Soundproofing rubber composite material, method for its production and use

Abstract

The application provides a sound insulation rubber composite material and a preparation method and application thereof, and belongs to the technical field of rubber, and the preparation method comprises the following steps: butyl rubber and ethylene-propylene-diene rubber are added into a banbury mixer for plasticizing, then carbon black, a metal oxide compound, a modifying additive, a vulcanization activator and an antioxidant are added for mixing, vulcanization accelerators and vulcanization agents are further added for mixing, and then glue is discharged to obtain a rubber compound; the rubber compound is placed in an open mill for thin mixing and storage to obtain a mixed rubber; the mixed rubber is vulcanized on a flat vulcanizing machine to obtain the sound insulation rubber composite material; wherein the metal oxide compound is prepared by calcining and crushing cerium dioxide, titanium dioxide and silicon dioxide; and the modifying additive is prepared by using a functional polymer and modified hollow glass microbeads; the sound insulation rubber composite material has good sound insulation performance and durability, and the preparation process is simple.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of rubber, and particularly relates to a sound insulation rubber synthetic material and a preparation method and application thereof. BACKGROUND

[0002] Rubber material, as an important industrial raw material, has been widely used in many fields due to its good elasticity, wear resistance and anti-aging performance. Natural rubber is derived from rubber tree latex, while synthetic rubber is made by chemical methods. Both of them have excellent physical and mechanical properties and are suitable for manufacturing tires, seals and other products. With the development of technology and changes in market demand, rubber materials with improved specific functions have emerged, one of which is sound insulation rubber material. This special rubber not only inherits the advantages of traditional rubber, but also optimizes its molecular structure to enhance the sound insulation effect, becoming an ideal sound insulation material in fields such as building decoration and automobile manufacturing. The main advantages of sound insulation rubber material include good sound insulation effect, flexibility and easy processing, which can effectively reduce external noise interference and is widely used in sound insulation treatment of building walls, floors and ceilings, as well as automobile interior sound insulation, improving people's quality of life.

[0003] However, the shortcomings of existing sound insulation rubber materials cannot be ignored. For example, in order to achieve good sound insulation effect, sound insulation rubber often needs a certain thickness, which increases the overall structure weight, which is not suitable for automobile manufacturing and other application scenarios; the performance of sound insulation rubber may decline in extreme environments such as high temperature or low temperature, affecting its service life and sound insulation effect; some sound insulation rubber may contain harmful chemicals to the human body or the environment, posing environmental and safety risks during production, use and disposal; in addition, due to the complex production process of sound insulation rubber and the high price of raw materials, the overall cost is high, increasing the use cost.

[0004] In order to overcome the above-mentioned shortcomings of sound insulation rubber material, currently, other lightweight high-strength materials or nanomaterials can be added to combine with rubber to reduce the weight of sound insulation rubber material; specific anti-aging agents, heat stabilizers and other additives can be added to improve the weather resistance of sound insulation rubber, solving the problem of performance decline in extreme environments; green and environmentally friendly sound insulation rubber is developed, replacing traditional petroleum-based raw materials with green and non-toxic raw materials, thereby reducing the use of harmful chemicals. However, these methods increase the difficulty of production process and raw material cost, making it difficult to achieve large-scale commercialization. Therefore, it is urgent to develop a preparation method of sound insulation rubber synthetic material, which not only has good sound insulation effect and durability, but also has simple process and is suitable for popularization and application. SUMMARY

[0005] The present application aims to provide a soundproof rubber composite material, which further improves the soundproof performance and durability of the rubber material by adding a metal oxide compound and a specific modifying agent into the rubber raw material.

[0006] To achieve the above object, the present application provides the following technical solutions.

[0007] The present application provides a soundproof rubber composite material, which comprises the following raw materials in parts by weight:

[0008] 60-80 parts by weight of butyl rubber, 20-40 parts by weight of ethylene-propylene-diene rubber, 20-30 parts by weight of carbon black, 3-7 parts by weight of a metal oxide compound, 7-13 parts by weight of a modifying agent, 10-15 parts by weight of a vulcanization activator, 2-4 parts by weight of a vulcanization accelerator, 1-3 parts by weight of a vulcanizing agent, and 2-5 parts by weight of an antioxidant.

[0009] Preferably, the vulcanization activator is a mixture of stearic acid and zinc oxide in a weight ratio of 3-5:3.

[0010] Preferably, the vulcanization accelerator is one or a mixture of two or more of N-tert-butyl-2-benzothiazole sulfenamide, N-cyclohexyl-2-benzothiazole sulfenamide, diphenyl disulfide, zinc dimethyl dithiocarbamate, and zinc diethyl dithiocarbamate.

[0011] Preferably, the vulcanization accelerator is a mixture of N-tert-butyl-2-benzothiazole sulfenamide and zinc diethyl dithiocarbamate in a weight ratio of 1:1-3.

[0012] Preferably, the vulcanizing agent is sulfur.

[0013] Preferably, the antioxidant is one or a mixture of two or more of antioxidant RD, antioxidant MB, antioxidant 4010, antioxidant D, and antioxidant BLE.

[0014] Preferably, the antioxidant is a mixture of antioxidant RD and antioxidant MB in a weight ratio of 3:1-3.

[0015] Preferably, the preparation method of the metal oxide compound comprises the following steps:

[0016] Mixing 1-3 parts by weight of cerium dioxide, 2-4 parts by weight of titanium dioxide, and 8-12 parts by weight of silicon dioxide uniformly, then pressing into a cylindrical sample, calcining the cylindrical sample, crushing, and sieving the crushed sample to obtain the metal oxide compound.

[0017] The metal oxide compound prepared by the method can effectively improve the sound insulation performance of the sound insulation rubber composite material. The metal oxide compound is composed of cerium dioxide, titanium dioxide and silicon dioxide, and each component has unique physical and chemical properties and plays an important role in enhancing the overall performance of the rubber material.

[0018] Firstly, the silicon dioxide provides necessary physical support as a matrix material, ensuring the structural integrity of the composite material. Its porosity promotes multiple reflections and scattering of sound waves on its internal surface, increasing the path length of sound waves in the material, thereby improving the sound absorption efficiency. In addition, the high stability and durability of silicon dioxide help maintain the performance stability of the composite material during long-term use.

[0019] Secondly, cerium dioxide can maintain the structural stability of the material at high temperatures due to its good thermal and chemical stability. More importantly, its catalytic activity can promote the conversion of sound wave energy into heat energy, and part of the sound energy is absorbed and converted into other forms of energy such as heat energy, further enhancing the sound absorption performance of the material. At the same time, cerium dioxide can also capture free radicals during combustion, inhibit the occurrence of chain reactions, and delay or prevent the spread of flames, thereby improving the flame retardant performance of the material.

[0020] Thirdly, titanium dioxide not only has excellent chemical stability and photocatalytic activity, but also can effectively increase the reflection path of sound waves in the material due to its special crystal structure. This increases the propagation distance of sound waves in the material, enhances the absorption and scattering efficiency of sound waves, and improves the overall sound insulation effect. In addition, the addition of titanium dioxide also helps to promote the formation of carbon layer, which can play a role in heat and oxygen isolation during combustion, thereby further improving the flame retardant performance of the material.

[0021] The metal oxide compound of the present application is subjected to a calcination and rapid cooling and crushing process in sequence, which can form a loose pore structure, which is beneficial to the absorption and scattering of sound waves, and also provides a certain degree of elasticity for the material, which helps to attenuate vibration.

[0022] Further, the preparation method of the metal oxide compound comprises the following steps:

[0023] 1-3 parts by weight of cerium dioxide, 2-4 parts by weight of titanium dioxide and 8-12 parts by weight of silicon dioxide are mixed uniformly, then pressed into a cylindrical sample under the condition of 0.1-0.5 MPa, the diameter of the cylindrical sample is 0.5-1 cm, the height is 1-2 cm, then the cylindrical sample is calcined at 1100-1400℃ for 100-200 min, after the end, the cylindrical sample is crushed under the condition of liquid nitrogen at-160~-140℃ for 30-40 min, and then sieved through a 120-180 mesh screen to obtain the metal oxide compound.

[0024] Preferably, the preparation method of the modified additive comprises the following steps:

[0025] 5-10 parts by weight of hollow glass microspheres are added to 60-80 parts by weight of sodium hydroxide aqueous solution, stirred, filtered, washed with water, and dried to obtain activated hollow glass microspheres; 4-6 parts by weight of N-(β-aminoethyl)-γ-aminopropyl methyl dimethoxysilane is uniformly mixed with 40-50 parts by weight of ethanol aqueous solution, then 2-5 parts by weight of activated hollow glass microspheres is added, heated and stirred, filtered, and dried to obtain modified hollow glass microspheres;

[0026] 1-4 parts by weight of phenylphosphonic dichloride and 5-10 parts by weight of N-(4-aminophenyl) maleimide are added to 70-90 parts by weight of dimethyl sulfoxide, stirred, then 1-2 parts by weight of potassium hydroxide is added, heated and reacted, reduced pressure distillation, and dried to obtain a maleimide-containing intermediate; 3-5 parts by weight of the maleimide-containing intermediate, 1-2 parts by weight of maleic anhydride, and 40-60 parts by weight of dimethylbenzene are uniformly mixed, heated under nitrogen atmosphere, then 0.04-0.06 parts by weight of azobisisobutyronitrile is added to react, reduced pressure distillation, and dried to obtain a functional polymer;

[0027] 2-4 parts by weight of the functional polymer is added to 40-60 parts by weight of dimethyl sulfoxide, stirred, then 1-2 parts by weight of the modified hollow glass microspheres is added, heated and stirred, filtered, and dried to obtain the modified additive.

[0028] The modified additive is also added to synergize with other components, further improving the sound insulation performance and aging resistance of the sound insulation rubber synthetic material. In the preparation process of the modified additive, the activated hollow glass microspheres are surface treated in a sodium hydroxide solution, which increases the active sites on the surface of the microspheres and improves the interfacial compatibility and bonding strength between the microspheres and other materials. The activated hollow glass microspheres not only retain the original dense shell and hollow internal structure, but also enhance the ability of sound waves to reflect inside due to the change in surface properties, increase the sound wave propagation path length, and thus consume more sound wave energy, effectively improving the sound insulation effect. In addition, the dispersion of these microspheres in the rubber matrix can form a vibration loss mechanism at the micro level, further enhancing the sound insulation performance of the damping silicone rubber.

[0029] Further, the grafting reaction of N-(β-aminoethyl)-γ-aminopropyl methyl dimethoxysilane and activated hollow glass microspheres makes the silane molecules firmly attached to the surface of the microspheres, which not only enhances the reactivity between the microspheres and the subsequent polymer, but also endows the microspheres with additional functional properties, such as improved dispersibility and stability. The modified hollow glass microspheres can be uniformly distributed in the rubber matrix, avoiding the occurrence of agglomeration, and ensuring that each microsphere can play the best sound insulation and reinforcing role.

[0030] The intermediate generated by the substitution reaction between phenyl phosphinic dichloride and N-(4-aminophenyl) maleimide has a phosphorus-containing group, which endows the modified additive with excellent flame retardant performance. The functional polymer introduces maleic anhydride through copolymerization, which not only enhances the mechanical properties of the material, but also helps to capture free radicals during combustion due to its special chemical structure, inhibits flame spread, and improves the overall flame retardant grade. The combination of the functional polymer and the modified hollow glass microspheres forms a modified additive with a high synergistic effect. This additive not only significantly improves the sound insulation effect when added to the rubber matrix, but also further enhances the flame retardant performance due to the presence of the phosphorus-containing group. At the same time, due to the good dispersibility and stability brought by silane grafting, the material's aging resistance is improved.

[0031] Further, the preparation method of the modified additive comprises the following steps:

[0032] 5-10 parts by weight of hollow glass microspheres are added to 60-80 parts by weight of 2-5 wt% sodium hydroxide aqueous solution, stirred at room temperature and 400-600 rpm for 20-30 min, filtered, washed with water until neutral, and dried to obtain activated hollow glass microspheres; 4-6 parts by weight of N-(β-aminoethyl)-γ-aminopropyl methyl dimethoxysilane is uniformly mixed with 40-50 parts by weight of 60-70 wt% ethanol aqueous solution, then 2-5 parts by weight of activated hollow glass microspheres is added, stirred at 70-80℃ and 100-300 rpm for 5-10 h, filtered, and dried to obtain modified hollow glass microspheres;

[0033] 1-4 parts by weight of phenylphosphonic dichloride, 5-10 parts by weight of N-(4-aminophenyl)maleimide are added into 70-90 parts by weight of dimethyl sulfoxide, stirred at room temperature at 400-600 rpm for 7-15 min, then 1-2 parts by weight of potassium hydroxide is added, heated to 55-70 DEG C and reacted for 7-12 h, dimethyl sulfoxide is removed by distillation under reduced pressure, dried to obtain a maleimide-containing intermediate; 3-5 parts by weight of the maleimide-containing intermediate, 1-2 parts by weight of maleic anhydride and 40-60 parts by weight of xylene are uniformly mixed, heated to 90-95 DEG C under nitrogen atmosphere, then 0.04-0.06 parts by weight of azobisisobutyronitrile is added and reacted for 3-5 h, xylene is removed by distillation under reduced pressure, dried to obtain the functional polymer;

[0034] 2-4 parts by weight of the functional polymer are added into 40-60 parts by weight of dimethyl sulfoxide, stirred at room temperature at 400-600 rpm for 10-20 min, then 1-2 parts by weight of the modified hollow glass beads are added, stirred at 65-75 DEG C at 100-300 rpm for 5-8 h, filtered and dried to obtain the modified auxiliary agent.

[0035] The application further provides a preparation method of the sound insulation rubber synthetic material.

[0036] The butyl rubber and the ethylene-propylene-diene rubber are added into a mixing mill according to the raw material formula, plasticated for 1-3 min, then the carbon black, the metal oxide compound, the modified auxiliary agent, the vulcanization activator and the antioxidant are mixed for 2-5 min, then the vulcanization accelerator and the vulcanizing agent are continuously mixed for 2-5 min, and the rubber compound is obtained; the rubber compound is placed on an open mill and thin passed for 3-5 times, and then stored for 20-25 h to obtain the mixed rubber; the mixed rubber is vulcanized on a flat vulcanizing machine for 20-40 min to obtain the sound insulation rubber synthetic material.

[0037] Preferably, the temperature of the mixing mill is 65-75 DEG C, and the rotating speed is 70-90 rpm.

[0038] Preferably, the roller distance of the open mill is 0.5-1.0 mm, and the temperature is 55-65 DEG C.

[0039] Preferably, the temperature of the flat vulcanizing machine is 150-170 DEG C, and the pressure is 8-12 MPa.

[0040] The application further provides application of the sound insulation rubber synthetic material in preparation of building materials and automobile materials.

[0041] Compared with the prior art, the application has the following advantages and beneficial effects:

[0042] 1. The application provides a sound insulation rubber composite material and a preparation method thereof, which comprises the following steps: adding a metal oxide compound and a specific modified additive into a raw material formula, and cooperating with butyl rubber, ethylene-propylene-diene rubber and carbon black, wherein the metal oxide compound is prepared by calcining and crushing cerium dioxide, titanium dioxide and silicon dioxide, and the modified additive is prepared by a functional polymer and modified hollow glass microspheres, so that the sound insulation performance and durability of the rubber material are further improved.

[0043] 2. The metal oxide compound prepared in the application can effectively improve the sound insulation performance of the sound insulation rubber composite material, wherein the silicon dioxide provides necessary physical support as a matrix material, ensures the structural integrity of the composite material, and its porosity promotes multiple reflection and scattering of sound waves on its internal surface, increases the propagation path length of sound waves in the material, the catalytic activity of the cerium dioxide can promote the conversion of sound wave energy into heat energy, part of the sound energy is absorbed and converted into other forms of energy such as heat energy, further enhancing the sound absorption performance of the material, and the special crystal structure of the titanium dioxide can effectively increase the reflection path of sound waves in the material, which increases the propagation distance of sound waves in the material, enhances the absorption and scattering efficiency of sound waves, and improves the overall sound insulation effect.

[0044] 3. The application also adds a modified additive to synergize with other components, further improving the sound insulation performance and aging resistance of the sound insulation rubber composite material, wherein the modified additive uses hollow glass microspheres with surface activation and silane grafting to enhance sound wave reflection and energy dissipation, and the phosphorus-containing groups in the functional polymer provide excellent flame retardancy, and the silane improves dispersibility and interfacial bonding force. The synergistic effect of these components not only prolongs the sound wave propagation path to improve the sound insulation effect, but also enhances the aging resistance of the material, ensuring long-term use stability and high-efficiency sound insulation. DETAILED DESCRIPTION

[0045] The technical solutions in the embodiments of the application will be described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the application, not all. Based on the embodiments in the application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of the application.

[0046] Butyl rubber, brand: 268, specific gravity: 0.92, Mooney viscosity: 51MU (ML1+8, 125℃), unsaturation: 1.7mol%, manufacturer: Exxon Mobil Chemical Company, USA.

[0047] Ethylene-propylene-diene rubber, brand: 4045M, Mooney viscosity: 45MU (ML1+4, 125℃), ethylene content: 44.5wt%, manufacturer: Japan Mitsui Chemical Co., Ltd.

[0048] Carbon black, brand: N550, manufacturer: Jineng Technology Co., Ltd.

[0049] Hollow glass microbeads, model: HL60S, particle size D50: 35μm, manufacturer: Zhengzhou Saintlight Hollow Microbead New Material Co., Ltd.

[0050] Example 1

[0051] The present embodiment provides a sound insulation rubber synthetic material, which is composed of the following raw materials in parts by weight:

[0052] 70 parts by weight of butyl rubber, 30 parts by weight of ethylene-propylene-diene rubber, 25 parts by weight of carbon black, 5 parts by weight of metal oxide composite, 10 parts by weight of modified auxiliary agent, 12 parts by weight of vulcanization activator, 3 parts by weight of vulcanization accelerator, 2 parts by weight of vulcanizing agent, and 3.5 parts by weight of antioxidant.

[0053] The vulcanization activator is a mixture of stearic acid and zinc oxide in a weight ratio of 4:3;

[0054] The vulcanization accelerator is a mixture of N-tert-butyl-2-benzothiazole sulfenamide and zinc diethyldithiocarbamate in a weight ratio of 1:2;

[0055] The vulcanizing agent is sulfur;

[0056] The antioxidant is a mixture of antioxidant RD and antioxidant MB in a weight ratio of 3:2.

[0057] The preparation method of the metal oxide composite comprises the following steps:

[0058] Mix 2 parts by weight of cerium dioxide, 3 parts by weight of titanium dioxide, and 10 parts by weight of silicon dioxide uniformly, then press into a cylindrical sample under the condition of 0.2MPa, the diameter of the cylindrical sample is 1cm, and the height is 1.5cm, then calcine the cylindrical sample under the condition of 1250℃ for 150min, after the end, crush the cylindrical sample under the condition of liquid nitrogen of-150℃ for 35min, then pass through a 150-mesh sieve after crushing, to obtain the metal oxide composite.

[0059] The preparation method of the modified auxiliary agent comprises the following steps:

[0060] 8 parts by weight of hollow glass microspheres were added to 70 parts by weight of a 3 wt% sodium hydroxide aqueous solution, stirred at room temperature and 500 rpm for 25 min, filtered, washed with water until neutral, and dried to obtain activated hollow glass microspheres; 5 parts by weight of N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane was uniformly mixed with 45 parts by weight of a 65 wt% ethanol aqueous solution, then 3 parts by weight of the activated hollow glass microspheres was added, stirred at 75℃ and 200 rpm for 8 h, filtered, and dried to obtain modified hollow glass microspheres;

[0061] 2.5 parts by weight of phenylphosphinic dichloride and 7 parts by weight of N-(4-aminophenyl)maleimide were added to 80 parts by weight of dimethyl sulfoxide, stirred at room temperature and 500 rpm for 10 min, then 1.5 parts by weight of potassium hydroxide was added, heated to 60℃ and reacted for 10 h, dimethyl sulfoxide was removed by distillation under reduced pressure, and dried to obtain a maleimide-containing intermediate; 4 parts by weight of the maleimide-containing intermediate, 1.5 parts by weight of maleic anhydride, and 50 parts by weight of dimethylbenzene were uniformly mixed, heated to 92℃ under a nitrogen atmosphere, then 0.05 parts by weight of azobisisobutyronitrile was added and reacted for 4 h, dimethylbenzene was removed by distillation under reduced pressure, and dried to obtain a functional polymer;

[0062] 3.2 parts by weight of the functional polymer was added to 50 parts by weight of dimethyl sulfoxide, stirred at room temperature and 500 rpm for 15 min, then 1.6 parts by weight of the modified hollow glass microspheres was added, stirred at 70℃ and 200 rpm for 6 h, filtered, and dried to obtain a modified additive.

[0063] The embodiment provides a preparation method of a sound insulation rubber synthetic material, and the method comprises the following steps:

[0064] According to a raw material formula, butyl rubber and ethylene-propylene-diene rubber are added into a banbury mixer for plasticizing for 2 min, then carbon black, a metal oxide compound, a modified additive, a vulcanization activator, and an antioxidant are mixed for 3 min, then a vulcanization accelerator and a vulcanizing agent are continuously mixed for 3 min, and then glue is discharged to obtain a rubber compound; the rubber compound is placed on an open mill for thin passing 4 times, and then is placed for 24 h to obtain a mixed rubber; and the mixed rubber is placed on a flat vulcanizing machine for vulcanization for 30 min to obtain the sound insulation rubber synthetic material. The temperature of the banbury mixer is 70℃, and the rotating speed is 80 rpm; the roll distance of the open mill is 1.0 mm, and the temperature is 60℃; and the temperature of the flat vulcanizing machine is 160℃, and the pressure is 10 MPa.

[0065] Embodiment 2

[0066] The embodiment provides a sound insulation rubber synthetic material, and the material comprises the following raw materials in parts by weight:

[0067] 60 parts by weight of butyl rubber, 20 parts by weight of ethylene-propylene-diene rubber, 20 parts by weight of carbon black, 3 parts by weight of metal oxide compound, 7 parts by weight of modification aid, 10 parts by weight of vulcanization activator, 2 parts by weight of vulcanization accelerator, 1 part by weight of vulcanizing agent, and 2 parts by weight of antioxidant. The vulcanization activator is a mixture of stearic acid and zinc oxide in a weight ratio of 3:3; the vulcanization accelerator is a mixture of N-tert-butyl-2-benzothiazole sulfenamide and zinc diethyl dithiocarbamate in a weight ratio of 1:1; the vulcanizing agent is sulfur; and the antioxidant is a mixture of antioxidant RD and antioxidant MB in a weight ratio of 3:1.

[0068] The metal oxide compound is prepared by the same method as in Embodiment 1.

[0069] The modification aid is prepared by the same method as in Embodiment 1.

[0070] The present embodiment provides a preparation method of soundproof rubber synthetic material, comprising the following steps:

[0071] Butyl rubber and ethylene-propylene-diene rubber are added into an internal mixer according to the raw material formula, and plasticated for 1 min, then carbon black, metal oxide compound, modification aid, vulcanization activator and antioxidant are added and mixed for 2 min, then vulcanization accelerator and vulcanizing agent are added and mixed for 5 min, and the rubber compound is obtained; the rubber compound is placed on an open mill and thin passed for 3 times, and then stored for 20 h to obtain a mixed rubber; the mixed rubber is vulcanized on a flat vulcanizing machine for 20 min to obtain the soundproof rubber synthetic material. The temperature of the internal mixer is 65°C, and the rotating speed is 70 rpm; the roll gap of the open mill is 0.5 mm, and the temperature is 55°C; the temperature of the flat vulcanizing machine is 150°C, and the pressure is 8 MPa.

[0072] Embodiment 3

[0073] The present embodiment provides a soundproof rubber synthetic material, comprising the following raw materials in parts by weight:

[0074] 80 parts by weight of butyl rubber, 40 parts by weight of ethylene-propylene-diene rubber, 30 parts by weight of carbon black, 7 parts by weight of metal oxide compound, 13 parts by weight of modification aid, 15 parts by weight of vulcanization activator, 4 parts by weight of vulcanization accelerator, 3 parts by weight of vulcanizing agent, and 5 parts by weight of antioxidant. The vulcanization activator is a mixture of stearic acid and zinc oxide in a weight ratio of 5:3; the vulcanization accelerator is a mixture of N-tert-butyl-2-benzothiazole sulfenamide and zinc diethyl dithiocarbamate in a weight ratio of 1:3; the vulcanizing agent is sulfur; and the antioxidant is a mixture of antioxidant RD and antioxidant MB in a weight ratio of 3:3.

[0075] The metal oxide compound is prepared by the same method as in Embodiment 1.

[0076] The preparation method of the modified auxiliary agent is the same as that in Embodiment 1.

[0077] The embodiment provides a preparation method of a sound insulation rubber composite material, including the following steps:

[0078] The butyl rubber and the ethylene-propylene-diene rubber are added into a mixing mill according to the raw material formula, and plasticated for 3 min, then the carbon black, the metal oxide compound, the modified auxiliary agent, the vulcanization activator and the antioxidant are added and mixed for 5 min, then the vulcanization accelerator and the vulcanizing agent are added and mixed for 2 min, and the glue is discharged to obtain a rubber compound; the rubber compound is placed on an open mill and thin passed for 5 times, and then is parked for 25 h to obtain a mixed rubber; the mixed rubber is vulcanized on a flat vulcanizing machine for 40 min to obtain the sound insulation rubber composite material. The temperature of the mixing mill is 75 DEG C, and the rotating speed is 90 rpm; the roll distance of the open mill is 1.0 mm, and the temperature is 65 DEG C; the temperature of the flat vulcanizing machine is 170 DEG C, and the pressure is 12 MPa.

[0079] Comparative Example 1

[0080] The difference between the comparative example and Embodiment 1 is that the preparation method of the metal oxide compound is different, and specifically as follows: the preparation method of the metal oxide compound includes the following steps: 3 parts by weight of titanium dioxide and 10 parts by weight of silicon dioxide are uniformly mixed, then are pressed into a cylindrical sample under the condition of 0.2 MPa, the diameter of the cylindrical sample is 1 cm, and the height is 1.5 cm, then the cylindrical sample is calcined at 1250 DEG C for 150 min, after the end, the cylindrical sample is crushed under the condition of liquid nitrogen at-150 DEG C for 35 min, and after crushing, is sieved through a 150 mesh screen to obtain the metal oxide compound.

[0081] Comparative Example 2

[0082] The difference between the comparative example and Embodiment 1 is that the preparation method of the metal oxide compound is different, and specifically as follows: the preparation method of the metal oxide compound includes the following steps: 2 parts by weight of cerium dioxide and 10 parts by weight of silicon dioxide are uniformly mixed, then are pressed into a cylindrical sample under the condition of 0.2 MPa, the diameter of the cylindrical sample is 1 cm, and the height is 1.5 cm, then the cylindrical sample is calcined at 1250 DEG C for 150 min, after the end, the cylindrical sample is crushed under the condition of liquid nitrogen at-150 DEG C for 35 min, and after crushing, is sieved through a 150 mesh screen to obtain the metal oxide compound.

[0083] Comparative Example 3

[0084] The difference between the comparative example and Embodiment 1 is that the preparation method of the modified auxiliary agent is different, and specifically as follows: the preparation method of the modified auxiliary agent includes the following steps:

[0085] The 2.5 parts by weight of phenyl phosphinic dichloride, 7 parts by weight of N-(4-aminophenyl) maleimide are added to 80 parts by weight of dimethyl sulfoxide, stirred at room temperature, 500 rpm for 10 min, then 1.5 parts by weight of potassium hydroxide is added, heated to 60°C for 10 h, and the dimethyl sulfoxide is removed by distillation under reduced pressure, dried to obtain a maleimide-containing intermediate; 4 parts by weight of the maleimide-containing intermediate, 1.5 parts by weight of maleic anhydride and 50 parts by weight of xylene are mixed uniformly, heated to 92°C under nitrogen atmosphere, then 0.05 parts by weight of azobisisobutyronitrile is added and reacted for 4 h, the xylene is removed by distillation under reduced pressure, and dried to obtain a functional polymer;

[0086] The 3.2 parts by weight of the functional polymer is added to 50 parts by weight of dimethyl sulfoxide, stirred at room temperature, 500 rpm for 15 min, then 1.6 parts by weight of hollow glass microbeads is added, stirred at 70°C, 200 rpm for 6 h, filtered, and dried to obtain a modified adjuvant.

[0087] Comparative Example 4

[0088] The difference between this comparative example and Example 1 is that the preparation method of the modified adjuvant is different, specifically as follows: the preparation method of the modified adjuvant comprises the following steps:

[0089] The 8 parts by weight of hollow glass microbeads is added to 70 parts by weight of 3 wt% sodium hydroxide aqueous solution, stirred at room temperature, 500 rpm for 25 min, filtered, washed with water until neutral, and dried to obtain activated hollow glass microbeads; 5 parts by weight of 3-aminopropyl triethoxysilane is mixed uniformly with 45 parts by weight of 65 wt% ethanol aqueous solution, then 3 parts by weight of the activated hollow glass microbeads is added, stirred at 75°C, 200 rpm for 8 h, filtered, and dried to obtain modified hollow glass microbeads;

[0090] The 2.5 parts by weight of phenyl phosphinic dichloride, 7 parts by weight of N-(4-aminophenyl) maleimide are added to 80 parts by weight of dimethyl sulfoxide, stirred at room temperature, 500 rpm for 10 min, then 1.5 parts by weight of potassium hydroxide is added, heated to 60°C for 10 h, and the dimethyl sulfoxide is removed by distillation under reduced pressure, dried to obtain a maleimide-containing intermediate; 4 parts by weight of the maleimide-containing intermediate, 1.5 parts by weight of maleic anhydride and 50 parts by weight of xylene are mixed uniformly, heated to 92°C under nitrogen atmosphere, then 0.05 parts by weight of azobisisobutyronitrile is added and reacted for 4 h, the xylene is removed by distillation under reduced pressure, and dried to obtain a functional polymer;

[0091] The 3.2 parts by weight of functional polymer were added to 50 parts by weight of dimethyl sulfoxide, stirred at room temperature for 15 min at 500 rpm, then 1.6 parts by weight of modified hollow glass beads were added, stirred at 70°C for 6 h at 200 rpm, filtered, and dried to obtain the modified adjuvant.

[0092] Comparative Example 5

[0093] The difference between this comparative example and Example 1 is that the preparation method of the modified adjuvant is different, specifically as follows: the preparation method of the modified adjuvant comprises the following steps:

[0094] The 8 parts by weight of hollow glass beads were added to 70 parts by weight of 3 wt% sodium hydroxide aqueous solution, stirred at room temperature for 25 min at 500 rpm, filtered, washed with water until neutral, and dried to obtain activated hollow glass beads; 5 parts by weight of N-(β-aminoethyl)-γ-aminopropyl methyldimethoxysilane was uniformly mixed with 45 parts by weight of 65 wt% ethanol aqueous solution, then 3 parts by weight of activated hollow glass beads were added, stirred at 75°C for 8 h at 200 rpm, filtered, and dried to obtain the modified adjuvant.

[0095] Comparative Example 6

[0096] The difference between this comparative example and Example 1 is that the preparation method of the modified adjuvant is different, specifically as follows: the preparation method of the modified adjuvant comprises the following steps:

[0097] The 8 parts by weight of hollow glass beads were added to 70 parts by weight of 3 wt% sodium hydroxide aqueous solution, stirred at room temperature for 25 min at 500 rpm, filtered, washed with water until neutral, and dried to obtain activated hollow glass beads; 5 parts by weight of N-(β-aminoethyl)-γ-aminopropyl methyldimethoxysilane was uniformly mixed with 45 parts by weight of 65 wt% ethanol aqueous solution, then 3 parts by weight of activated hollow glass beads were added, stirred at 75°C for 8 h at 200 rpm, filtered, and dried to obtain the modified adjuvant.

[0098] The 4 parts by weight of N-(4-aminophenyl) maleimide, 1.5 parts by weight of maleic anhydride, and 50 parts by weight of dimethylbenzene were uniformly mixed, heated to 92°C under a nitrogen atmosphere, then 0.05 parts by weight of azobisisobutyronitrile was added and reacted for 4 h, the dimethylbenzene was removed by distillation under reduced pressure, and dried to obtain the functional polymer.

[0099] The 3.2 parts by weight of functional polymer were added to 50 parts by weight of dimethyl sulfoxide, stirred at room temperature for 15 min at 500 rpm, then 1.6 parts by weight of modified hollow glass beads were added, stirred at 70°C for 6 h at 200 rpm, filtered, and dried to obtain the modified adjuvant.

[0100] Performance Test

[0101] The sound insulation rubber composite materials obtained in Examples 1-3 and Comparative Examples 1-6 were subjected to performance testing. Among them, the sound insulation performance was determined at room temperature using a 7758 four-microphone standing wave tube (B&K, Denmark) (standing wave tube method), the test frequency was 50-1600HZ, and the data at 1000Hz were taken for comparison of the sound insulation performance, the sample size was 100mm in diameter and 3mm in thickness. The flame retardant performance (oxygen index) was determined according to the standard GB / T2406.2-2009. The aging resistance was determined according to the standard GB / T3512-2014, the test conditions were 100℃ aging for 168h, the tensile strength and elongation at break of the material before and after aging were determined (GB / T528-2009), and the retention rate was calculated, the retention rate % = mechanical property after aging / property before aging x 100%. The results are shown in Table 1.

[0102] Table 1: Performance test results of sound insulation rubber composite materials

[0103]

[0104]

[0105] From the above performance test results, it can be seen that the sound insulation rubber composite materials prepared in Examples 1-3 have excellent sound insulation performance, flame retardant performance and aging resistance, especially the sound insulation rubber composite material of Example 1 has the most outstanding comprehensive performance, because the present application uses specific modified additives and metal oxide compounds, which significantly improves the sound insulation performance, flame retardant performance and aging resistance of the sound insulation rubber composite material.

[0106] In comparison, Comparative Examples 1-6 did not use the necessary technical solutions, resulting in a significant difference in the corresponding performance tests compared to Examples 1-3. In Comparative Examples 1-2, specific metal oxide compounds were not used, and in Comparative Examples 5-6, self-made modified additives were not used. The results show that this leads to a decrease in the sound insulation performance, flame retardant performance and aging resistance of the sound insulation rubber composite material. The above experimental results further prove the importance of the technical solutions defined in the present application to its technical effects.

[0107] The above is a preferred embodiment of the present application. It should be noted that for those skilled in the art, without departing from the principles of the present application, a number of improvements and refinements can be made, and these improvements and refinements should also be considered within the scope of protection of the present application.

Claims

1. A sound-insulating rubber synthetic material, characterized in that, Including the following parts by weight of raw materials: 60-80 parts by weight of butyl rubber, 20-40 parts by weight of ethylene propylene diene monomer (EPDM) rubber, 20-30 parts by weight of carbon black, 3-7 parts by weight of metal oxide composite, 7-13 parts by weight of modifying agent, 10-15 parts by weight of vulcanization activator, 2-4 parts by weight of vulcanization accelerator, 1-3 parts by weight of vulcanizing agent, and 2-5 parts by weight of antioxidant. The metal oxide composite is made by calcining and crushing cerium dioxide, titanium dioxide and silicon dioxide; the preparation method of the metal oxide composite includes: mixing 1-3 parts by weight of cerium dioxide, 2-4 parts by weight of titanium dioxide and 8-12 parts by weight of silicon dioxide evenly, then pressing it into a cylindrical sample, then calcining the cylindrical sample, crushing it, pulverizing it and sieving it to obtain the metal oxide composite. The modified additive is made of functional polymer and modified hollow glass microspheres; The preparation method of the modified additive includes the following steps: Add 5-10 parts by weight of hollow glass microspheres to 60-80 parts by weight of sodium hydroxide aqueous solution, stir, filter, wash with water, and dry to obtain activated hollow glass microspheres; mix 4-6 parts by weight of N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane with 40-50 parts by weight of ethanol aqueous solution, then add 2-5 parts by weight of activated hollow glass microspheres, heat and stir, filter, and dry to obtain modified hollow glass microspheres; 1-4 parts by weight of phenylphosphonic dichloride and 5-10 parts by weight of N-(4-aminophenyl)maleimide were added to 70-90 parts by weight of dimethyl sulfoxide, stirred, and then 1-2 parts by weight of potassium hydroxide were added. The mixture was heated to react, distilled under reduced pressure, and dried to obtain an intermediate containing maleimide. 3-5 parts by weight of the intermediate containing maleimide, 1-2 parts by weight of maleic anhydride, and 40-60 parts by weight of xylene were mixed evenly, heated under a nitrogen atmosphere, and then 0.04-0.06 parts by weight of azobisisobutyronitrile were added to react. The mixture was distilled under reduced pressure and dried to obtain the functional polymer. Add 2-4 parts by weight of the functional polymer to 40-60 parts by weight of dimethyl sulfoxide, stir, then add 1-2 parts by weight of modified hollow glass microspheres, heat and stir, filter, and dry to obtain the modified additive.

2. The sound-insulating rubber synthetic material according to claim 1, characterized in that, The method for preparing the metal oxide composite includes the following steps: Mix 1-3 parts by weight of cerium dioxide, 2-4 parts by weight of titanium dioxide and 8-12 parts by weight of silicon dioxide evenly, and then press them into cylindrical samples under 0.1-0.5 MPa conditions. The cylindrical samples have a diameter of 0.5-1 cm and a height of 1-2 cm. Then, calcine the cylindrical samples at 1100-1400℃ for 100-200 min. After that, pulverize the cylindrical samples under liquid nitrogen conditions at -160~-140℃ for 30-40 min. After pulverizing, pass the samples through a 120-180 mesh sieve to obtain a metal oxide composite.

3. The sound-insulating rubber synthetic material according to claim 1, characterized in that, The preparation method of the modified additive includes the following steps: Add 5-10 parts by weight of hollow glass microspheres to 60-80 parts by weight of 2-5 wt% sodium hydroxide aqueous solution, stir for 20-30 min at room temperature and 400-600 rpm, filter, wash with water until neutral, and dry to obtain activated hollow glass microspheres; mix 4-6 parts by weight of N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane with 40-50 parts by weight of 60-70 wt% ethanol aqueous solution, then add 2-5 parts by weight of activated hollow glass microspheres, stir for 5-10 h at 70-80℃ and 100-300 rpm, filter, and dry to obtain modified hollow glass microspheres; 1-4 parts by weight of phenylphosphonic dichloride and 5-10 parts by weight of N-(4-aminophenyl)maleimide were added to 70-90 parts by weight of dimethyl sulfoxide. The mixture was stirred at room temperature and 400-600 rpm for 7-15 min. Then, 1-2 parts by weight of potassium hydroxide were added, and the mixture was heated to 55-70℃ for 7-12 h. The dimethyl sulfoxide was removed by vacuum distillation, and the mixture was dried to obtain an intermediate containing maleimide. 3-5 parts by weight of the intermediate containing maleimide, 1-2 parts by weight of maleic anhydride, and 40-60 parts by weight of xylene were mixed evenly and heated to 90-95℃ under a nitrogen atmosphere. Then, 0.04-0.06 parts by weight of azobisisobutyronitrile were added and the mixture was reacted for 3-5 h. The xylene was removed by vacuum distillation, and the mixture was dried to obtain the functional polymer. Add 2-4 parts by weight of the functional polymer to 40-60 parts by weight of dimethyl sulfoxide, stir at room temperature and 400-600 rpm for 10-20 min, then add 1-2 parts by weight of modified hollow glass microspheres, stir at 65-75℃ and 100-300 rpm for 5-8 h, filter, and dry to obtain the modified additive.

4. The sound-insulating rubber synthetic material according to claim 1, characterized in that, The activator for sulfidation is a mixture of stearic acid and zinc oxide in a weight ratio of 3-5:3; the sulfiding agent is sulfur.

5. The sound-insulating rubber synthetic material according to claim 1, characterized in that, The vulcanization accelerator is one or a mixture of two or more of N-tert-butyl-2-benzothiazole sulfenamide, N-cyclohexyl-2-benzothiazole sulfenamide, dibenzothiazole disulfide, zinc dimethyl dithiocarbamate, and zinc diethyl dithiocarbamate; the antioxidant is one or a mixture of two or more of antioxidant RD, antioxidant MB, antioxidant 4010, antioxidant D, and antioxidant BLE.

6. The sound-insulating rubber synthetic material according to claim 5, characterized in that, The vulcanization accelerator is a mixture of N-tert-butyl-2-benzothiazole sulfenamide and zinc diethyl dithiocarbamate in a weight ratio of 1:1-3; the antioxidant is a mixture of antioxidant RD and antioxidant MB in a weight ratio of 3:1-3.

7. The method for preparing the sound-insulating rubber synthetic material according to any one of claims 1-6, characterized in that, Includes the following steps: According to the raw material formula, butyl rubber and EPDM rubber are added to a mixer and plasticized for 1-3 minutes. Then, carbon black, metal oxide compound, modifier, vulcanization activator, and antioxidant are added and mixed for 2-5 minutes. Then, vulcanization accelerator and vulcanizing agent are added and mixed for another 2-5 minutes. The rubber is discharged to obtain the rubber compound. The rubber compound is passed through a two-roll mill 3-5 times and then left to stand for 20-25 hours to obtain the compound. The compound is then placed on a flat vulcanizing machine and vulcanized for 20-40 minutes to obtain the sound-insulating rubber synthetic material.

8. The application of the sound-insulating rubber synthetic material according to any one of claims 1-6 in the preparation of building materials and automotive materials.

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