CN111978669A - High-strength sound insulation SiO2-maleic anhydride synergistically modified isoprene rubber and preparation method thereof - Google Patents

High-strength sound insulation SiO2-maleic anhydride synergistically modified isoprene rubber and preparation method thereof Download PDF

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CN111978669A
CN111978669A CN202010938834.2A CN202010938834A CN111978669A CN 111978669 A CN111978669 A CN 111978669A CN 202010938834 A CN202010938834 A CN 202010938834A CN 111978669 A CN111978669 A CN 111978669A
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isoprene rubber
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訾孟涛
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Abstract

The invention relates to the technical field of isoprene rubber and discloses high-strength sound insulation SiO2The maleic anhydride synergistically modified isoprene rubber comprises the following formula raw materials and components: nano SiO2Maleic anhydride grafted isoprene rubber, activator zinc oxide, activator stearic acid, vulcanization accelerator CZ, elemental sulfur. The high-strength sound insulation SiO2Maleic anhydride synergistically modified isoprene rubber, mesoporous nano SiO2The hollow microsphere has a unique hollow structure and rich mesoporous structures, maleic anhydride is used as a crosslinking center, p-menthane hydroperoxide is used as an initiator to initiate maleic anhydride and alkenyl functionalized mesoporous nano SiO2The cross-linking polymerization of hollow microsphere and isoprene improves the nano SiO2The interface compatibility and the dispersibility of the hollow microspheres and the isoprene rubber are enhanced, the tensile strength of the isoprene rubber is enhanced, and the mesoporous nano SiO2The hollow microspheres have excellent absorption loss and reflection attenuation effects on sound waves, and show excellent sound absorption and sound insulation effects.

Description

High-strength sound insulation SiO2-maleic anhydride synergistically modified isoprene rubber and preparation method thereof
Technical Field
The invention relates to the technical field of isoprene rubber, in particular to high-strength sound insulation SiO2Maleic anhydride synergistically modified isoprene rubber and a preparation method thereof.
Background
Noise pollution and water pollution, air pollution and solid waste pollution become four major pollutions of the contemporary society, and the main sources of the noise pollution, traffic noise, industrial noise, building noise, social noise and the like can be divided into: the sound insulation material refers to a material, a member or a structure which can block sound transmission or weaken transmitted sound energy, such as solid bricks, gypsum boards, sound insulation felts, fiberboards and the like, and develops a novel high-efficiency sound insulation material which is an effective way for solving the problem of noise pollution.
The rubber is a high-elasticity polymer material with reversible deformation, can generate larger deformation under the action of small external force, can recover to the original shape after the external force is removed, can be divided into natural rubber and synthetic rubber, such as cis-polyisoprene natural rubber, isoprene rubber, styrene butadiene rubber, butadiene rubber and the like, the rubber industry is one of important basic industries of national economy, the product mainly comprises light industrial rubber products for daily use, medical use and the like, the product has very wide application in heavy industries and emerging industries of traffic, building, machinery, electronics and the like, and the nano SiO has very wide application2Is a commonly used reinforcing filler for rubber materials, but the nano SiO2The surface contains a large amount of polar silicon hydroxyl groups, resulting in nano SiO2Has poor interface action with natural rubber, isoprene rubber and the like and poor dispersibility, thereby having good compatibility with nano SiO2The surface functional modification is carried out, the compatibility and the dispersibility with materials such as isoprene rubber are improved, and the application of the isoprene rubber materials in the aspects of sound insulation, sound absorption and the like is widened to become a research hotspot.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides high-strength sound insulation SiO2Maleic anhydride synergistically modified isoprene rubberThe glue and the preparation method solve the problem of nano SiO2The interface function with isoprene rubber is poor.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: high-strength sound insulation SiO2Maleic anhydride co-modified isoprene rubber: comprises the following raw materials and components, namely nano SiO2Maleic anhydride grafted isoprene rubber, an activator zinc oxide, an activator stearic acid, a vulcanization accelerator CZ and elemental sulfur, wherein the mass ratio of the maleic anhydride grafted isoprene rubber to the activator stearic acid to the vulcanization accelerator CZ is 100:3-6:1.5-2.5:0.5-1: 2-3.
Preferably, the high-strength sound-insulating SiO2The preparation method of the maleic anhydride synergistically modified isoprene rubber comprises the following steps:
(1) adding a mixed solvent of deionized water and ethanol into a reaction bottle, wherein the volume ratio of the deionized water to the ethanol is 3-5:1, adding hexadecyl trimethyl ammonium bromide component 1, stirring at room temperature at a constant speed for 2-4h until the solution is clear, adding ammonia water to adjust the pH of the solution to 9-10, dropwise adding tetraethoxysilane component 1 while stirring, heating to 35-45 ℃ in a constant temperature reactor, reacting at a constant speed for 10-20min, dropwise adding 3-aminopropyl triethoxysilane, reacting for 10-20min, dropwise adding tetraethoxysilane component 2, reacting for 18-24h, standing and aging for 20-30h, filtering the solution to remove the solvent, washing the precipitated product with deionized water and ethanol until the precipitated product is neutral, and drying.
(2) And (2) placing the precipitation product in the step (1) into a deionized water solvent, adding sodium carbonate and hexadecyl trimethyl ammonium bromide component 2, uniformly dispersing by ultrasonic, heating to 35-45 ℃ in a constant temperature reactor, reacting for 3-5h under uniform stirring, filtering, washing a solid product, and drying.
(3) Putting the solid product obtained in the step (2) into an ethanol solvent, adding ammonium nitrate, ultrasonically dispersing uniformly, heating to 75-85 ℃ in a constant-temperature reactor, stirring at a constant speed, refluxing for 10-15h, filtering, washing and drying to obtain the mesoporous nano SiO2Hollow microspheres.
(4) Adding toluene solvent and mesoporous nano SiO into a reaction bottle2Ultrasonically dispersing the hollow microspheres uniformly, adding alkenyl silane coupling agent, and heating to 1 in a constant-temperature reactorStirring at constant speed at 10-130 deg.C for 5-10h, distilling under reduced pressure, washing and drying to obtain alkenyl functionalized mesoporous nano SiO2Hollow microspheres.
(5) Adding toluene solvent and alkenyl functionalized mesoporous nano SiO into a reaction bottle2Uniformly dispersing hollow microspheres by ultrasonic wave, adding isoprene, maleic anhydride and an initiator, placing the mixture in a reaction kettle, heating the mixture to 110 ℃ in a nitrogen atmosphere, reacting for 5-10h, distilling the solution under reduced pressure, washing and drying to prepare the nano SiO2Maleic anhydride grafted isoprene rubber.
(6) Mixing nano SiO2Putting maleic anhydride grafted isoprene rubber, an activator zinc oxide, an activator stearic acid and a vulcanization accelerator CZ into an internal mixer for mixing, adding elemental sulfur, putting the mixture into an open mill for mixing, vulcanizing, thinly passing and discharging to prepare the high-strength sound-insulation SiO2Maleic anhydride co-modified isoprene rubber.
Preferably, the mass ratio of the hexadecyl trimethyl ammonium bromide component 1, the ethyl orthosilicate component 1, the 3-aminopropyl triethoxysilane, the ethyl orthosilicate component 2, the sodium carbonate, the hexadecyl trimethyl ammonium bromide component 2 and the ammonium nitrate in the steps (1), (2) and (3) is 32-38:100:80-120:100-150:400-450:5-7: 50-65.
Preferably, the constant temperature reactor in the step (1) comprises a magnetic heating stirrer, an oil bath pot is arranged above the magnetic heating stirrer, a heat preservation layer is fixedly connected to the outer side of the oil bath pot, a base is fixedly connected to the lower portion of the inner portion of the oil bath pot, a limiting groove is fixedly connected to the upper portion of the base, a spring telescopic rod is fixedly connected to the inner portion of the limiting groove, a connecting block is fixedly connected to the upper portion of the spring telescopic rod, an objective table is fixedly connected to the connecting block, and a reaction bottle is arranged above the.
Preferably, the alkenyl silane coupling agent in the step (4) is any one of vinyltrimethoxysilane or vinyltriethoxysilane, and mesoporous nano-SiO2The mass ratio of the hollow microspheres is 1-4: 10.
Preferably, the initiator in the step (5) is p-menthane hydroperoxide, and the alkenyl functionalized mesoporous nano SiO is2The mass ratio of the hollow microspheres to the isoprene to the maleic anhydride to the initiator hydrogen peroxide is 4-20:100:1-5: 0.002-0.01.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
the high-strength sound insulation SiO2Maleic anhydride synergistically modified isoprene rubber, using ethyl orthosilicate and 3-aminopropyltriethoxysilane as silicon sources, using hexadecyl trimethyl ammonium bromide as a template agent, removing an organic-inorganic hybrid silica layer by a sol-gel method and selective etching, and reserving an outer inorganic hybrid silica layer, thereby preparing the mesoporous nano SiO2The hollow microsphere has unique hollow structure and rich mesoporous structure, and specific surface area is larger than that of common nanometer SiO2The grafting rate of the p-alkenyl silane coupling agent can be improved greatly, maleic anhydride is used as a crosslinking center, p-menthane hydroperoxide is used as an initiator to initiate the maleic anhydride to generate active free radicals, so that alkenyl functionalized mesoporous nano SiO is obtained2Cross-linking and polymerizing the hollow microspheres, maleic anhydride and isoprene, and bridging the nano SiO by the maleic anhydride2The hollow microspheres are chemically and covalently grafted to the base body of isoprene rubber, so that the nano SiO is improved2The interface compatibility and the dispersibility of the hollow microspheres and the isoprene rubber obviously enhance the mechanical properties of the isoprene rubber, such as tensile strength and the like, and the mesoporous nano SiO2The unique hollow structure and rich mesoporous structure of the hollow microsphere have excellent absorption loss and reflection attenuation effects on sound waves, so that SiO (silicon dioxide) is enabled to be2The maleic anhydride synergistically modified isoprene rubber shows excellent sound absorption and sound insulation effects, and the practical application of the isoprene rubber is widened.
Drawings
FIG. 1 is a schematic front view of an oil bath pan;
FIG. 2 is an enlarged schematic view of the spring extension rod;
fig. 3 is a schematic view of stage adjustment.
1-magnetic heating stirrer; 2-oil bath pan; 3, insulating layer; 4-a base; 5-limiting groove; 6-spring telescopic rod; 7-connecting blocks; 8-an object stage; 9-reaction flask.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: high-strength sound insulation SiO2Maleic anhydride co-modified isoprene rubber: comprises the following raw materials and components, namely nano SiO2Maleic anhydride grafted isoprene rubber, an activator zinc oxide, an activator stearic acid, a vulcanization accelerator CZ and elemental sulfur, wherein the mass ratio of the maleic anhydride grafted isoprene rubber to the activator stearic acid to the vulcanization accelerator CZ is 100:3-6:1.5-2.5:0.5-1: 2-3.
High-strength sound insulation SiO2The preparation method of the maleic anhydride synergistically modified isoprene rubber comprises the following steps:
(1) adding a mixed solvent of deionized water and ethanol into a reaction bottle, wherein the volume ratio of the deionized water to the ethanol is 3-5:1, adding 1 part of hexadecyl trimethyl ammonium bromide, stirring at room temperature at a constant speed for 2-4h until the solution is clarified, adding ammonia water to adjust the pH of the solution to 9-10, dropwise adding 1 part of tetraethoxysilane while stirring, in a constant temperature reactor, wherein the constant temperature reactor comprises a magnetic heating stirrer, an oil bath pot is arranged above the magnetic heating stirrer, a heat preservation layer is fixedly connected to the outer side of the oil bath pot, a base is fixedly connected to the lower part inside the oil bath pot, a limit groove is fixedly connected to the upper part of the base, a spring telescopic rod is fixedly connected to the inner part of the limit groove, a connecting block is fixedly connected to the upper part of the spring telescopic rod, an objective table is fixedly connected to the connecting block, and then dropwise adding 3-aminopropyltriethoxysilane, reacting for 10-20min, dropwise adding tetraethoxysilane component 2, reacting for 18-24h, standing and aging for 20-30h, filtering the solution to remove the solvent, washing the precipitated product with deionized water and ethanol until the product is neutral, and drying.
(2) And (2) placing the precipitation product in the step (1) into a deionized water solvent, adding sodium carbonate and hexadecyl trimethyl ammonium bromide component 2, uniformly dispersing by ultrasonic, heating to 35-45 ℃ in a constant temperature reactor, reacting for 3-5h under uniform stirring, filtering, washing a solid product, and drying.
(3) Putting the solid product in the step (2) into an ethanol solvent and adding ammonium nitrate, wherein the hexadecyl trimethyl in the steps (1), (2) and (3)Ammonium bromide component 1, ethyl orthosilicate component 1, 3-aminopropyltriethoxysilane, ethyl orthosilicate component 2, sodium carbonate, hexadecyl trimethyl ammonium bromide component 2 and ammonium nitrate in the mass ratio of 32-38:100:80-120: 100: 150:400-2Hollow microspheres.
(4) Adding toluene solvent and mesoporous nano SiO into a reaction bottle2The hollow microspheres are added with any one of vinyltrimethoxysilane or vinyltriethoxysilane and mesoporous nano SiO after being uniformly dispersed by ultrasonic2The mass ratio of the hollow microspheres is 1-4:10, the mixture is heated to 110-2Hollow microspheres.
(5) Adding toluene solvent and alkenyl functionalized mesoporous nano SiO into a reaction bottle2Uniformly dispersing hollow microspheres by ultrasonic, adding isoprene, maleic anhydride and an initiator p-menthane hydroperoxide with the mass ratio of 4-20:100:1-5:0.002-0.01, placing the mixture in a reaction kettle, heating the mixture to 100 ℃ and 110 ℃ in the atmosphere of nitrogen, reacting for 5-10h, distilling the solution under reduced pressure, washing and drying to prepare the nano SiO2Maleic anhydride grafted isoprene rubber.
(6) Mixing nano SiO2Putting maleic anhydride grafted isoprene rubber, an activator zinc oxide, an activator stearic acid and a vulcanization accelerator CZ into an internal mixer for mixing, adding elemental sulfur, putting the mixture into an open mill for mixing, vulcanizing, thinly passing and discharging to prepare the high-strength sound-insulation SiO2Maleic anhydride co-modified isoprene rubber.
Example 1
(1) Adding a deionized water and ethanol mixed solvent into a reaction bottle, wherein the volume ratio of the deionized water to the ethanol mixed solvent is 3:1, adding hexadecyl trimethyl ammonium bromide component 1, stirring at a constant speed for 2 hours at room temperature until the solution is clarified, adding ammonia water to adjust the pH value of the solution to 9, dropwise adding tetraethoxysilane component 1 while stirring, in a constant temperature reactor, wherein the constant temperature reactor comprises a magnetic heating stirrer, an oil bath pot is arranged above the magnetic heating stirrer, a heat preservation layer is fixedly connected to the outer side of the oil bath pot, a base is fixedly connected to the lower part of the inner part of the oil bath pot, a limiting groove is fixedly connected to the upper part of the base, a spring telescopic rod is fixedly connected to the inner part of the limiting groove, a connecting block is fixedly connected to the upper part of the spring telescopic rod, a carrying table is fixedly connected to the connecting block, a reaction, reacting for 10min, then dropwise adding the tetraethoxysilane component 2, reacting for 18h, standing and aging for 20h, filtering the solution to remove the solvent, washing the precipitated product by using deionized water and ethanol until the product is neutral and drying.
(2) And (2) placing the precipitation product in the step (1) into a deionized water solvent, adding sodium carbonate and hexadecyl trimethyl ammonium bromide component 2, uniformly dispersing by ultrasonic, heating to 35 ℃ in a constant temperature reactor, reacting for 3 hours under uniform stirring, filtering, washing a solid product, and drying.
(3) Putting the solid product in the step (2) into an ethanol solvent and adding ammonium nitrate, wherein the mass ratio of the hexadecyl trimethyl ammonium bromide component 1, the ethyl orthosilicate component 1, the 3-aminopropyl triethoxysilane, the ethyl orthosilicate component 2, the sodium carbonate, the hexadecyl trimethyl ammonium bromide component 2 and the ammonium nitrate in the steps (1), (2) and (3) is 32:100:80:100:400:5:50, heating to 75 ℃ in a constant-temperature reactor after uniform ultrasonic dispersion, stirring at a constant speed for reflux reaction for 10 hours, filtering, washing and drying to prepare the mesoporous nano SiO2Hollow microspheres.
(4) Adding toluene solvent and mesoporous nano SiO into a reaction bottle2The hollow microspheres are added with vinyl trimethoxy silane and mesoporous nano SiO after being uniformly dispersed by ultrasonic2The mass ratio of the hollow microspheres is 1:10, the mixture is heated to 110 ℃ in a constant temperature reactor, stirred at a constant speed for reaction for 5 hours, and then is subjected to reduced pressure distillation, washing and drying to prepare the alkenyl functionalized mesoporous nano SiO2Hollow microspheres.
(5) Adding toluene solvent and alkenyl functionalized mesoporous nano SiO into a reaction bottle2Hollow microspheres, adding isoprene, maleic anhydride and initiator after ultrasonic dispersionPutting p-menthane hydrogen oxide with the mass ratio of 4:100:1:0.002 in a reaction kettle, heating to 100 ℃ in the nitrogen atmosphere, reacting for 5 hours, distilling the solution under reduced pressure, washing and drying to prepare nano SiO2Maleic anhydride grafted isoprene rubber.
(6) Mixing nano SiO2Putting maleic anhydride grafted isoprene rubber, an activator zinc oxide, an activator stearic acid and a vulcanization accelerator CZ into an internal mixer for mixing, adding elemental sulfur, wherein the mass ratio of the elemental sulfur to the elemental sulfur is 100:3:1.5:0.5:2, putting the mixture into an open mill for mixing, vulcanizing, thinly passing and discharging to prepare the high-strength sound-insulation SiO2Maleic anhydride co-modified isoprene rubber material 1.
Example 2
(1) Adding a deionized water and ethanol mixed solvent into a reaction bottle, wherein the volume ratio of the deionized water to the ethanol mixed solvent is 5:1, adding hexadecyl trimethyl ammonium bromide component 1, stirring at room temperature at a constant speed for 4 hours until the solution is clear, adding ammonia water to adjust the pH value of the solution to 10, dropwise adding tetraethoxysilane component 1 while stirring, arranging an oil bath pot above the constant temperature reactor, wherein the constant temperature reactor comprises a magnetic heating stirrer, the magnetic heating stirrer is fixedly provided with an oil bath pot, the outer side of the oil bath pot is fixedly connected with a heat insulation layer, the inner lower part of the oil bath pot is fixedly connected with a base, the upper part of the base is fixedly connected with a limiting groove, the inner part of the limiting groove is fixedly connected with a spring telescopic rod, the upper part of the spring telescopic rod is fixedly connected with a connecting block, the connecting block is fixedly connected with an objective table, reacting for 20min, then dropwise adding the tetraethoxysilane component 2, reacting for 18h, standing and aging for 30h, filtering the solution to remove the solvent, washing the precipitated product by using deionized water and ethanol until the product is neutral and drying.
(2) And (2) placing the precipitation product in the step (1) into a deionized water solvent, adding sodium carbonate and hexadecyl trimethyl ammonium bromide component 2, uniformly dispersing by ultrasonic, heating to 35 ℃ in a constant temperature reactor, uniformly stirring for reaction for 5 hours, filtering, washing a solid product, and drying.
(3) Putting the solid product in the step (2) into an ethanol solvent and adding ammonium nitrate, wherein the step (1)The mass ratio of hexadecyl trimethyl ammonium bromide component 1, ethyl orthosilicate component 1, 3-aminopropyl triethoxysilane, ethyl orthosilicate component 2, sodium carbonate, hexadecyl trimethyl ammonium bromide component 2 and ammonium nitrate in (2) and (3) is 34:100:90:115:420:5.6:55, after uniform ultrasonic dispersion, the mixture is heated to 85 ℃ in a constant temperature reactor, stirred at a constant speed for reflux reaction for 15 hours, filtered, washed and dried to prepare the mesoporous nano SiO2Hollow microspheres.
(4) Adding toluene solvent and mesoporous nano SiO into a reaction bottle2The hollow microspheres are added with vinyl triethoxysilane after being dispersed uniformly by ultrasonic wave and then are mixed with mesoporous nano SiO2The mass ratio of the hollow microspheres is 2:10, the mixture is heated to 110 ℃ in a constant temperature reactor, stirred at a constant speed for reaction for 10 hours, and then is subjected to reduced pressure distillation, washing and drying to prepare the alkenyl functionalized mesoporous nano SiO2Hollow microspheres.
(5) Adding toluene solvent and alkenyl functionalized mesoporous nano SiO into a reaction bottle2Ultrasonically dispersing hollow microspheres uniformly, adding isoprene, maleic anhydride and an initiator p-menthane hydroperoxide with the mass ratio of 10:100:2:0.004, placing the hollow microspheres in a reaction kettle, heating to 110 ℃ in the nitrogen atmosphere, reacting for 10 hours, distilling the solution under reduced pressure, washing and drying to obtain the nano SiO2Maleic anhydride grafted isoprene rubber.
(6) Mixing nano SiO2Putting maleic anhydride grafted isoprene rubber, an activator zinc oxide, an activator stearic acid and a vulcanization accelerator CZ into an internal mixer for mixing, then adding elemental sulfur, wherein the mass ratio of the elemental sulfur to the elemental sulfur is 100:4:1.8:0.6:2.4, putting the mixture into an open mill for mixing, vulcanizing, thinly passing and discharging to prepare the high-strength sound-insulation SiO2Maleic anhydride co-modified isoprene rubber material 2.
Example 3
(1) Adding a deionized water and ethanol mixed solvent into a reaction bottle, wherein the volume ratio of the deionized water to the ethanol mixed solvent is 4:1, adding hexadecyl trimethyl ammonium bromide component 1, stirring at room temperature at a constant speed for 3 hours until the solution is clear, adding ammonia water to adjust the pH value of the solution to 10, dropwise adding tetraethoxysilane component 1 while stirring, arranging an oil bath pot above the constant temperature reactor, wherein the constant temperature reactor comprises a magnetic heating stirrer, the magnetic heating stirrer is fixedly provided with an oil bath pot, the outer side of the oil bath pot is fixedly connected with a heat insulation layer, the inner lower part of the oil bath pot is fixedly connected with a base, the upper part of the base is fixedly connected with a limiting groove, the inner part of the limiting groove is fixedly connected with a spring telescopic rod, the upper part of the spring telescopic rod is fixedly connected with a connecting block, the connecting block is fixedly connected with an objective table, reacting for 15min, then dropwise adding the tetraethoxysilane component 2, reacting for 20h, standing and aging for 25h, filtering the solution to remove the solvent, washing the precipitated product by deionized water and ethanol until the product is neutral, and drying.
(2) And (2) placing the precipitation product in the step (1) into a deionized water solvent, adding sodium carbonate and hexadecyl trimethyl ammonium bromide component 2, uniformly dispersing by ultrasonic, heating to 40 ℃ in a constant temperature reactor, reacting for 4 hours under uniform stirring, filtering, washing a solid product, and drying.
(3) Putting the solid product in the step (2) into an ethanol solvent and adding ammonium nitrate, wherein the mass ratio of the hexadecyl trimethyl ammonium bromide component 1, the ethyl orthosilicate component 1, the 3-aminopropyl triethoxysilane, the ethyl orthosilicate component 2, the sodium carbonate, the hexadecyl trimethyl ammonium bromide component 2 and the ammonium nitrate in the steps (1), (2) and (3) is 36:100:105:140:440:6.5:60, heating to 80 ℃ in a constant temperature reactor after ultrasonic dispersion is uniform, stirring at constant speed for reflux reaction for 12h, filtering, washing and drying to prepare the mesoporous nano SiO2Hollow microspheres.
(4) Adding toluene solvent and mesoporous nano SiO into a reaction bottle2The hollow microspheres are added with vinyl triethoxysilane after being dispersed uniformly by ultrasonic wave and then are mixed with mesoporous nano SiO2The mass ratio of the hollow microspheres is 3:10, the mixture is heated to 120 ℃ in a constant temperature reactor, stirred at a constant speed for reaction for 8 hours, and then is subjected to reduced pressure distillation, washing and drying to prepare the alkenyl functionalized mesoporous nano SiO2Hollow microspheres.
(5) Adding toluene solvent and alkenyl functionalized mesoporous nano SiO into a reaction bottle2Hollow microspheres, adding isoprene, maleic anhydride and initiator for peroxidation after ultrasonic dispersionPutting the mixture into a reaction kettle, heating the mixture to 110 ℃ in a nitrogen atmosphere, reacting for 10 hours, distilling the solution under reduced pressure, washing and drying to prepare the nano SiO, wherein the mass ratio of the four is 15:100:3.5:0.0072Maleic anhydride grafted isoprene rubber.
(6) Mixing nano SiO2Putting maleic anhydride grafted isoprene rubber, an activator zinc oxide, an activator stearic acid and a vulcanization accelerator CZ into an internal mixer for mixing, then adding elemental sulfur, wherein the mass ratio of the elemental sulfur to the elemental sulfur is 100:5:2.2:0.8:2.7, putting the mixture into an open mill for mixing, vulcanizing, thinly passing and discharging to prepare the high-strength sound-insulation SiO2Maleic anhydride co-modified isoprene rubber material 3.
Example 4
(1) Adding a deionized water and ethanol mixed solvent into a reaction bottle, wherein the volume ratio of the deionized water to the ethanol mixed solvent is 5:1, adding hexadecyl trimethyl ammonium bromide component 1, stirring at room temperature at a constant speed for 4 hours until the solution is clear, adding ammonia water to adjust the pH value of the solution to 10, dropwise adding tetraethoxysilane component 1 while stirring, arranging an oil bath pot above the constant temperature reactor, wherein the constant temperature reactor comprises a magnetic heating stirrer, the magnetic heating stirrer is fixedly provided with an oil bath pot, the outer side of the oil bath pot is fixedly connected with a heat insulation layer, the inner lower part of the oil bath pot is fixedly connected with a base, the upper part of the base is fixedly connected with a limiting groove, the inner part of the limiting groove is fixedly connected with a spring telescopic rod, the upper part of the spring telescopic rod is fixedly connected with a connecting block, the connecting block is fixedly connected with an objective table, reacting for 20min, then dropwise adding the tetraethoxysilane component 2, reacting for 24h, standing and aging for 30h, filtering the solution to remove the solvent, washing the precipitated product by using deionized water and ethanol until the product is neutral, and drying.
(2) And (2) placing the precipitation product in the step (1) into a deionized water solvent, adding sodium carbonate and hexadecyl trimethyl ammonium bromide component 2, uniformly dispersing by ultrasonic, heating to 45 ℃ in a constant temperature reactor, uniformly stirring for reaction for 5 hours, filtering, washing a solid product, and drying.
(3) Putting the solid product in the step (2) into an ethanol solvent and adding ammonium nitrate, wherein the step (1)The mass ratio of hexadecyl trimethyl ammonium bromide component 1, ethyl orthosilicate component 1, 3-aminopropyl triethoxysilane, ethyl orthosilicate component 2, sodium carbonate, hexadecyl trimethyl ammonium bromide component 2 and ammonium nitrate in the (2) and (3) is 38:100:120:150:450:7:65, after the ultrasonic dispersion is uniform, the mixture is heated to 85 ℃ in a constant temperature reactor, stirred at a constant speed for reflux reaction for 15 hours, filtered, washed and dried to prepare the mesoporous nano SiO2Hollow microspheres.
(4) Adding toluene solvent and mesoporous nano SiO into a reaction bottle2The hollow microspheres are added with vinyl trimethoxy silane and mesoporous nano SiO after being uniformly dispersed by ultrasonic2The mass ratio of the hollow microspheres is 4:10, the mixture is heated to 130 ℃ in a constant temperature reactor, stirred at a constant speed for reaction for 10 hours, and then is subjected to reduced pressure distillation, washing and drying to prepare the alkenyl functionalized mesoporous nano SiO2Hollow microspheres.
(5) Adding toluene solvent and alkenyl functionalized mesoporous nano SiO into a reaction bottle2Uniformly dispersing hollow microspheres by ultrasonic, adding isoprene, maleic anhydride and an initiator p-menthane hydroperoxide with the mass ratio of 20:100:5:0.01, placing the mixture into a reaction kettle, heating the mixture to 110 ℃ in the atmosphere of nitrogen, reacting the mixture for 10 hours, distilling the solution under reduced pressure, washing and drying the solution to obtain the nano SiO2Maleic anhydride grafted isoprene rubber.
(6) Mixing nano SiO2Putting maleic anhydride grafted isoprene rubber, an activator zinc oxide, an activator stearic acid and a vulcanization accelerator CZ into an internal mixer for mixing, adding elemental sulfur, wherein the mass ratio of the elemental sulfur to the elemental sulfur is 100:6:2.5:1:3, putting the mixture into an open mill for mixing, vulcanizing, thinly passing and discharging to prepare the high-strength sound-insulation SiO2Maleic anhydride co-modified isoprene rubber material 4.
Comparative example 1
(1) Adding a deionized water and ethanol mixed solvent into a reaction bottle, wherein the volume ratio of the deionized water to the ethanol mixed solvent is 4:1, adding hexadecyl trimethyl ammonium bromide component 1, stirring at room temperature at a constant speed for 4 hours until the solution is clear, adding ammonia water to adjust the pH value of the solution to 9, dropwise adding tetraethoxysilane component 1 while stirring, arranging an oil bath pot above the constant temperature reactor, wherein the constant temperature reactor comprises a magnetic heating stirrer, the magnetic heating stirrer is fixedly provided with an oil bath pot, the outer side of the oil bath pot is fixedly connected with a heat insulation layer, the inner lower part of the oil bath pot is fixedly connected with a base, the upper part of the base is fixedly connected with a limiting groove, the inner part of the limiting groove is fixedly connected with a spring telescopic rod, the upper part of the spring telescopic rod is fixedly connected with a connecting block, the connecting block is fixedly connected with an objective table, reacting for 10min, then dropwise adding the tetraethoxysilane component 2, reacting for 15h, standing and aging for 30h, filtering the solution to remove the solvent, washing the precipitated product by using deionized water and ethanol until the product is neutral, and drying.
(2) And (2) placing the precipitation product in the step (1) into a deionized water solvent, adding sodium carbonate and hexadecyl trimethyl ammonium bromide component 2, uniformly dispersing by ultrasonic, heating to 30 ℃ in a constant temperature reactor, reacting for 2 hours under uniform stirring, filtering, washing a solid product, and drying.
(3) Putting the solid product in the step (2) into an ethanol solvent and adding ammonium nitrate, wherein the mass ratio of the hexadecyl trimethyl ammonium bromide component 1, the ethyl orthosilicate component 1, the 3-aminopropyl triethoxysilane, the ethyl orthosilicate component 2, the sodium carbonate, the hexadecyl trimethyl ammonium bromide component 2 and the ammonium nitrate in the steps (1), (2) and (3) is 30:100:70:160:480:8:45, heating to 85 ℃ in a constant temperature reactor after uniform ultrasonic dispersion, stirring at a constant speed for reflux reaction for 15h, filtering, washing and drying to prepare the mesoporous nano SiO2Hollow microspheres.
(4) Adding toluene solvent and mesoporous nano SiO into a reaction bottle2The hollow microspheres are added with vinyl triethoxysilane after being dispersed uniformly by ultrasonic wave and then are mixed with mesoporous nano SiO2The mass ratio of the hollow microspheres is 0.5:10, the mixture is heated to 110 ℃ in a constant temperature reactor, stirred at a constant speed for reaction for 5 hours, and then is subjected to reduced pressure distillation, washing and drying to prepare the alkenyl functionalized mesoporous nano SiO2Hollow microspheres.
(5) Adding toluene solvent and alkenyl functionalized mesoporous nano SiO into a reaction bottle2Hollow microspheres, adding isoprene, maleic anhydride and initiator p-menthane hydroperoxide after ultrasonic dispersionThe mass ratio of the four is 2:100:0.6:0.0012, the mixture is placed in a reaction kettle, the mixture is heated to 110 ℃ in the nitrogen atmosphere, the reaction is carried out for 5 hours, the solution is decompressed and distilled, washed and dried, and the nano SiO is prepared2Maleic anhydride grafted isoprene rubber.
(6) Mixing nano SiO2Putting maleic anhydride grafted isoprene rubber, an activator zinc oxide, an activator stearic acid and a vulcanization accelerator CZ into an internal mixer for mixing, adding elemental sulfur, and putting the mixture into an open mill for mixing, vulcanizing, thinly passing and discharging to prepare the high-strength sound insulation SiO2Maleic anhydride co-modified isoprene rubber comparative material 1.
High-strength soundproof SiO in the test examples and comparative examples using a WDW-200 type microcomputer controlled electronic universal tester2Tensile strength of maleic anhydride co-modified isoprene rubber material, test standard ISO/DIS 37-1990.
Figure BDA0002672910050000121
Figure BDA0002672910050000131
High strength acoustical SiO in the examples and comparative examples were tested using an AWA6122A standing wave tube acoustic absorption coefficient tester2The sound insulation performance of the maleic anhydride synergistic modified isoprene rubber material is tested according to the GB/T16731-1997.
Item Example 1 Example 2 Example 3 Example 4 Comparative example 1
Hertz (HZ) 500 500 500 500 500
Coefficient of sound absorption 0.38 0.51 0.47 0.32 0.24
Hertz (HZ) 2000 2000 2000 2000 2000
Coefficient of sound absorption 0.64 0.86 0.91 0.59 0.36
In summary, this high-strength sound insulation SiO2Maleic acidThe preparation method comprises the steps of using ethyl orthosilicate and 3-aminopropyltriethoxysilane as silicon sources and hexadecyl trimethyl ammonium bromide as a template agent to remove an organic-inorganic hybrid silica layer by a sol-gel method and selective etching, and reserving an outer inorganic hybrid silica layer to prepare the mesoporous nano SiO2The hollow microsphere has unique hollow structure and rich mesoporous structure, and specific surface area is larger than that of common nanometer SiO2The grafting rate of the p-alkenyl silane coupling agent can be improved greatly, maleic anhydride is used as a crosslinking center, p-menthane hydroperoxide is used as an initiator to initiate the maleic anhydride to generate active free radicals, so that alkenyl functionalized mesoporous nano SiO is obtained2Cross-linking and polymerizing the hollow microspheres, maleic anhydride and isoprene, and bridging the nano SiO by the maleic anhydride2The hollow microspheres are chemically and covalently grafted to the base body of isoprene rubber, so that the nano SiO is improved2The interface compatibility and the dispersibility of the hollow microspheres and the isoprene rubber obviously enhance the mechanical properties of the isoprene rubber, such as tensile strength and the like, and the mesoporous nano SiO2The unique hollow structure and rich mesoporous structure of the hollow microsphere have excellent absorption loss and reflection attenuation effects on sound waves, so that SiO (silicon dioxide) is enabled to be2The maleic anhydride synergistically modified isoprene rubber shows excellent sound absorption and sound insulation effects, and the practical application of the isoprene rubber is widened.

Claims (6)

1. High-strength sound insulation SiO2-maleic anhydride co-modified isoprene rubber, characterized in that: comprises the following raw materials and components, namely nano SiO2Maleic anhydride grafted isoprene rubber, an activator zinc oxide, an activator stearic acid, a vulcanization accelerator CZ and elemental sulfur, wherein the mass ratio of the maleic anhydride grafted isoprene rubber to the activator stearic acid to the vulcanization accelerator CZ is 100:3-6:1.5-2.5:0.5-1: 2-3.
2. The high-strength sound-insulating SiO 2-maleic anhydride synergistically-modified isoprene rubber according to claim 1, wherein: the high-strength sound insulation SiO2The preparation method of the maleic anhydride synergistically modified isoprene rubber comprises the following steps:
(1) adding a hexadecyl trimethyl ammonium bromide component 1 into a mixed solvent of deionized water and ethanol with the volume ratio of 3-5:1, stirring at room temperature for 2-4h until the solution is clear, adding ammonia water to adjust the pH value of the solution to 9-10, dropwise adding an ethyl orthosilicate component 1, heating in a constant temperature reactor to 35-45 ℃, reacting for 10-20min, dropwise adding 3-aminopropyl triethoxysilane, reacting for 10-20min, dropwise adding an ethyl orthosilicate component 2, reacting for 18-24h, standing and aging for 20-30h, filtering, washing a precipitate and drying;
(2) putting the precipitation product in the step (1) into a deionized water solvent, adding sodium carbonate and a hexadecyl trimethyl ammonium bromide component 2, performing ultrasonic dispersion uniformly, heating to 35-45 ℃ in a constant temperature reactor, reacting for 3-5h, filtering, washing a solid product, and drying;
(3) putting the solid product obtained in the step (2) into an ethanol solvent, adding ammonium nitrate, performing ultrasonic dispersion uniformly, heating to 75-85 ℃ in a constant-temperature reactor, performing reflux reaction for 10-15h, filtering, washing and drying to obtain mesoporous nano SiO2Hollow microspheres;
(4) adding mesoporous nano SiO into toluene solvent2Uniformly dispersing the hollow microspheres by ultrasonic, adding an alkenyl silane coupling agent, heating to 110-130 ℃ in a constant-temperature reactor, reacting for 5-10h, distilling under reduced pressure, washing and drying to prepare the alkenyl functionalized mesoporous nano SiO2Hollow microspheres;
(5) adding alkenyl functionalized mesoporous nano SiO into toluene solvent2Uniformly dispersing hollow microspheres by ultrasonic wave, adding isoprene, maleic anhydride and an initiator, placing the mixture in a reaction kettle, heating the mixture to 110 ℃ in a nitrogen atmosphere, reacting for 5-10h, distilling under reduced pressure, washing and drying to prepare the nano SiO2-maleic anhydride grafted isoprene rubber;
(6) mixing nano SiO2Putting maleic anhydride grafted isoprene rubber, an activator zinc oxide, an activator stearic acid and a vulcanization accelerator CZ into an internal mixer for mixing, adding elemental sulfur, putting the mixture into an open mill for mixing, vulcanizing, thinly passing and discharging to prepare the high-strength sound-insulation SiO2Maleic anhydride co-modified isoprene rubber.
3. The high-strength sound-insulating SiO 2-maleic anhydride synergistically-modified isoprene rubber according to claim 2, wherein: the mass ratio of the hexadecyl trimethyl ammonium bromide component 1, the ethyl orthosilicate component 1, the 3-aminopropyl triethoxysilane, the ethyl orthosilicate component 2, the sodium carbonate, the hexadecyl trimethyl ammonium bromide component 2 and the ammonium nitrate in the steps (1), (2) and (3) is 32-38:100:80-120: 100: 150:400-450:5-7: 50-65.
4. The high-strength sound-insulating SiO 2-maleic anhydride synergistically-modified isoprene rubber according to claim 2, wherein: the constant temperature reactor in step (1) includes that magnetic heating agitator, magnetic heating agitator top are provided with the oil bath pot, oil bath pot outside fixedly connected with heat preservation, the inside below fixedly connected with base of oil bath pot, base top fixedly connected with spacing groove, spacing inslot portion fixedly connected with spring telescopic link, spring telescopic link top fixedly connected with connecting block, connecting block fixedly connected with objective table, the objective table top is provided with the reaction flask.
5. The high-strength sound-insulating SiO 2-maleic anhydride synergistically-modified isoprene rubber according to claim 2, wherein: the alkenyl silane coupling agent in the step (4) is any one of vinyl trimethoxy silane or vinyl triethoxy silane and mesoporous nano SiO2The mass ratio of the hollow microspheres is 1-4: 10.
6. The high-strength sound-insulating SiO 2-maleic anhydride synergistically-modified isoprene rubber according to claim 2, wherein: the initiator in the step (5) is p-menthane hydroperoxide, and alkenyl functionalized mesoporous nano SiO2The mass ratio of the hollow microspheres to the isoprene to the maleic anhydride to the initiator hydrogen peroxide is 4-20:100:1-5: 0.002-0.01.
CN202010938834.2A 2020-09-09 2020-09-09 High-strength sound insulation SiO2-maleic anhydride synergistically modified isoprene rubber and preparation method thereof Withdrawn CN111978669A (en)

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