CN112662115A - Rubber-based damping material and preparation method thereof - Google Patents
Rubber-based damping material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a rubber-based damping material which is characterized by being prepared from the following components in parts by weight: 20-30 parts of dithiothreitol modified vinyl-terminated liquid fluorosilicone rubber, 60-80 parts of epoxy SBS resin, 10-20 parts of 2- [3- (2H-benzotriazole-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate/allyl cyanoacetate/polyethylene glycol monoallyl ether/3, 5-diamino-1H-pyrazole-4-allyl carboxylate copolymer, 15-25 parts of fly ash, 3-6 parts of rare earth oxide nano-structure fiber and 1-3 parts of coupling agent. The invention also provides a preparation method of the rubber-based damping material. The rubber-based damping material disclosed by the invention has the advantages of good mechanical property, good aging resistance, obvious damping effect, low heat generation and excellent comprehensive performance and performance stability.
Description
Technical Field
The invention relates to the technical field of rubber sizing materials, in particular to a rubber-based damping material and a preparation method thereof.
Background
With the rapid development of modern industry, mechanical equipment tends to be high-speed, efficient and automatic in engineering, and the problems of vibration, noise and the like caused by the mechanical equipment are more and more prominent, thereby causing serious threats to the safety of lives and properties of people. The attenuation and elimination of harmful vibration and noise have very important significance in the fields of rail transit, buildings, precision instruments and the like. How to effectively reduce vibration and noise becomes one of the problems to be solved urgently in the current society industry.
The damping technology is an important method for controlling structural resonance and noise, and the damping material is the key for realizing shock absorption and noise reduction. The rubber material has unique dynamic viscoelasticity and large hysteresis loss, and can be widely applied to the fields of machinery, buildings, automobiles, railways, aviation and the like as a damping material. The fundamental reason why the rubber material generates the damping action is the hysteresis phenomenon and the mechanical loss of the polymer under the action of the alternating stress, the larger the mechanical loss of the material is, the wider the glass-transition temperature range is, the temperature range value is more consistent with the external environment, and the better the damping effect is.
The existing rubber-based damping material generally has the defects of low tensile strength, high heat generation, poor aging resistance and narrow vitrification conversion area, and can not meet the requirements of wide temperature range and wide frequency damping when used as a damping material. In order to solve the problems, blending, copolymerization and inorganic filling are commonly used at present, and the methods can improve the internal consumption peak of the material and broaden the glass transition region of the material to a certain extent, so as to improve the damping performance of the material, however, the improvement range is limited.
For example, chinese patent application No. 201310111532.8 relates to a damping material based on blending of butyl rubber and natural rubber and a preparation method thereof. The composite material consists of natural rubber, butyl rubber, petroleum resin, carbon black, an accelerant and an auxiliary agent, and the damping material is prepared by the following steps: firstly, mixing 50-100 parts of natural rubber, 35-70 parts of petroleum resin, 2-10 parts of an auxiliary agent and 35-70 parts of carbon black, and then adding 0-200 parts of butyl rubber and 2-10 parts of a vulcanizing agent into the mixture to be uniformly mixed into tablets; finally, the obtained rubber material is hot-pressed and molded at the temperature of 5-10M Pa, 100-200 ℃ to obtain the damping material. The damping material obtained by the invention has the advantages that the damping performance of the material is greatly improved while the better mechanical property is ensured, and the application range is wide. Meanwhile, the preparation method is simple in process and easy for industrial production. But the mechanical property is lower, and the damping effect needs to be further improved.
Therefore, the rubber-based damping material with good mechanical property, good aging resistance, remarkable damping effect, low heat generation and excellent comprehensive performance and performance stability is developed, meets the market demand, has wide market value and application prospect, and has very important significance for promoting the development of the damping material.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides the rubber-based damping material which has the advantages of good mechanical property, good aging resistance, obvious damping effect, low heat generation and excellent comprehensive performance and performance stability. Meanwhile, the invention also provides a preparation method of the rubber-based damping material, and the preparation method is simple and easy to implement, convenient to operate and control, low in equipment dependence, high in preparation efficiency and finished product qualification rate, and suitable for industrial popularization and application.
In order to achieve the aim, the invention adopts the technical scheme that the rubber-based damping material is characterized by being prepared from the following components in parts by weight: 20-30 parts of dithiothreitol modified vinyl-terminated liquid fluorosilicone rubber, 60-80 parts of epoxy SBS resin, 10-20 parts of 2- [3- (2H-benzotriazole-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate/allyl cyanoacetate/polyethylene glycol monoallyl ether/3, 5-diamino-1H-pyrazole-4-allyl carboxylate copolymer, 15-25 parts of fly ash, 3-6 parts of rare earth oxide nano-structure fiber and 1-3 parts of coupling agent.
Preferably, the coupling agent is at least one of a silane coupling agent KH550, a silane coupling agent KH560 and a silane coupling agent KH 570.
Preferably, the rare earth oxide nano-structure fiber is La2Zr2O7Nanostructured fibers having an average diameter of 2 μm and an average particle size per unit particle of 80nm, most suitably according to the literature "preparation and properties of nanostructured fibers of rare earth oxides [ D]Tanghuijian, Shandong university, 2011 "Zhonglz-3 preparation method.
Preferably, the particle size of the fly ash is 800-1200 meshes.
Preferably, the preparation method of the 2- [3- (2H-benzotriazole-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate/allyl cyanoacetate/polyethylene glycol monoallyl ether/3, 5-diamino-1H-pyrazole-4-carboxylic acid allyl ester copolymer comprises the following steps: adding 2- [3- (2H-benzotriazole-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate, allyl cyanoacetate, polyethylene glycol monoallyl ether, 3, 5-diamino-1H-pyrazole-4-carboxylic acid allyl ester and an initiator into a high boiling point solvent, stirring and reacting for 3-6 hours at 65-75 ℃ in an inert gas atmosphere, precipitating in water, washing the precipitated polymer with ethanol for 3-6 times, and finally drying in a vacuum drying oven at 85-95 ℃ to constant weight to obtain 2- [3- (2H-benzotriazole-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate/allyl cyanoacetate/polyethylene glycol monoallyl ether/3, 5-diamino-1H-pyrazole-4-carboxylic acid allyl ester copolymer.
Preferably, the mass ratio of the 2- [3- (2H-benzotriazole-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate, allyl cyanoacetate, polyethylene glycol monoallyl ether, 3, 5-diamino-1H-pyrazole-4-carboxylic acid allyl ester, the initiator and the high boiling point solvent is 1 (1-2):0.4 (0.3-0.6): 0.03-0.05): 12-20.
Preferably, the initiator is at least one of azobisisobutyronitrile and azobisisoheptonitrile; the high boiling point solvent is at least one of dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone; the inert gas is any one of nitrogen, helium, neon and argon.
Preferably, the epoxy SBS resin is obtained by epoxidizing SBS resin, is thermoplastic elastomer polystyrene-butadiene-styrene block copolymer, and has a molecular weight of 3-6 ten thousand, a styrene mass content of 15-35% and an epoxy group mass fraction of 3-25%.
Preferably, the preparation method of the dithiothreitol modified vinyl-terminated liquid fluorosilicone rubber comprises the following steps: adding dithiothreitol, vinyl-terminated liquid fluorosilicone rubber and a photoinitiator into an organic solvent, uniformly stirring, irradiating for 45-65 minutes under ultraviolet light with the wavelength of 350-380nm at room temperature, washing for 3-5 times by using 1mol/L sodium hydroxide solution after the reaction is finished, then washing for 3-6 times, and finally performing rotary evaporation to remove the solvent and a small amount of unreacted monomers to obtain the dithiothreitol modified vinyl-terminated liquid fluorosilicone rubber.
Preferably, the molar ratio of dithiothreitol to vinyl-terminated liquid fluorosilicone rubber to photoinitiator to organic solvent is 1:1 (0.008-0.012) to (7-12).
Preferably, the molecular formula of the vinyl-terminated liquid fluorosilicone rubber is as follows: CH (CH)2＝CH(Si(CH2CH2CF3)(CH3)O)n-CH＝CH2，n＝50-1000。
Preferably, the photoinitiator is at least one of benzophenone, benzoin ethyl ether and benzoin methyl ether.
The organic solvent is not limited as long as it can perform a dispersing action, and is preferably any one of tetrahydrofuran, ethyl acetate, and N, N-dimethylformamide.
Another objective of the present invention is to provide a method for preparing the rubber-based damping material, which is characterized by comprising the following steps: the rubber-based damping material is prepared by mixing the components in parts by weight to obtain a mixture, and then adding the mixture into a double-screw extruder for blending and extrusion.
Adopt the produced beneficial effect of above-mentioned technical scheme to lie in:
(1) the preparation method of the rubber-based damping material provided by the invention is simple and feasible, convenient to operate and control, small in equipment dependence, high in preparation efficiency and finished product qualification rate, and suitable for industrial popularization and application.
(2) The rubber-based damping material provided by the invention overcomes the defects that the existing rubber-based damping material generally has low tensile strength, high heat generation, poor aging resistance and narrow vitrification conversion area, and can not meet the requirements of wide temperature range and wide frequency damping when being used as a damping material; through the synergistic effect of the components, the prepared rubber-based damping material has the advantages of good mechanical property, good aging resistance, remarkable damping effect, low heat generation, and excellent comprehensive performance and performance stability.
(3) In the rubber-based damping material provided by the invention, the epoxy group on the epoxy SBS resin can respectively react with dithiothreitol modified vinyl-terminated liquid fluorosilicone rubber and 2- [3- (2H-benzotriazole-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate/allyl cyanoacetate/polyethylene glycol monoallyl ether/3, 5-diamino-1H-pyrazole-4-allyl carboxylate copolymer in the preparation and forming process of the damping material to form a complex three-dimensional network structure, all the components are connected in a chemical bond form and can also interact through hydrogen bonds, thereby effectively improving the comprehensive performance and the performance stability, the damping effect of the prepared material is better, and the effective damping temperature range and the effective damping frequency range are wider.
(4) The rubber-based damping material provided by the invention takes dithiothreitol modified vinyl-terminated liquid fluorosilicone rubber, epoxy SBS resin and 2- [3- (2H-benzotriazole-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate/allyl cyanoacetate/polyethylene glycol monoallyl ether/3, 5-diamino-1H-pyrazole-4-allyl carboxylate copolymer as base materials, and fully utilizes the advantages and synergistic action of the base materials, so that the prepared damping material not only has a wider damping temperature range, but also has higher mechanical property, reduces the internal heat generation of the damping material, and has the advantages of high tensile strength, low heat generation and aging resistance.
(5) According to the rubber-based damping material provided by the invention, through the molecular design of the base material, sulfenyl, fluorine-containing side chains, cyano-groups, pyrazolyl and amino side chains are introduced on a molecular chain, and the damping effect is effectively improved through the synergistic effect of increasing the number of the side chains and increasing the polarity of the side chains. Through the filling modification of the fly ash and the rare earth oxide nano-structure fiber, the mechanical property of the damping material can be improved through a dispersion strengthening mechanism, and the preparation cost can be reduced. The rare earth oxide nano-structure fiber has outstanding surface effect, small-size effect and quantum confinement effect, and can form weak adhesion and interface friction with a polymer base material, thereby obtaining high damping; the introduction of rare earth elements enables the damping performance to be better. A benzotriazole structure is introduced into a molecular chain of the copolymer, so that the aging resistance and durability of the material can be effectively improved, and the flame retardance of the material can also be improved.
Detailed Description
In order to make the technical solutions of the present invention better understood and make the above features, objects, and advantages of the present invention more comprehensible, the present invention is further described with reference to the following examples. The examples are intended to illustrate the invention only and are not intended to limit the scope of the invention.
The rare earth oxide nanostructured fiber used in the following examples of the present invention is La2Zr2O7Nanostructured fibers having an average diameter of 2 μm and an average particle size per unit particle of 80nm were prepared and characterized according to the literature "preparation of nanostructured fibers of rare earth oxides" [ D ]]Tanghuijian, Shandong university, 2011 "Zhonglz-3 preparation method. The epoxy SBS resin is obtained by epoxidizing SBS resin, is thermoplastic elastomer polystyrene-butadiene-styrene block copolymer, has molecular weight of 5 ten thousand, styrene content of 25% by mass and epoxy group content of 15% by mass; the molecular formula of the vinyl-terminated liquid fluorosilicone rubber is as follows: CH (CH)2＝CH(Si(CH2CH2CF3)(CH3)O)n-CH＝CH2N is 800; other raw materials were all purchased commercially.
Example 1
The rubber-based damping material is characterized by being prepared from the following components in parts by weight: 20 parts of dithiothreitol modified vinyl-terminated liquid fluorosilicone rubber, 60 parts of epoxy SBS resin, 10 parts of 2- [3- (2H-benzotriazole-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate/allyl cyanoacetate/polyethylene glycol monoallyl ether/3, 5-diamino-1H-pyrazole-4-allyl carboxylate copolymer, 15 parts of fly ash, 3 parts of rare earth oxide nano-structured fiber and 1 part of coupling agent.
The coupling agent is a silane coupling agent KH 550; the particle size of the fly ash is 800 meshes.
The preparation method of the 2- [3- (2H-benzotriazole-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate/allyl cyanoacetate/polyethylene glycol monoallyl ether/3, 5-diamino-1H-pyrazole-4-allyl carboxylate copolymer comprises the following steps: adding 2- [3- (2H-benzotriazole-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate, allyl cyanoacetate, polyethylene glycol monoallyl ether, 3, 5-diamino-1H-pyrazole-4-carboxylic acid allyl ester and an initiator into a high boiling point solvent, stirring and reacting for 3 hours at 65 ℃ in an inert gas atmosphere, then precipitating in water, washing the precipitated polymer with ethanol for 3-6 times, and finally drying in a vacuum drying oven at 85 ℃ to constant weight to obtain 2- [3- (2H-benzotriazole-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate/allyl cyanoacetate/polyethylene glycol monoallyl ether/3, 5-diamino-1H-pyrazole-4-carboxylic acid allyl ester copolymer.
The mass ratio of the 2- [3- (2H-benzotriazole-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate, allyl cyanoacetate, polyethylene glycol monoallyl ether, 3, 5-diamino-1H-pyrazole-4-allyl carboxylate, an initiator and a high-boiling point solvent is 1:1:0.4:0.3:0.03: 12; the initiator is azobisisobutyronitrile; the high boiling point solvent is dimethyl sulfoxide; the inert gas is nitrogen.
The preparation method of the dithiothreitol modified vinyl-terminated liquid fluorosilicone rubber comprises the following steps: adding dithiothreitol, vinyl-terminated liquid fluorosilicone rubber and a photoinitiator into an organic solvent, uniformly stirring, irradiating for 45 minutes at room temperature under ultraviolet light with the wavelength of 350nm, washing for 3 times by using 1mol/L sodium hydroxide solution after the reaction is finished, washing for 3 times, and finally performing rotary evaporation to remove the solvent and a small amount of unreacted monomers to obtain the dithiothreitol modified vinyl-terminated liquid fluorosilicone rubber.
The molar ratio of dithiothreitol to vinyl-terminated liquid fluorosilicone rubber to photoinitiator to organic solvent is 1:1:0.008: 7; the photoinitiator is benzophenone; the organic solvent is tetrahydrofuran.
The preparation method of the rubber-based damping material is characterized by comprising the following steps of: the rubber-based damping material is prepared by mixing the components in parts by weight to obtain a mixture, and then adding the mixture into a double-screw extruder for blending and extrusion.
Example 2
The rubber-based damping material is characterized by being prepared from the following components in parts by weight: 23 parts of dithiothreitol modified vinyl-terminated liquid fluorosilicone rubber, 65 parts of epoxy SBS resin, 13 parts of 2- [3- (2H-benzotriazole-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate/allyl cyanoacetate/polyethylene glycol monoallyl ether/3, 5-diamino-1H-pyrazole-4-allyl carboxylate copolymer, 17 parts of fly ash, 4 parts of rare earth oxide nano-structured fiber and 1.5 parts of coupling agent.
The coupling agent is a silane coupling agent KH 560; the particle size of the fly ash is 900 meshes.
The preparation method of the 2- [3- (2H-benzotriazole-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate/allyl cyanoacetate/polyethylene glycol monoallyl ether/3, 5-diamino-1H-pyrazole-4-allyl carboxylate copolymer comprises the following steps: adding 2- [3- (2H-benzotriazole-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate, allyl cyanoacetate, polyethylene glycol monoallyl ether, 3, 5-diamino-1H-pyrazole-4-carboxylic acid allyl ester and an initiator into a high boiling point solvent, stirring and reacting for 4 hours at 68 ℃ in an inert gas atmosphere, precipitating in water, washing the precipitated polymer for 4 times by using ethanol, and finally drying in a vacuum drying oven at 88 ℃ to constant weight to obtain the 2- [3- (2H-benzotriazole-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate/allyl cyanoacetate/polyethylene glycol monoallyl ether/3, 5-diamino-1H-pyrazole-4-carboxylic acid allyl ester copolymer.
The mass ratio of the 2- [3- (2H-benzotriazole-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate, allyl cyanoacetate, polyethylene glycol monoallyl ether, 3, 5-diamino-1H-pyrazole-4-allyl carboxylate, an initiator and a high-boiling point solvent is 1:1.2:0.4:0.4:0.035: 14; the initiator is azobisisoheptonitrile; the high boiling point solvent is N, N-dimethylformamide; the inert gas is helium.
The preparation method of the dithiothreitol modified vinyl-terminated liquid fluorosilicone rubber comprises the following steps: adding dithiothreitol, vinyl-terminated liquid fluorosilicone rubber and a photoinitiator into an organic solvent, uniformly stirring, irradiating for 50 minutes under ultraviolet light with the wavelength of 360nm at room temperature, washing for 4 times by using 1mol/L sodium hydroxide solution after the reaction is finished, washing for 4 times, and finally performing rotary evaporation to remove the solvent and a small amount of unreacted monomers to obtain the dithiothreitol modified vinyl-terminated liquid fluorosilicone rubber.
The molar ratio of dithiothreitol to vinyl-terminated liquid fluorosilicone rubber to photoinitiator to organic solvent is 1:1:0.009: 8; the photoinitiator is benzoin ethyl ether; the organic solvent is ethyl acetate.
The preparation method of the rubber-based damping material is characterized by comprising the following steps of: the rubber-based damping material is prepared by mixing the components in parts by weight to obtain a mixture, and then adding the mixture into a double-screw extruder for blending and extrusion.
Example 3
The rubber-based damping material is characterized by being prepared from the following components in parts by weight: 25 parts of dithiothreitol modified vinyl-terminated liquid fluorosilicone rubber, 70 parts of epoxy SBS resin, 15 parts of 2- [3- (2H-benzotriazole-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate/allyl cyanoacetate/polyethylene glycol monoallyl ether/3, 5-diamino-1H-pyrazole-4-allyl carboxylate copolymer, 20 parts of fly ash, 4.5 parts of rare earth oxide nano-structure fiber and 2 parts of coupling agent.
The coupling agent is a silane coupling agent KH 570; the particle size of the fly ash is 1000 meshes.
The preparation method of the 2- [3- (2H-benzotriazole-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate/allyl cyanoacetate/polyethylene glycol monoallyl ether/3, 5-diamino-1H-pyrazole-4-allyl carboxylate copolymer comprises the following steps: adding 2- [3- (2H-benzotriazole-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate, allyl cyanoacetate, polyethylene glycol monoallyl ether, 3, 5-diamino-1H-pyrazole-4-carboxylic acid allyl ester and an initiator into a high boiling point solvent, stirring and reacting for 4.5 hours at 70 ℃ in an inert gas atmosphere, precipitating in water, washing the precipitated polymer with ethanol for 5 times, and finally drying in a vacuum drying oven at 90 ℃ to constant weight to obtain the 2- [3- (2H-benzotriazole-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate/allyl cyanoacetate/polyethylene glycol monoallyl ether/3, 5-diamino-1H-pyrazole-4-carboxylic acid allyl ester copolymer.
The mass ratio of the 2- [3- (2H-benzotriazole-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate, allyl cyanoacetate, polyethylene glycol monoallyl ether, 3, 5-diamino-1H-pyrazole-4-allyl carboxylate, an initiator and a high-boiling point solvent is 1:1.5:0.4:0.45:0.04: 16; the initiator is azobisisobutyronitrile; the high boiling point solvent is N, N-dimethylacetamide; the inert gas is neon.
The preparation method of the dithiothreitol modified vinyl-terminated liquid fluorosilicone rubber comprises the following steps: adding dithiothreitol, vinyl-terminated liquid fluorosilicone rubber and a photoinitiator into an organic solvent, uniformly stirring, irradiating for 55 minutes under ultraviolet light with the wavelength of 365nm at room temperature, washing for 4 times by using 1mol/L sodium hydroxide solution after the reaction is finished, washing for 5 times, and finally performing rotary evaporation to remove the solvent and a small amount of unreacted monomers to obtain the dithiothreitol modified vinyl-terminated liquid fluorosilicone rubber.
The molar ratio of dithiothreitol to vinyl-terminated liquid fluorosilicone rubber to photoinitiator to organic solvent is 1:1:0.01: 9; the photoinitiator is benzoin ethyl ether; the organic solvent is N, N-dimethylformamide.
The preparation method of the rubber-based damping material is characterized by comprising the following steps of: the rubber-based damping material is prepared by mixing the components in parts by weight to obtain a mixture, and then adding the mixture into a double-screw extruder for blending and extrusion.
Example 4
The rubber-based damping material is characterized by being prepared from the following components in parts by weight: 28 parts of dithiothreitol modified vinyl-terminated liquid fluorosilicone rubber, 77 parts of epoxy SBS resin, 18 parts of 2- [3- (2H-benzotriazole-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate/allyl cyanoacetate/polyethylene glycol monoallyl ether/3, 5-diamino-1H-pyrazole-4-allyl carboxylate copolymer, 23 parts of fly ash, 5.5 parts of rare earth oxide nano-structured fiber and 2.5 parts of coupling agent.
The coupling agent is formed by mixing a silane coupling agent KH550, a silane coupling agent KH560 and a silane coupling agent KH570 according to the mass ratio of 1:3: 2; the particle size of the fly ash is 1100 meshes.
The preparation method of the 2- [3- (2H-benzotriazole-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate/allyl cyanoacetate/polyethylene glycol monoallyl ether/3, 5-diamino-1H-pyrazole-4-allyl carboxylate copolymer comprises the following steps: adding 2- [3- (2H-benzotriazole-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate, allyl cyanoacetate, polyethylene glycol monoallyl ether, 3, 5-diamino-1H-pyrazole-4-carboxylic acid allyl ester and an initiator into a high boiling point solvent, stirring and reacting for 5.5 hours at 73 ℃ in an inert gas atmosphere, precipitating in water, washing the precipitated polymer with ethanol for 6 times, and finally drying in a vacuum drying oven at 93 ℃ to constant weight to obtain the 2- [3- (2H-benzotriazole-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate/allyl cyanoacetate/polyethylene glycol monoallyl ether/3, 5-diamino-1H-pyrazole-4-carboxylic acid allyl ester copolymer.
The mass ratio of the 2- [3- (2H-benzotriazole-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate, allyl cyanoacetate, polyethylene glycol monoallyl ether, 3, 5-diamino-1H-pyrazole-4-carboxylic acid allyl ester, the initiator and the high-boiling point solvent is 1:1.8:0.4:0.55:0.046: 18.
The initiator is formed by mixing azodiisobutyronitrile and azodiisoheptonitrile according to the mass ratio of 3: 5; the high boiling point solvent is formed by mixing dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone according to a mass ratio of 1:2:1: 3; the inert gas is argon.
The preparation method of the dithiothreitol modified vinyl-terminated liquid fluorosilicone rubber comprises the following steps: adding dithiothreitol, vinyl-terminated liquid fluorosilicone rubber and a photoinitiator into an organic solvent, uniformly stirring, irradiating for 63 minutes at room temperature under ultraviolet light with the wavelength of 375nm, washing for 5 times by using 1mol/L sodium hydroxide solution after the reaction is finished, then washing for 6 times, and finally performing rotary evaporation to remove the solvent and a small amount of unreacted monomers to obtain the dithiothreitol modified vinyl-terminated liquid fluorosilicone rubber.
The molar ratio of dithiothreitol to vinyl-terminated liquid fluorosilicone rubber to the photoinitiator to the organic solvent is 1:1:0.011: 11; the photoinitiator is formed by mixing benzophenone, benzoin ethyl ether and benzoin methyl ether according to the mass ratio of 1:3: 2; the organic solvent is tetrahydrofuran.
The preparation method of the rubber-based damping material is characterized by comprising the following steps of: the rubber-based damping material is prepared by mixing the components in parts by weight to obtain a mixture, and then adding the mixture into a double-screw extruder for blending and extrusion.
Example 5
The rubber-based damping material is characterized by being prepared from the following components in parts by weight: 30 parts of dithiothreitol modified vinyl-terminated liquid fluorosilicone rubber, 80 parts of epoxy SBS resin, 20 parts of 2- [3- (2H-benzotriazole-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate/allyl cyanoacetate/polyethylene glycol monoallyl ether/3, 5-diamino-1H-pyrazole-4-allyl carboxylate copolymer, 25 parts of fly ash, 6 parts of rare earth oxide nano-structured fiber and 3 parts of coupling agent.
The coupling agent is a silane coupling agent KH 550; the particle size of the fly ash is 1200 meshes.
The preparation method of the 2- [3- (2H-benzotriazole-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate/allyl cyanoacetate/polyethylene glycol monoallyl ether/3, 5-diamino-1H-pyrazole-4-allyl carboxylate copolymer comprises the following steps: adding 2- [3- (2H-benzotriazole-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate, allyl cyanoacetate, polyethylene glycol monoallyl ether, 3, 5-diamino-1H-pyrazole-4-carboxylic acid allyl ester and an initiator into a high boiling point solvent, stirring and reacting for 6 hours at 75 ℃ in an inert gas atmosphere, precipitating in water, washing the precipitated polymer for 6 times by using ethanol, and finally drying in a vacuum drying oven at 95 ℃ to constant weight to obtain the 2- [3- (2H-benzotriazole-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate/allyl cyanoacetate/polyethylene glycol monoallyl ether/3, 5-diamino-1H-pyrazole-4-carboxylic acid allyl ester copolymer.
The mass ratio of the 2- [3- (2H-benzotriazole-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate to the allyl cyanoacetate to the polyethylene glycol monoallyl ether to the allyl 3, 5-diamino-1H-pyrazole-4-carboxylate to the initiator to the high-boiling-point solvent is 1:2:0.4:0.6:0.05: 20; the initiator is azobisisobutyronitrile; the high boiling point solvent is N-methyl pyrrolidone; the inert gas is nitrogen.
The preparation method of the dithiothreitol modified vinyl-terminated liquid fluorosilicone rubber comprises the following steps: adding dithiothreitol, vinyl-terminated liquid fluorosilicone rubber and a photoinitiator into an organic solvent, uniformly stirring, then illuminating for 65 minutes at room temperature under ultraviolet light with the wavelength of 380nm, after the reaction is finished, washing for 5 times by using 1mol/L sodium hydroxide solution, then washing for 6 times, and finally performing rotary evaporation to remove the solvent and a small amount of unreacted monomers to obtain the dithiothreitol modified vinyl-terminated liquid fluorosilicone rubber.
The molar ratio of dithiothreitol to vinyl-terminated liquid fluorosilicone rubber to photoinitiator to organic solvent is 1:1:0.012: 12; the photoinitiator is benzophenone; the organic solvent is N, N-dimethylformamide.
The preparation method of the rubber-based damping material is characterized by comprising the following steps of: the rubber-based damping material is prepared by mixing the components in parts by weight to obtain a mixture, and then adding the mixture into a double-screw extruder for blending and extrusion.
Comparative example 1
The present example provides a rubber-based damping material, the formulation and preparation method of which are substantially the same as those in example 1, except that: the dithiothreitol modified vinyl-terminated liquid fluorosilicone rubber was not added.
Comparative example 2
The present example provides a rubber-based damping material, the formulation and preparation method of which are substantially the same as those in example 1, except that: no 2- [3- (2H-benzotriazol-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate/allyl cyanoacetate/polyethylene glycol monoallyl ether/3, 5-diamino-1H-pyrazole-4-carboxylic acid allyl ester copolymer was added.
Comparative example 3
The present example provides a rubber-based damping material, the formulation and preparation method of which are substantially the same as those in example 1, except that: no rare earth oxide nanostructured fibers were added.
Comparative example 4
The present example provides a rubber-based damping material, the formulation and preparation method of which are substantially the same as those in example 1, except that: 2- [3- (2H-benzotriazol-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate was not added.
The rubber-based damping materials in the above examples 1 to 5 and comparative examples 1 to 4 were subjected to performance tests, the test results are shown in table 1; the test method is as follows: the tensile property is tested according to GB/T528-1998, the tensile speed is 500mm/min, and the test temperature is 25 ℃; the hardness was tested according to GB/T531-1999; the damping performance is subjected to dynamic mechanical test analysis by using a DMA242C type dynamic mechanical analyzer (Nachi corporation, Germany), and the test conditions are as follows: the stretching mode, the scanning temperature range is-100-130 deg.C, the heating rate is 3 deg.C/min, and the test frequency is 0.1Hz, 1Hz and 10 Hz. Wherein the testing frequency of the effective damping temperature range is 10Hz, and the reference temperature of the effective damping frequency range is 25 ℃.
TABLE 1 Performance test results of rubber-based damping materials
As can be seen from table 1, the rubber-based damping material disclosed in the examples of the present invention has excellent tensile strength, hardness and damping effect, which are the result of the synergy of the components.
The foregoing shows and describes the general principles and broad features of the present invention and advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. The rubber-based damping material is characterized by being prepared from the following components in parts by weight: 20-30 parts of dithiothreitol modified vinyl-terminated liquid fluorosilicone rubber, 60-80 parts of epoxy SBS resin, 10-20 parts of 2- [3- (2H-benzotriazole-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate/allyl cyanoacetate/polyethylene glycol monoallyl ether/3, 5-diamino-1H-pyrazole-4-allyl carboxylate copolymer, 15-25 parts of fly ash, 3-6 parts of rare earth oxide nano-structure fiber and 1-3 parts of coupling agent.
2. The rubber-based damping material of claim 1, wherein the coupling agent is at least one of a silane coupling agent KH550, a silane coupling agent KH560, and a silane coupling agent KH 570.
3. The rubber-based damping material of claim 1, wherein the rare earth oxide nanostructured fiber is La2Zr2O7Nanostructured fibers having an average diameter of 2 μm and an average particle size per unit particle of 80 nm; the particle size of the fly ash is 800-1200 meshes.
4. The rubber-based damping material of claim 1, wherein the 2- [3- (2H-benzotriazol-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate/allyl cyanoacetate/polyethylene glycol monoallyl ether/3, 5-diamino-1H-pyrazole-4-carboxylic acid allyl ester copolymer is prepared by a process comprising the steps of: adding 2- [3- (2H-benzotriazole-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate, allyl cyanoacetate, polyethylene glycol monoallyl ether, 3, 5-diamino-1H-pyrazole-4-carboxylic acid allyl ester and an initiator into a high boiling point solvent, stirring and reacting for 3-6 hours at 65-75 ℃ in an inert gas atmosphere, precipitating in water, washing the precipitated polymer with ethanol for 3-6 times, and finally drying in a vacuum drying oven at 85-95 ℃ to constant weight to obtain 2- [3- (2H-benzotriazole-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate/allyl cyanoacetate/polyethylene glycol monoallyl ether/3, 5-diamino-1H-pyrazole-4-carboxylic acid allyl ester copolymer.
5. The rubber-based damping material of claim 4, wherein the mass ratio of the 2- [3- (2H-benzotriazole-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate, allyl cyanoacetate, polyethylene glycol monoallyl ether, allyl 3, 5-diamino-1H-pyrazole-4-carboxylate, initiator, and high boiling point solvent is 1 (1-2):0.4 (0.3-0.6): 0.03-0.05): 12-20.
6. The rubber-based damping material of claim 4, wherein the initiator is at least one of azobisisobutyronitrile, azobisisoheptonitrile; the high boiling point solvent is at least one of dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone; the inert gas is any one of nitrogen, helium, neon and argon.
7. The rubber-based damping material of claim 1, wherein the epoxy SBS resin is obtained by epoxidizing SBS resin, is thermoplastic elastomer polystyrene-butadiene-styrene block copolymer, has a molecular weight of 3-6 ten thousand, a styrene mass content of 15-35%, and an epoxy group mass fraction of 3-25%.
8. The rubber-based damping material of claim 1, wherein the preparation method of dithiothreitol modified vinyl-terminated liquid fluorosilicone rubber comprises the following steps: adding dithiothreitol, vinyl-terminated liquid fluorosilicone rubber and a photoinitiator into an organic solvent, uniformly stirring, irradiating for 45-65 minutes under ultraviolet light with the wavelength of 350-380nm at room temperature, washing for 3-5 times by using 1mol/L sodium hydroxide solution after the reaction is finished, then washing for 3-6 times, and finally performing rotary evaporation to remove the solvent and a small amount of unreacted monomers to obtain the dithiothreitol modified vinyl-terminated liquid fluorosilicone rubber.
9. The rubber-based damping material of claim 8, wherein the molar ratio of dithiothreitol, vinyl-terminated liquid fluorosilicone rubber, photoinitiator and organic solvent is 1:1 (0.008-0.012): (7-12); the molecular formula of the vinyl-terminated liquid fluorosilicone rubber is as follows: CH (CH)2＝CH(Si(CH2CH2CF3)(CH3)O)n-CH＝CH2N is 50-1000; the photoinitiator is at least one of benzophenone, benzoin ethyl ether and benzoin methyl ether; the organic solvent is any one of tetrahydrofuran, ethyl acetate and N, N-dimethylformamide.
10. A method for preparing a rubber-based damping material according to any of claims 1-9, comprising the steps of: the rubber-based damping material is prepared by mixing the components in parts by weight to obtain a mixture, and then adding the mixture into a double-screw extruder for blending and extrusion.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114773849A (en) * | 2022-03-09 | 2022-07-22 | 金发科技股份有限公司 | High-temperature-resistant damping thermoplastic silicone rubber material capable of being repeatedly processed and preparation method and application thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114773849A (en) * | 2022-03-09 | 2022-07-22 | 金发科技股份有限公司 | High-temperature-resistant damping thermoplastic silicone rubber material capable of being repeatedly processed and preparation method and application thereof |
| CN114773849B (en) * | 2022-03-09 | 2023-08-29 | 金发科技股份有限公司 | High-temperature-resistant damping thermoplastic silicone rubber material capable of being repeatedly processed and preparation method and application thereof |
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