A type NBR specimens according to GB 528-2009 standard, with a specimen thickness of 2 mm, a tensile test setting speed of 500 ± 5 mm / min, a calibration distance of 25 mm, a given elongation of 300%, and a test temperature of 25 ± 1 °C.

[0032] Furthermore, the tearing performance test was conducted on a right-angle NBR specimen according to GB 529-2008 standard, the specimen thickness was 2 mm, the tensile test speed was set at 500±5 mm / min, and the test temperature was 25±1°C.

[0033] Furthermore, the dynamic mechanical analyzer (DMA) selected the film stretching mode, constant temperature frequency sweep, temperature of 25°C, frequency of 0.1-200 Hz, and strain amplitude of 15 μm.

[0034] Example 4 Under the condition of 20 to 30 ℃, 100 parts of nitrile rubber matrix are uniformly plasticized on an open mill for 5-10 minutes, and after 3-6 thin passes, they are allowed to stand for 12-16 minutes for use. Subsequently, 100 parts of the plasticized nitrile rubber matrix, 1.5 parts of sulfur, 40 parts of hindered phenol AO-1010, 5 parts of zinc oxide, 2 parts of stearic acid, 2 parts of antioxidant 4020, 40 parts of carbon black and the mixed 2 parts of DM accelerator and 0.25 parts of TMTD accelerator are sequentially added into the open mill and mixed for 20-30 minutes. After all the compounding agents and rubber materials are evenly mixed, the mixed rubber is packed in a triangle bag and allowed to stand for 24 hours for use. After standing for 24 hours, the rubber mix was plasticized again for 3-5 minutes. After the rubber mix was plasticized evenly, a thin sheet was cut out. The rubber mix was vulcanized for 8-15 minutes using a flat plate vulcanizer at a temperature of 160°C and a pressure of 10 MPa using a high-temperature mold to obtain a vulcanized nitrile rubber damping rubber material.

[0035] The vulcanized rubber is first cut and trimmed, and then put into a rubber punching machine to make the test specimens required for the test, and then DMA damping performance test, rubber tensile and tearing test are carried out respectively.

[0036] Furthermore, the tensile properties were tested on dumbbell-shaped 1A type NBR specimens according to GB 528-2009 standard, with a specimen thickness of 2 mm, a tensile test setting speed of 500 ± 5 mm / min, a calibration distance of 25 mm, a given elongation of 300%, and a test temperature of 25 ± 1 °C.

[0037] Furthermore, the tearing performance test was conducted on a right-angle NBR specimen according to GB 529-2008 standard, the specimen thickness was 2 mm, the tensile test speed was set at 500±5 mm / min, and the test temperature was 25±1°C.

[0038] Furthermore, the dynamic mechanical analyzer (DMA) selected the film stretching mode, constant temperature frequency sweep, temperature of 25°C, frequency of 0.1-200 Hz, and strain amplitude of 15 μm.

[0039] Example 5 Under the condition of 20 to 30 ℃, 100 parts of nitrile rubber matrix are uniformly plasticized on an open mill for 5-10 minutes, and after 3-6 thin passes, they are allowed to stand for 12-16 minutes for use. Subsequently, 100 parts of the plasticized nitrile rubber matrix, 1.5 parts of sulfur, 40 parts of hindered phenol AO-1010, 5 parts of zinc oxide, 2 parts of stearic acid, 2 parts of antioxidant 4020, 40 parts of carbon black and the mixed 2 parts of DM accelerator and 0.25 parts of TMTD accelerator are sequentially added into the open mill and mixed for 20-30 minutes. After all the compounding agents and rubber materials are evenly mixed, the mixed rubber is packed in a triangle bag and allowed to stand for 24 hours for use. After standing for 24 hours, the rubber mix was plasticized again for 3-5 minutes. After the rubber mix was plasticized evenly, a thin sheet was cut out. The rubber mix was vulcanized for 8-15 minutes using a flat plate vulcanizer at a temperature of 160°C and a pressure of 10 MPa using a high-temperature mold to obtain a vulcanized nitrile rubber damping rubber material.

[0040] The vulcanized rubber is first cut and trimmed, and then put into a rubber punching machine to make the test specimens required for the test, and then DMA damping performance test, rubber tensile and tearing test are carried out respectively.

[0041] Furthermore, the tensile properties were tested on dumbbell-shaped 1A type NBR specimens according to GB 528-2009 standard, with a specimen thickness of 2 mm, a tensile test setting speed of 500 ± 5 mm / min, a calibration distance of 25 mm, a given elongation of 300%, and a test temperature of 25 ± 1 °C.

[0042] Furthermore, the tearing performance test was conducted on a right-angle NBR specimen according to GB 529-2008 standard, the specimen thickness was 2 mm, the tensile test speed was set at 500±5 mm / min, and the test temperature was 25±1°C.

[0043] Furthermore, the dynamic mechanical analyzer (DMA) selected the film stretching mode, constant temperature frequency sweep, temperature of 25°C, frequency of 0.1-200 Hz, and strain amplitude of 15 μm.

[0044] Examples 1 to 5 are examples in which the content of hindered phenol AO-1010 added is changed. The amount of hindered phenol AO-1010 added is increased from 0 to 40 parts, and the other materials and processes are unchanged. Figure 1 It can be seen that Example 5, i.e., the hindered phenol / nitrile rubber damping rubber material with 40 parts of hindered phenol AO-1010 added, has the largest loss factor at each frequency, and its damping performance is better than that of the materials prepared in other embodiments.

[0045] Examples 1 to 5 are examples in which the content of hindered phenol AO-1010 added is changed. The amount of hindered phenol AO-1010 added is increased from 0 to 40 parts, and the other materials and processes are unchanged. Figure 2 It can be seen that the hindered phenol / nitrile rubber damping rubber material in Example 1, in which the hindered phenol AO-1010 is added in 0 parts, has the greatest tensile strength. Figure 3 It can be seen that Example 5, i.e., the hindered phenol / nitrile rubber damping rubber material with 40 parts of hindered phenol AO-1010 added, has the largest tensile fracture rate.

[0046] Further, from Figure 1 , Figure 2 and Figure 3 It can be seen that the addition of hindered phenol AO-1010 can effectively improve the damping performance of nitrile rubber in each frequency band, but it will also reduce the mechanical properties of the material to varying degrees. When the hindered phenol AO-1010 is added in an amount of 10-20 parts, the mechanical properties of the material are maintained while the damping performance is significantly improved. This application uses this addition amount as the addition amount of hindered phenol / nitrile rubber damping rubber material to meet the actual requirements of damping and mechanical properties.

[0047] Those skilled in the art will readily appreciate other embodiments of the present invention after considering the specification and practicing the schemes disclosed herein. The present invention is intended to cover any variations, uses or adaptations of the present invention that follow the general principles of the present invention and include common knowledge or customary techniques in the art that are not disclosed in this disclosure. The description and examples are to be considered exemplary only, and the true scope and spirit of the present invention are indicated by the claims.

Claims

1. A hindered phenol AO-1010 / nitrile rubber composite damping material, characterized in that: It includes nitrile rubber matrix, zinc oxide, stearic acid, sulfur, carbon black, antioxidant 4020, accelerator DM, accelerator TMTD and hindered phenol AO-1010; wherein the above raw materials are divided into the following parts by mass: 100 parts of nitrile rubber matrix, 4-7 parts of zinc oxide, 1-2 parts of stearic acid, 1-2 parts of sulfur, 35-45 parts of carbon black, 1-2 parts of antioxidant 4020, 1-2 parts of accelerator DM, 0.15-0.25 parts of accelerator TMTD and 10-20 parts of hindered phenol AO-1010.

2. The hindered phenol AO-1010 / nitrile rubber composite damping material according to claim 1, characterized in that: The hindered phenol AO-1010 forms a hydrogen bond with the nitrile rubber matrix to form a composite material body.

3. A method for preparing the hindered phenol AO-1010 / nitrile rubber composite damping material as claimed in claim 1, characterized in that: include: Step 1, at 20-30° C., uniformly plasticize the nitrile rubber matrix on an open mill for 5-10 minutes, and after 3-6 thin passes, stand for 12-16 minutes for standby use, then sequentially add the plasticized nitrile rubber matrix, zinc oxide, stearic acid, sulfur, carbon black, antioxidant 4020, accelerator DM, accelerator TMTD and hindered phenol AO-1010 to the open mill and mix for 20-30 minutes, after all the compounding agents and rubber materials are uniformly mixed, pack the mixed rubber into a triangle bag, and stand for 24 hours for standby use; Step 2, plasticize the rubber mix obtained in step 1 again for 3-5 minutes, and after the rubber mix is ​​plasticized evenly, thinly slice it out, and use a flat plate vulcanizer with a high-temperature mold to vulcanize the rubber mix for 8-15 minutes to obtain a vulcanized hindered phenol AO-1010 / nitrile rubber damping rubber material.

4. The method for preparing the hindered phenol AO-1010 / nitrile rubber composite damping material according to claim 3, characterized in that: During mixing in step 1, the nitrile rubber matrix, sulfur, hindered phenol AO-1010, zinc oxide, stearic acid, antioxidant 4020, carbon black and the mixed accelerator should be added to the mixing mill in this order.

5. The method for preparing the hindered phenol AO-1010 / nitrile rubber composite damping material according to claim 3, characterized in that: During vulcanization in step 2, the mixed rubber should be mixed at a temperature of 155-165°C and a pressure of 8-15Mpa.

6. An application of the hindered phenol AO-1010 / nitrile rubber composite damping material as claimed in claim 1 in high-speed train corrugated floors, side wall attached damping plates and automobile engine suspension vibration reduction.

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