High-damping wide-temperature-range rubber and preparation method thereof

Abstract

The invention provides high-damping wide-temperature-range rubber and a preparation method thereof, and relates to the technical field of functional polymer materials. The high-damping wide-temperature-range rubber comprises the following components in parts by mass: 50-70 parts of natural rubber; 30-50 parts of butyl rubber; 0.5 to 1.0 part of corrugated mica; 1.5 to 2.5 parts of an anti-aging agent; 30-40 parts of carbon black; 45-70 parts of an inorganic filler; 3-5 parts of a plasticizer; 0.8 to 1.2 parts of sulfur; and 0.5 to 1.5 parts of accelerant. The rubber material has excellent damping performance.

Description

Technical Field

[0001] The invention relates to the technical field of functional polymer materials, and in particular to a high-damping wide-temperature range rubber and a preparation method thereof. Background Art

[0002] Shock-absorbing rubber is a vulcanized rubber product that prevents the transmission of vibration and impact or acts as a buffer. It is widely used in vibration isolation of mechanical production equipment, transportation equipment and buildings. Natural rubber is widely used in shock-absorbing rubber due to its excellent comprehensive performance, but natural rubber has a low damping coefficient and a narrow damping temperature range, and its application in situations requiring low temperature and high shock-absorbing performance is subject to certain restrictions. In order to improve the damping performance and damping temperature range of natural rubber, the commonly used method currently includes adding butyl rubber to natural rubber. However, due to the high temperature sensitivity of butyl rubber, it is still impossible to provide a stable shock-absorbing and noise-reducing material under low temperature conditions. Therefore, the preparation of a high-damping, low-thermal-sensitivity rubber material has become a technical problem that technicians in this field urgently need to solve. Summary of the invention

[0003] 1. Technical issues to be solved

[0004] In view of the deficiencies in the prior art, the present invention provides a high-damping wide-temperature range rubber and a preparation method thereof, which solves the technical problem that the damping performance and damping temperature range of the existing rubber materials cannot meet the requirements of low temperature and high shock absorption performance.

[0005] (II) Technical solution

[0006] To achieve the above objectives, the present invention is implemented through the following technical solutions:

[0007] In a first aspect, the present invention provides a high-damping wide-temperature range rubber, comprising the following components in parts by weight:

[0008] Natural rubber 50-70;

[0009]

[0010] Preferably, the antioxidant is selected from amine antioxidants or phenolic antioxidants.

[0011] Preferably, the amine antioxidant is selected from any one of a ketoamine antioxidant, an aldehyde amine antioxidant or a diaromatic secondary amine antioxidant.

[0012] Preferably, the phenolic antioxidant is selected from 4,4-dihydroxybiphenyl.

[0013] Preferably, the inorganic filler is selected from any one of clay, talc, wollastonite powder, asbestos, silicon aluminum carbon black, and sepiolite.

[0014] Preferably, the plasticizer is selected from naphthenic mineral oils.

[0015] Preferably, the accelerator is selected from any one of 1,3-di-o-tolylguanidine, N-tert-butyl-2-benzothiazole sulfenamide, and N-oxydiethylene-2-benzothiazole sulfenamide.

[0016] In a second aspect, the present invention provides a method for preparing the high-damping wide-temperature range rubber according to the first aspect, comprising the following steps:

[0017] S1. Mixing natural rubber and butyl rubber at a temperature of 110° C. to 130° C. for 100 seconds to 120 seconds to obtain plasticized rubber;

[0018] S2, mixing the plasticized rubber at a temperature of 110° C.-130° C. for 50-60 seconds, adding corrugated mica and an antioxidant thereto and mixing for 50-60 seconds, then adding carbon black, an inorganic filler and a plasticizer and mixing for 100 seconds-120 seconds, then adding sulfur and an accelerator and mixing for 20 seconds-40 seconds, and cooling for standby use;

[0019] S3, the material after mixing in the above step 2) is loaded into a mold, pressurized, and vulcanized to obtain a high-damping wide-temperature range rubber.

[0020] Preferably, the corrugated mica is prepared according to the following method:

[0021] S1, adding a dispersant and a silane coupling agent to water and dispersing them evenly, then adding flaky mica with a particle size of 200-220 mesh to prepare a colloidal suspension;

[0022] S2. Alternately emitting a combination of low-frequency, medium-frequency and high-frequency ultrasonic waves into the colloidal suspension, wherein the low frequency is 25-35 kHz, the working time is 30-50 minutes, the medium frequency is 65-90 kHz, the working time is 50-70 minutes, the high frequency is 125-180 kHz, the working time is 70-90 minutes, and then drying at 120-140° C. for 1-1.5 hours to obtain corrugated mica.

[0023] Preferably, the silane coupling agent is 3-aminopropyltrimethoxysilane or (3-aminopropyl)triethoxysilane.

[0024] (III) Beneficial effects

[0025] The present invention provides a high-damping wide-temperature range rubber and a preparation method thereof. Compared with the prior art, the present invention has the following beneficial effects:

[0026] The high damping wide temperature range rubber of the present invention comprises natural rubber, butyl rubber, corrugated mica, antioxidant, carbon black, inorganic filler, plasticizer, sulfur, accelerator, and the surface of the corrugated mica has a shape similar to corrugation, which increases the specific surface area of ​​mica and the contact area between mica particles and rubber molecules. As the contact area between the corrugated mica and the rubber molecules increases, the temporary structure formed by the van der Waals force increases, and this structure is easy to decompose and easy to generate. In dynamic strain, the continuous decomposition and generation of this structure bring about the hysteresis loss of the material. Secondly, the specific surface area of ​​the corrugated mica increases, and the friction between the mica particles and the particles also increases. Thus, the rubber material prepared shows a larger tanδ and has a relatively excellent damping effect. In addition, the addition of sulfur and accelerators improves the vulcanization effect of rubber, thereby ensuring that the damping temperature range of the rubber material of the present invention is relatively wide. DETAILED DESCRIPTION

[0027] In order to make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are clearly and completely described. Obviously, the described embodiments are 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.

[0028] The embodiments of the present application provide a high-damping wide-temperature range rubber and a preparation method thereof, thereby solving the technical problem that the damping performance and damping temperature range of existing rubber materials cannot meet the requirements of low temperature and high shock absorption performance.

[0029] The technical solution in the embodiment of the present application is to solve the above technical problems, and the overall idea is as follows:

[0030] The preparation method of the corrugated mica of the present invention comprises the following steps: S1, adding a dispersant and a silane coupling agent to water for uniform dispersion, and then adding flaky mica with a particle size of 200-220 meshes to prepare a colloidal suspension; S2, alternately emitting a low-frequency, medium-frequency, and high-frequency ultrasonic combination into the colloidal suspension, wherein the low frequency is 25-35 kHz, the working time is 30-50 minutes, the medium frequency is 65-90 kHz, the working time is 50-70 minutes, and the high frequency is 125-180 kHz, the working time is 70-90 minutes, and then drying at 120-140° C. for 1-1.5 hours to obtain the corrugated mica. Under the synergistic effect of the dispersant, the silane coupling agent and the alternately emitted ultrasonic waves, the surface of the corrugated mica prepared by the method has a corrugated shape, thereby increasing the specific surface area of ​​the mica and the contact area between the mica particles and the rubber molecules. As the contact area between corrugated mica and rubber molecules increases, the number of temporary structures formed by van der Waals forces increases. This structure is easy to decompose and easy to generate. In dynamic strain, the continuous decomposition and generation of this structure brings about hysteresis loss of the material. Secondly, the specific surface area of ​​corrugated mica increases, and the friction between mica particles also increases. Therefore, the prepared rubber material shows a larger tanδ, and the corrugated mica provides a better damping effect for the rubber material.

[0031] In order to better understand the above technical solution, the above technical solution will be described in detail below in conjunction with specific implementation methods.

[0032] Example 1

[0033] This embodiment provides a method for preparing a high-damping wide-temperature range rubber material, comprising the following steps:

[0034] S1. Add natural rubber and brominated butyl rubber into an internal mixer according to Table 1 and mix them at 130°C for 100s. After mixing, remove the rubber to obtain plasticized rubber. The removal temperature is 120°C.

[0035] S2, adding the plasticized rubber into an internal mixer and mixing at a temperature of 130° C. for 60 seconds, adding corrugated mica and 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline thereto and mixing for 60 seconds, then adding carbon black, clay, and cycloalkyl mineral oil N4010 and mixing for 120 seconds, then adding sulfur and 1,3-di-o-tolylguanidine and mixing for 40 seconds, unloading, cooling and setting aside;

[0036] S3. Adjust the temperature of the vulcanizer to 140°C and the working pressure to 8 MPa, preheat the mold for 1 hour, then load the material mixed in S2 into the mold, pressurize, and vulcanize to obtain high-damping wide-temperature range rubber.

[0037] The corrugated mica was prepared as follows:

[0038] The pH of pure water was adjusted to 7, and then BYK-190 and 3-aminopropyltrimethoxysilane were added thereto and dispersed evenly, and then flaky mica with a particle size of 200 mesh was added to prepare a colloidal suspension;

[0039] A combination of low frequency, medium frequency and high frequency ultrasonic waves is alternately emitted into the colloidal suspension, wherein the low frequency is 25 kHz and the working time is 30 minutes, the medium frequency is 65 kHz and the working time is 50 minutes, and the high frequency is 125 kHz and the working time is 70 minutes, and then dried at 120°C for 1.5 hours to obtain corrugated mica, the surface of which has a corrugated shape similar to that of the corrugation.

[0040] Table 1 Amount of each raw material used in Examples 1-3

[0041]

[0042] Example 2

[0043] This embodiment provides a method for preparing high-damping wide-temperature range rubber, comprising the following steps:

[0044] S1. Add natural rubber and brominated butyl rubber into an internal mixer according to Table 1 and mix them at a temperature of 110° C. for 120 seconds. After mixing, perform rubber removal to obtain plasticized rubber. The rubber removal temperature is 120° C.;

[0045] S2, adding the plasticized rubber into an internal mixer and mixing at a temperature of 110° C. for 50 seconds, adding corrugated mica and 3-hydroxybutyraldehyde-α-naphthylamine thereto and mixing for 50 seconds, then adding carbon black, talcum powder, and naphthyl mineral oil N4010 and mixing for 100 seconds, then adding sulfur and N-tert-butyl-2-benzothiazolesulfonamide and mixing for 20 seconds, unloading, cooling and standby;

[0046] S3. Adjust the temperature of the vulcanizer to 140°C and the working pressure to 8 MPa, preheat the mold for 1 hour, then load the material mixed in S2 into the mold, pressurize, and vulcanize to obtain high-damping wide-temperature range rubber.

[0047] The corrugated mica was prepared as follows:

[0048] The pH of pure water was adjusted to 7, and then sodium methylenebisnaphthalenesulfonate and (3-aminopropyl)triethoxysilane were added to the pure water and dispersed evenly, and then flaky mica with a particle size of 210 mesh was added to prepare a colloidal suspension;

[0049] A combination of low frequency, medium frequency and high frequency ultrasonic waves is alternately emitted into the colloidal suspension, wherein the low frequency is 30 kHz and the working time is 40 minutes, the medium frequency is 80 kHz and the working time is 60 minutes, and the high frequency is 130 kHz and the working time is 80 minutes, and then dried at 130°C for 1.2 hours to obtain corrugated mica, the surface of which has a corrugated shape similar to that of the corrugated mica.

[0050] Example 3

[0051] This embodiment provides a method for preparing high-damping wide-temperature range rubber, comprising the following steps:

[0052] S1. Add natural rubber and brominated butyl rubber into an internal mixer according to Table 1 and mix them at 120°C for 110s. After mixing, remove the rubber to obtain plasticized rubber. The removal temperature is 120°C.

[0053] S2, adding the plasticized rubber into an internal mixer and mixing at a temperature of 120° C. for 55 seconds, adding corrugated mica and 4,4-dihydroxybiphenyl thereto and mixing for 55 seconds, then adding carbon black, wollastonite powder, and naphthenic mineral oil N4010 and mixing for 110 seconds, then adding sulfur and N-oxydiethylene-2-benzothiazolesulfonamide and mixing for 30 seconds, unloading, cooling and standby;

[0054] S3. Adjust the temperature of the vulcanizer to 140°C and the working pressure to 8 MPa, preheat the mold for 1 hour, then load the material mixed in S2 into the mold, pressurize, and vulcanize to obtain high-damping wide-temperature range rubber.

[0055] The corrugated mica was prepared as follows:

[0056] The pH of pure water was adjusted to 7, and then BYK-190 and 3-aminopropyltrimethoxysilane were added to the pure water and dispersed evenly, and then flaky mica with a particle size of 220 mesh was added to prepare a colloidal suspension;

[0057] A combination of low frequency, medium frequency and high frequency ultrasonic waves is alternately emitted into the colloidal suspension, wherein the low frequency is 35 kHz, the working time is 50 minutes, the medium frequency is 90 kHz, the working time is 70 minutes, and the high frequency is 180 kHz, the working time is 90 minutes, and then the colloidal suspension is dried at 140°C for 1 hour to obtain corrugated mica, the surface of which has a corrugated shape similar to that of the corrugation.

[0058] Comparative Example 1

[0059] The difference between this comparative example and Example 1 is that the preparation method of the corrugated mica is different, which is as follows: the pH of pure water is adjusted to 7, and then flaky mica is added to the pure water to prepare a colloidal suspension; then a combination of low-frequency, medium-frequency, and high-frequency ultrasonic waves is alternately emitted into the colloidal suspension, and the rest is the same as Example 1 to obtain corrugated mica. The corrugated mica prepared by this process has less similar corrugated shapes on the surface.

[0060] Comparative Example 2

[0061] The difference between this comparative example and Example 1 is that the preparation method of the corrugated mica is different, which is as follows: the pH of pure water is adjusted to 7, and then BYK-190 and 3-aminopropyltrimethoxysilane are added to the pure water and dispersed evenly, and then flaky mica with a particle size of 200 mesh is added to prepare a colloidal suspension; the colloidal suspension is dried at 120° C. for 1.5 hours. The other conditions are the same as those in Example 1. The surface of the corrugated mica prepared by this process does not have a similar corrugated shape.

[0062] The high damping wide temperature range rubber prepared in Examples 1-3 and Comparative Examples 1-2 was tested for damping performance by a dynamic mechanical analyzer (DMA) using a platform excitation method. The temperature range was -80 to 80°C, the heating rate was 3°C / min, the frequency was 22Hz, and the loss factors at -10°C and 23°C in the test results were recorded in Table 2 (represented as tanδ -10 , tanδ 23 ), calculate the difference in loss factor △tanδ and the percentage change in loss factor. The calculation formula is as follows. The results are shown in Table 2.

[0063] △tanδ=tanδ -10 -tanδ 23 ;

[0064] Percentage = △tanδ / tanδ 23 ;

[0065] Table 2 Test results of rubber prepared in Examples 1-3 and Comparative Examples 1-2

[0066] <![CDATA[tanδ -10 ]]> <![CDATA[tanδ 23 ]]> △tanδ percentage Comparative Example 1 0.2784 0.1569 0.1215 77.44％ Comparative Example 2 0.2833 0.1462 0.1371 93.78％ Example 1 0.2378 0.1983 0.0395 19.92％ Example 2 0.2572 0.1975 0.0597 30.23％ Example 3 0.2451 0.1854 0.0597 32.20％

[0067] From the analysis of Table 2, it can be seen that the tanδ of the rubber materials prepared in Examples 1-3 23 They reached 0.1983, 0.1975, and 0.1854 respectively, which is similar to tanδ -10 Compared with the control examples 1 and 2, the percentage changes of the loss factors are 19.92%, 30.23%, and 32.20%, respectively. Therefore, the rubber materials prepared in Examples 1-3 have excellent damping performance and a wide damping temperature range. 23They are 0.1569 and 0.1462 respectively, and the percentage changes of loss factors are as high as 77.44% and 93.78% respectively. Therefore, the damping performance is poor and the damping temperature range is also narrow. This is because the high-damping wide-temperature range rubber of the present invention includes natural rubber, butyl rubber, corrugated mica, antioxidant, carbon black, inorganic filler, plasticizer, sulfur, and accelerator. The surface of the corrugated mica has a corrugated shape, which increases the specific surface area of ​​the mica and the contact area between the mica particles and the rubber molecules. As the contact area between the corrugated mica and the rubber molecules increases, the temporary structure formed by the van der Waals force increases. This structure is easy to decompose and easy to generate. In dynamic strain, the continuous decomposition and generation of this structure is the main factor causing hysteresis loss. Secondly, the specific surface area of ​​the corrugated mica increases, and the friction between the mica particles and the particles also increases. Therefore, the prepared rubber material shows a larger tanδ and has a better damping effect. In addition, the addition of sulfur and accelerators improves the vulcanization effect of the rubber, thereby ensuring that the damping temperature range of the rubber material of the present invention is relatively wide.

[0068] It should be noted that, in this article, relational terms such as first and second, etc. are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Moreover, the terms "include", "comprise" or any other variants thereof are intended to cover non-exclusive inclusion, so that a process, method, article or device including a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements inherent to such process, method, article or device. In the absence of further restrictions, the elements defined by the sentence "comprise a ..." do not exclude the existence of other identical elements in the process, method, article or device including the elements.

[0069] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit the same. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that the technical solutions described in the aforementioned embodiments may still be modified, or some of the technical features may be replaced by equivalents. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A high damping wide temperature range rubber, characterized in that: The composition comprises the following components in parts by weight:

2. The high damping wide temperature range rubber according to claim 1, characterized in that: The antioxidant is selected from amine antioxidants or phenolic antioxidants.

3. The high damping wide temperature range rubber according to claim 2, characterized in that: The amine antioxidant is selected from any one of ketoamine antioxidants, aldehydeamine antioxidants or diaromatic secondary amine antioxidants.

4. The high damping wide temperature range rubber according to claim 2, characterized in that: The phenolic antioxidant is selected from 4,4-dihydroxybiphenyl.

5. The high damping wide temperature range rubber according to claim 1, characterized in that: The inorganic filler is selected from any one of clay, talc, wollastonite, asbestos, silicon aluminum carbon black and sepiolite.

6. The high damping wide temperature range rubber according to claim 1, characterized in that: The plasticizer is selected from naphthenic mineral oils.

7. The high damping wide temperature range rubber according to claim 1, characterized in that: The accelerator is selected from any one of 1,3-di-o-tolylguanidine, N-tert-butyl-2-benzothiazole sulfenamide, and N-oxydiethylene-2-benzothiazole sulfenamide.

8. A method for preparing the high damping wide temperature range rubber according to any one of claims 1 to 7, characterized in that: The steps include: S1. Mixing natural rubber and butyl rubber at a temperature of 110° C. to 130° C. for 100 seconds to 120 seconds to obtain plasticized rubber; S2, mixing the plasticized rubber at a temperature of 110° C.-130° C. for 50-60 seconds, adding corrugated mica and an antioxidant thereto and mixing for 50-60 seconds, then adding carbon black, an inorganic filler and a plasticizer and mixing for 100 seconds-120 seconds, then adding sulfur and an accelerator and mixing for 20 seconds-40 seconds, and cooling for standby use; S3, the material after mixing in the above step 2) is loaded into a mold, pressurized, and vulcanized to obtain a high-damping wide-temperature range rubber.

9. The preparation method according to claim 8, characterized in that: The corrugated mica is prepared according to the following method: S1, adding a dispersant and a silane coupling agent to water and dispersing them evenly, then adding flaky mica with a particle size of 200-220 mesh to prepare a colloidal suspension; S2. Alternately emitting a combination of low-frequency, medium-frequency and high-frequency ultrasonic waves into the colloidal suspension, wherein the low frequency is 25-35 kHz, the working time is 30-50 minutes, the medium frequency is 65-90 kHz, the working time is 50-70 minutes, the high frequency is 125-180 kHz, the working time is 70-90 minutes, and then drying at 120-140° C. for 1-1.5 hours to obtain corrugated mica.

10. The preparation method according to claim 9, characterized in that: The silane coupling agent is 3-aminopropyltrimethoxysilane or (3-aminopropyl)triethoxysilane.

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