Modified brominated butyl rubber composite damping material and preparation method thereof

Abstract

The invention discloses a modified brominated butyl rubber composite damping material and a preparation method thereof, and relates to the field of rubber materials.The preparation method comprises the steps that a brominated butyl rubber composition and an aging agent are subjected to primary banburying, and cerium dioxide / brominated butyl rubber is obtained; heating and uniformly mixing the internally mixed cerium dioxide / brominated butyl rubber and epoxy resin composition at a constant temperature, and then carrying out secondary internal mixing to obtain a cerium dioxide / brominated butyl rubber / epoxy resin intermediate composite material; and carrying out open milling on the intermediate composite material, and then carrying out vulcanization molding to obtain the modified brominated butyl rubber composite damping material. The problems that the temperature range is narrow, the damping performance at the low temperature is poor, the aging phenomenon is prone to occurring in the using process, and the service life is affected are solved, the prepared composite material has the advantages of being stable at the high temperature, good in damping performance, good in ultraviolet stability and the like, and the provided preparation method is simple in process.

Description

Technical Field

[0001] The invention relates to the field of rubber materials, and in particular to a modified brominated butyl rubber composite damping material and a preparation method thereof. Background Art

[0002] Bromobutyl rubber is an isobutylene-isoprene copolymer elastomer containing active bromine. Since bromobutyl rubber has a basically saturated main chain of butyl rubber, it has many characteristics of butyl polymers, such as higher physical strength, better vibration reduction performance, low permeability, etc. However, due to the high density of side methyl groups on the molecular chain, the high internal friction of molecular motion, the low glass transition temperature, and the poor damping performance at room temperature and above, bromobutyl rubber has greatly limited its application.

[0003] Epoxy resin refers to a polymer compound containing two or more epoxy groups in the main chain. Its epoxy groups can react with amine and anhydride curing agents to form a three-dimensional cross-linked network structure, which has excellent physical and mechanical properties, electrical insulation properties, bonding properties and flexibility. Most cured epoxy resins have a glass transition temperature above 50°C and have good high-temperature damping properties, but their temperature range is narrow, their damping properties are poor at low temperatures, and they are prone to aging during use, which affects their service life.

[0004] The Chinese invention patent with announcement number CN 114213805 B discloses a high-toughness, high-damping graphene / styrene-butadiene rubber / epoxy resin composite material and its preparation method, but its preparation method is complicated, with many components, making it difficult to synthesize quickly and in large quantities, and the system does not involve research on aging properties, making it difficult to apply in practice. Summary of the invention

[0005] In view of this, the object of the present invention is to provide a modified brominated butyl rubber composite damping material and a preparation method thereof.

[0006] The objective of the present invention is achieved through the following technical solutions: <First aspect> The invention provides a modified brominated butyl rubber composite damping material, which is composed of 80 to 100 parts of brominated butyl rubber composition, 20 to 70 parts of epoxy resin composition and 2 to 20 parts of aging agent by mass.

[0007] As an embodiment, the aging agent is cerium dioxide.

[0008] In some embodiments, the aging agent is spherical cerium dioxide with a particle size not exceeding 20 nm.

[0009] As an embodiment, the brominated butyl rubber composition includes, by mass, 100 parts of brominated butyl rubber matrix, 11 to 23 parts of activator, 30 to 40 parts of reinforcing agent, 1 to 3 parts of vulcanizing agent and 2 to 6 parts of accelerator.

[0010] In some embodiments, the brominated butyl rubber composition includes, by weight: 100 parts of brominated butyl rubber base, 16 parts of activator, 30 parts of reinforcing agent, 1.5 parts of vulcanizing agent and 2.5 parts of accelerator.

[0011] In some embodiments, the activator is zinc dioxide and stearic acid, the reinforcing agent is carbon black, the vulcanizing agent is sulfur, and the accelerator is dimethyl disulfide and N-cyclohexyl-2-benzothiazole sulfonamide in a mass ratio of 1: (1.8-2.5).

[0012] As an embodiment, the epoxy resin composition is composed of a bisphenol A epoxy resin and an amine curing agent in a ratio of epoxy group to amine group of 1: (1-3).

[0013] In some embodiments, the epoxy resin composition is composed of a bisphenol A epoxy resin having an epoxy group to amine group ratio of 1:1 and an amine curing agent.

[0014] As an embodiment, the bisphenol A epoxy resin is one or more of E-42, E-51, and E-44.

[0015] As an embodiment, the amine curing agent is one or more of polyetheramine D-230 and polyamide 650.

[0016] In some embodiments, the amine curing agent is polyetheramine D-230.

[0017] <Second Aspect> The present invention provides a method for preparing a modified brominated butyl rubber composite damping material, comprising the following steps: S1, performing a first banburying of the brominated butyl rubber composition and an aging agent to obtain cerium dioxide / brominated butyl rubber; S2, heating and mixing the epoxy resin composition at a constant temperature, and then kneading it for a second time with cerium dioxide / bromobutyl rubber to obtain a cerium dioxide / bromobutyl rubber / epoxy resin intermediate composite material; S3, refining the intermediate composite material, and then vulcanizing and molding it to obtain the modified brominated butyl rubber composite damping material.

[0018] As an embodiment, the order of feeding materials in the first internal mixing is: brominated butyl rubber matrix, carbon black, zinc dioxide, cerium dioxide, stearic acid, sulfur, and accelerator.

[0019] As an embodiment, in step S1, the parameters of the first banburying are banburying at 60-70° C. for 10-20 min.

[0020] In some embodiments, in step S1, the first kneading is performed at 65° C. for 15 min.

[0021] As an embodiment, in step S2, the epoxy resin composition is stirred at 50-100° C. for 15-20 min to mix the system evenly.

[0022] In some embodiments, in step S2, the epoxy resin composition is stirred at 80° C. for 20 min to make the system uniformly mixed.

[0023] As an embodiment, in step S2, the parameters of the second banburying are banburying at 60-70° C. for 20-40 min.

[0024] In some embodiments, in step S2, the second kneading is performed at 65° C. for 30 min.

[0025] As an embodiment, the intermediate composite material is melted at 20-30° C. for 5-8 min.

[0026] In some embodiments, the intermediate composite material is smelted at room temperature for 6 minutes.

[0027] As an embodiment, the vulcanization molding parameters are 10-20 MPa, 130-150°C, and 10-20 min.

[0028] In some embodiments, the vulcanization molding parameters are 10 MPa, 150° C., and 15 min.

[0029] Compared with the prior art, the present invention has the following beneficial effects: The present invention provides a method for preparing a modified brominated butyl rubber composite damping material, wherein the butyl rubber composite material has good damping performance in a high temperature region by adding an epoxy resin composition, and the addition of cerium dioxide can optimize the damping performance and anti-aging performance of the modified epoxy resin, thereby ensuring the mechanical properties of the system under conditions of high temperature, ultraviolet, etc. Cerium dioxide has a special electronic layer structure, strong redox properties and ultraviolet absorption capacity, so adding cerium dioxide to a polymer material can improve the product's resistance to thermal oxygen aging and ultraviolet aging.

[0030] The main purpose of the cerium dioxide in the modified brominated butyl rubber composite damping material provided by the present invention is to optimize the mechanical properties and the thermal oxidation aging and ultraviolet aging resistance of the butyl rubber / epoxy resin composite material. Under the aging conditions of 80-120°C and 48h, the tensile strength retention rate and the elongation at break of the composite material gradually increase with the addition of cerium dioxide. Under 48h of ultraviolet irradiation, the tensile strength retention rate, tensile strength retention rate and elongation at break of the composite material increase with the addition of cerium dioxide. Therefore, cerium dioxide improves the anti-aging performance of the butyl rubber / epoxy resin composite material system.

[0031] The cerium dioxide in the modified brominated butyl rubber composite damping material provided by the present invention not only has the function of an antioxidant, but also promotes the mechanical properties of the butyl rubber / epoxy resin composite material system, ensures that the high-temperature damping does not fluctuate too much, improves the low-temperature damping performance, and broadens the damping temperature range. In order to improve the damping performance and range of rubber, it can be blended and modified.

[0032] The composite material prepared by the method provided by the present invention has the advantages of high temperature stability, good damping performance, good ultraviolet stability, etc., and the proposed preparation method has a simple process. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] Other features, objects and advantages of the present invention will become more apparent from the detailed description of non-limiting embodiments made with reference to the following drawings: Figure 1 The cross-sectional scanning electron microscope and cerium element distribution diagram of Example 1 of the present invention; Figure 2 The mechanical properties of various embodiments and comparative examples of the present invention; Figure 3 The damping performance of each embodiment of the present invention and the comparative example; Figure 4 The thermal oxidation aging mechanical properties of various embodiments and comparative examples of the present invention; Figure 5 The UV aging mechanical properties of various embodiments and comparative examples of the present invention are shown in FIG. DETAILED DESCRIPTION

[0034] The present invention is described in detail below in conjunction with embodiments. The following embodiments will help those skilled in the art to further understand the present invention, but are not intended to limit the present invention in any form. It should be noted that, for those of ordinary skill in the art, some adjustments and improvements can also be made without departing from the concept of the present invention. These all belong to the protection scope of the present invention.

[0035] This specific embodiment provides a method for preparing a modified brominated butyl rubber composite damping material (abbreviated as IIR).

[0036] Example 1 This embodiment provides a method for preparing a modified brominated butyl rubber composite damping material.

[0037] The raw materials are: 100 parts of brominated butyl rubber composition, 70 parts of epoxy resin composition, and 8 parts of cerium dioxide, wherein: The brominated butyl rubber composition is: 100 parts of brominated butyl rubber matrix, 14.5 parts of zinc dioxide, 1.5 parts of stearic acid, 30 parts of carbon black, 1.5 parts of sulfur, and accelerators (1 part of bisthiocarbonyl dimethylamine disulfide (TMTD) and 1.5 parts of N-cyclohexyl-2-benzothiazole sulfenamide (CZ)); The epoxy resin composition is composed of bisphenol A epoxy resin E-44 and polyetheramine D-230 in a molar ratio of epoxy group to amine group of 1:1; Cerium dioxide is spherical and has a particle size of 8-10nm.

[0038] A method for preparing a modified brominated butyl rubber composite damping material, comprising the following steps: S1. Mixing the brominated butyl rubber composition, adding the brominated butyl rubber matrix, carbon black, zinc dioxide, cerium dioxide, stearic acid, sulfur and accelerator into a mixing box in this order, mixing at 65°C for 15 minutes, and taking out the modified brominated butyl rubber.

[0039] S2, stirring the epoxy resin composition in a water bath at 80° C. for 20 min to mix evenly, then adding the epoxy resin composition and the modified brominated butyl rubber into an internal mixer, mixing at 65° C. for 30 min, and taking out to obtain an intermediate material; S3. The intermediate material of step S2 is milled on an open mill at room temperature for three times, each time for 2 min, and vulcanized in a flat vulcanizer under the conditions of 10 MPa, 150°C, and 15 min to obtain a modified brominated butyl rubber composite damping material.

[0040] Example 2 This embodiment provides a method for preparing a modified brominated butyl rubber composite damping material.

[0041] The raw materials are basically the same as those in Example 1, except that: The epoxy resin composition is used in an amount of 50 parts; The epoxy resin composition is replaced by: bisphenol A type epoxy resin E-42 and polyetheramine D-230 (curing agent) in a ratio of epoxy group: amine group = 1:1.

[0042] Example 3 This embodiment provides a method for preparing a modified brominated butyl rubber composite damping material.

[0043] The raw materials are basically the same as those in Example 1, except that: The amount of cerium dioxide is 6 parts; The epoxy resin composition is replaced by: bisphenol A epoxy resin E-51 and polyetheramine D-230 in a ratio of epoxy group to amino group = 1:1.

[0044] Comparative Example 1 This comparative example is basically the same as Example 1, except that: The raw materials do not contain epoxy resin composition.

[0045] In the steps, step S2 is omitted; the modified brominated butyl rubber produced in step S1 is used in the open refining in step S3; and a modified brominated butyl rubber composite damping material free of epoxy resin is obtained.

[0046] Comparative Example 2 This comparative example is basically the same as Example 2, except that: The raw materials do not contain cerium dioxide.

[0047] In step S1, cerium dioxide is omitted when feeding, so as to obtain a modified brominated butyl rubber composite damping material free of cerium dioxide.

[0048] Performance testing and analysis: The composite damping materials prepared in the embodiments and comparative examples are tested and analyzed below, and the properties tested include: cross-sectional morphology, damping temperature, thermal oxygen aging, ultraviolet aging, tensile performance test, and dynamic mechanical properties.

[0049] The sample size is prepared according to the national standard GB / T 528-2009.

[0050] Damping temperature properties: The damping performance was tested using a dynamic mechanical analyzer (DMA) with a temperature scan of -90 ℃-60 ℃, a frequency of 1 Hz, and an amplitude of 10 um.

[0051] Thermal oxidative aging: Use a forced air drying oven and age at 80 °C for 48 h in accordance with GB / T 3512-2014 (Hot air accelerated aging and heat resistance test for vulcanized rubber or thermoplastic rubber).

[0052] UV aging: Using a UV aging test chamber, according to GB / T16585-1996 (Test method for artificial weathering of vulcanized rubber (fluorescent UV lamp)) at a UV radiation intensity of 0.51 W / m 2 , aging for 48 h at a temperature of 50 °C and a humidity of 100%.

[0053] Mechanical properties test: The mechanical properties retention rate was tested using a universal tensile testing machine at a tensile rate of 200 mm / min.

[0054] like Figure 1 As shown, using a scanning electron microscope to perform EDS scanning on the cross section of the composite damping material, it can be seen that the cerium element is evenly dispersed in the image, indicating that the cerium dioxide particles are evenly distributed.

[0055] Figure 2 The mechanical properties test results of the embodiments and comparative examples are shown in FIG. 1 . The three embodiments containing cerium dioxide and epoxy / amine compositions show higher tensile strength and elongation at break.

[0056] Figure 3 The damping performance of each embodiment and the comparative example is shown. It can be seen that each embodiment has a good damping effect, with a peak appearing near 0° C. and near 70° C., and the peak values ​​of the loss factors are relatively high.

[0057] In Comparative Example 1, when no epoxy / amine composition is added, the loss factor has only a peak value at a relatively low temperature (-30~10 ℃), while in each embodiment, the damping operating temperature range (tanδ>0.3) at a relatively low temperature is significantly broadened, and a damping operating temperature range at a relatively high temperature (50~70 ℃) is also added.

[0058] In Comparative Example 2, when no cerium dioxide is added, the loss factor presents two peaks, but the damping operating temperature range is relatively narrow compared to that in each embodiment.

[0059] Figure 4 The test results of the mechanical property retention rate after 48 h of thermal oxidation aging of each embodiment and comparative example show that the retention rate of tensile strength and elongation at break after aging increases with the addition of cerium oxide, and even in Example 1, the retention rate of the two mechanical properties is increased to more than 100%.

[0060] Figure 5 The test results of the mechanical property retention rate after 48 h of UV aging for each embodiment and comparative example show that the retention rate of tensile strength and elongation at break after aging increases significantly with the addition of cerium oxide, and the retention rates of the two mechanical properties in several embodiments are increased to more than 100%.

[0061] Compared with the comparative example, each embodiment has good damping performance at both high and low temperatures. The addition of the epoxy / amine composition enables the rubber system to have good damping performance at high temperatures. The addition of cerium dioxide not only improves the thermal oxidation aging and ultraviolet aging resistance of the composite damping material, but also has a certain improvement effect on the loss factor, thereby improving the low-temperature damping loss factor of the system.

[0062] The above describes the specific embodiments of the present invention. It should be understood that the present invention is not limited to the above specific embodiments, and those skilled in the art may make various modifications or variations within the scope of the claims, which do not affect the essence of the present invention.

Claims

1. A modified brominated butyl rubber composite damping material, characterized in that: The invention is composed of 80 to 100 parts of brominated butyl rubber composition, 20 to 70 parts of epoxy resin composition and 2 to 20 parts of aging agent in parts by mass, wherein the brominated butyl rubber composition comprises: 100 parts of brominated butyl rubber matrix, 11 to 23 parts of activator, 30 to 40 parts of reinforcing agent, 1 to 3 parts of vulcanizing agent and 2 to 6 parts of accelerator, the aging agent is cerium dioxide, and the epoxy resin composition is composed of a bisphenol A type epoxy resin and an amine curing agent in a ratio of epoxy group to amine group of 1: (1 to 3).

2. The modified brominated butyl rubber composite damping material according to claim 1, characterized in that: The aging agent is spherical cerium dioxide with a particle size not exceeding 20 nm.

3. The modified brominated butyl rubber composite damping material according to claim 1, characterized in that: The bisphenol A type epoxy resin is one or more of E-42, E-51 and E-44; the amine curing agent is one or more of polyetheramine D-230 and polyamide 650.

4. The modified brominated butyl rubber composite damping material according to claim 1, characterized in that: The activator is zinc dioxide and stearic acid, the reinforcing agent is carbon black, the vulcanizing agent is sulfur, and the accelerator is dithiocarbonyl dimethylamine disulfide and N-cyclohexyl-2-benzothiazole sulfonamide.

5. A method for preparing the modified brominated butyl rubber composite damping material according to any one of claims 1 to 4, characterized in that: The following steps are involved: S1, performing a first banburying of the brominated butyl rubber composition and an aging agent to obtain cerium dioxide / brominated butyl rubber; S2, heating and mixing the epoxy resin composition at a constant temperature, and then kneading it for a second time with cerium dioxide / bromobutyl rubber to obtain a cerium dioxide / bromobutyl rubber / epoxy resin intermediate composite material; S3, refining the intermediate composite material, and then vulcanizing and molding it to obtain the modified brominated butyl rubber composite damping material.

6. The method for preparing the modified brominated butyl rubber composite damping material according to claim 5, characterized in that: In step S1, the parameters of the first banburying are banburying at 60-70° C. for 10-20 min.

7. The method for preparing the modified brominated butyl rubber composite damping material according to claim 5, characterized in that: In step S2, the heating and mixing at a constant temperature is stirring at 50-100°C for 15-20 min.

8. The method for preparing the modified brominated butyl rubber composite damping material according to claim 5, characterized in that: In step S2, the parameters of the second banburying are banburying at 60-70° C. for 20-40 min.

9. The method for preparing the modified brominated butyl rubber composite damping material according to claim 5, characterized in that: In step S3, the intermediate composite material is smelted at 20-30°C for 5-8 minutes.

10. The method for preparing the modified brominated butyl rubber composite damping material according to claim 5, characterized in that: The vulcanization molding parameters are 10-20 MPa, 130-150°C, and 10-20 min.

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