CN110938272B - Composite damping material and preparation method thereof - Google Patents
Composite damping material and preparation method thereof Download PDFInfo
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- CN110938272B CN110938272B CN201911314980.1A CN201911314980A CN110938272B CN 110938272 B CN110938272 B CN 110938272B CN 201911314980 A CN201911314980 A CN 201911314980A CN 110938272 B CN110938272 B CN 110938272B
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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Abstract
The invention provides a composite damping material and a preparation method thereof. The composite damping material provided by the invention comprises a polymer matrix and nano heteropoly acid particles dispersed in the polymer matrix; the polymer has a structure represented by formula (1). According to the invention, a specific acrylate compound structure is combined with a specific vinyl heterocyclic structure, wherein the vinyl heterocyclic structure provides association sites, then a polymer with the specific structure is combined with nano heteropoly acid particles, a plurality of association points exist between a polymer molecular chain and heteropoly acid particles, and physical association-ion interaction is generated; when the composite material receives external stimulation at high temperature, energy can be dissipated through the dissociation among the polymer chains, so that an excellent damping effect is achieved; in addition, the composite damping material provided by the invention has a good damping effect under low frequency, and can effectively realize vibration reduction and noise reduction under a wider frequency range.
Description
Technical Field
The invention relates to the technical field of vibration damping materials, in particular to a composite damping material and a preparation method thereof.
Background
With the rapid development of national economy and the wide use of high-speed machinery, the pollution of vibration and noise is increasingly serious, and the harm of noise and pollution is reflected in that: physical and mental injuries, interference with the normal use of equipment, instruments and equipment, and reduced concealment of weaponry. In view of the above problems, the method of using damping material to reduce vibration and noise is one of the main technical measures, and is the most economical, simple and effective method.
The polymer material has outstanding viscoelasticity, huge internal friction and super-strong damping effect, so the polymer material becomes the noise reduction material or the damping material which is most widely applied in the current engineering. The damping material is a vibration attenuation material, has the capability of consuming strain energy in the process of mechanical vibration transmission, reduces or transfers the resonance frequency of the structure, and is also called as a vibration damping material and a vibration damping material.
Damping materials generally require the temperature range and frequency range of effective damping to be as wide as possible to meet the use under different conditions. The glass transition temperature of the polyacrylate polymer can be selected from 107 ℃ (poly-tert-butyl methacrylate) and-70 ℃ (poly-octyl acrylate), and the acrylate polymer has excellent weather resistance, oil resistance, physical and mechanical properties and the like, so that the homopolymer or the copolymer of the acrylate polymer and the blend of the acrylate polymer are very suitable for designing damping materials. For example CN102161726A, CN1654512, utilize interpenetrating networks of acrylates with butyl rubber or polystyrene, resulting in excellent damping properties. However, the maximum temperature of the effective damping area of CN1654512 is below 120 ℃, the temperature range corresponding to the maximum resistance loss factor is 10-40 ℃, and the damping device is more suitable for damping under the room temperature condition; the maximum temperature of the effective damping area of CN102161726A is below 140 ℃. Therefore, the damping material is narrow in an effective high-temperature area, the damping effect of the high-temperature area is poor, and the high-temperature application of the damping material is limited; in addition, the preparation process of the damping material is complex.
Disclosure of Invention
In view of the above, the present invention provides a composite damping material and a preparation method thereof. The composite damping material provided by the invention can effectively improve the damping effect of the material in a high-temperature area and broaden the effective temperature range and width of the material.
The invention provides a composite damping material, which comprises a polymer matrix and nano heteropoly acid particles dispersed in the polymer matrix;
the polymer has a structure represented by formula (1):
wherein:
m is 100 to 3000, n is 3 to 420;
R1is H or methyl;
R2alkyl selected from C1-C8;
R3selected from the structures represented by formulas 3 a-3 c:
preferably, the heteropoly acid is selected from one or more of silicotungstic acid, phosphotungstic acid, molybdosilicic acid, molybdophosphoric acid, 11-molybdenum-1 vanadophosphoric acid, 10-molybdenum-2-vanadophosphoric acid, 9-molybdenum-3-vanadophosphoric acid and 18-tungstodiphosphoric acid.
Preferably, the molar ratio of the nano heteropoly acid particles to n in the polymer shown in the formula (1) is (0.5-1): 1.
Preferably, R2Selected from methyl, ethyl, butyl, hexyl or octyl.
Preferably, the particle size of the nano heteropoly acid particles is 0.5-6 nm.
The invention also provides a preparation method of the composite damping material in the technical scheme, which comprises the following steps:
a) under the action of an initiator, carrying out polymerization reaction on an acrylate monomer, a vinyl heterocyclic compound and a chain transfer agent to obtain a polymer matrix;
b) mixing the polymer matrix with nano heteropoly acid particles to obtain a composite damping material;
the acrylate monomer is one or more of acrylate and methacrylate;
the ester group in the acrylate monomer is an ester group of C1-C8;
the vinyl heterocyclic compound is selected from one or more of vinyl imidazole, 2-vinyl pyridine and 4-vinyl pyridine;
the chain transfer agent is 1- (O-ethylsulfonic acid group) ethylbenzene.
Preferably, in step a):
the molar ratio of the chain transfer agent to the acrylate monomer is 1: 100-3000;
the molar ratio of the acrylate monomer to the vinyl heterocyclic compound is (7-30) to 1.
Preferably, in step a):
the initiator is azobisisobutyronitrile;
the molar ratio of the initiator to the acrylate monomer is 0.2 to (100-3000).
Preferably, in step a):
the temperature of the polymerization reaction is 70-80 ℃, and the time is 8-24 h.
Preferably, the step b) specifically comprises:
b1) dissolving the polymer matrix in a solvent to obtain a polymer solution;
b2) dispersing the nano heteropoly acid particles in a solvent to obtain a heteropoly acid solution;
b3) mixing the polymer solution with a heteropoly acid solution, and drying to obtain a composite damping material;
the step b1) and the step b2) are not limited in sequence;
the molar ratio of the nano heteropoly acid particles to the vinyl heterocyclic structure on the polymer molecular chain in the polymer matrix is (0.5-1) to 1.
The invention provides a composite damping material, which comprises a polymer matrix and nano heteropoly acid particles dispersed in the polymer matrix; the polymer has a structure represented by the formula (1). According to the invention, a specific acrylate compound structure is combined with a specific vinyl heterocyclic structure, wherein the vinyl heterocyclic structure provides association sites, then a polymer with the specific structure is combined with nano heteropoly acid particles, a plurality of association points exist between a polymer molecular chain and heteropoly acid particles, and physical association-ion interaction is generated; when the composite material receives external stimulation at high temperature, energy can be dissipated through the dissociation among the polymer chains, so that an excellent damping effect is achieved; in addition, the composite damping material provided by the invention has a good damping effect under low frequency, and can effectively realize vibration reduction and noise reduction under a wider frequency range.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is a schematic structural diagram of the polymer molecular chain shown in formula (1) and the nano heteropoly acid particles in the composite damping material of the present invention;
FIG. 2 is a dynamic temperature sweep test analysis chart of the composite damping material obtained in example 1;
FIG. 3 is a dynamic temperature sweep test analysis chart of the composite damping material obtained in example 2;
FIG. 4 is a frequency sweep test analysis chart of the composite damping material obtained in example 2;
FIG. 5 is a comparison of the dynamic temperature scan curves for the material of example 3;
FIG. 6 is a frequency sweep test analysis chart of the composite damping material obtained in example 3;
FIG. 7 is a dynamic temperature sweep test analysis chart of the composite damping material obtained in example 4.
Detailed Description
The invention provides a composite damping material, which comprises a polymer matrix and nano heteropoly acid particles dispersed in the polymer matrix;
the polymer has a structure represented by formula (1):
wherein:
m is 100 to 3000, n is 3 to 420;
R1is H or AA group;
R2alkyl selected from C1-C8;
R3selected from the structures represented by formulas 3 a-3 c:
wherein the content of the first and second substances,
is a connection position; the end of the single bond in formula (1) does not show a methyl group.
According to the invention, a specific acrylate compound structure is combined with a specific vinyl heterocyclic structure, wherein the vinyl heterocyclic structure provides association sites, then a polymer with the specific structure is combined with nano heteropoly acid particles, a plurality of association points exist between a polymer molecular chain and heteropoly acid particles, and physical association-ion interaction is generated; when the composite material receives external stimulation at high temperature, energy can be dissipated through the dissociation among the polymer chains, so that an excellent damping effect is achieved.
In the present invention, m: n is preferably (7-30) to 1, and more preferably (7-10) to 1.
In the present invention, R2Is selected from alkyl of C1-C8. Preferably, R2Selected from methyl, ethyl, butyl, hexyl or octyl. The butyl group is selected from n-butyl, tert-butyl or isobutyl. The octyl group is preferably a n-octyl group.
In one embodiment of the invention, R1Is H, R2Is methyl. In another embodiment of the invention, R1Is H, R2Is ethyl. In another embodiment of the invention, R1Is H, R2Is n-butyl. In another embodiment of the invention, R1Is H, R2Is a tert-butyl group. In another embodiment of the invention, R1Is H, R2Is an isobutyl group. In another embodiment of the invention, R1Is H, R2Is n-octyl. In another embodiment of the invention, R1Is a methyl group, and the compound is,R2is n-butyl. In another embodiment of the invention, R1Is methyl, R2Is hexyl.
In the present invention, R3Selected from the structures represented by formulas 3 a-3 c:
wherein the content of the first and second substances,
is the attachment location.
In a preferred embodiment of the invention, R1Is methyl, R2Is hexyl, R3Is of formula 3b, or, R1Is methyl, R2Is hexyl, R3Is formula 3 c. By adopting the monomer, the temperature range of the composite damping material can be further widened.
In the invention, heteropoly acids, also known as Polyoxometalates (POMs), are monomolecular cluster compounds formed by connecting early transition metal atoms through oxygen coordination bridges, and have abundant chemical compositions and various topological structures. In the invention, the heteropoly acid is preferably one or more of silicotungstic acid, phosphotungstic acid, molybdosilicic acid, molybdophosphoric acid, 11-molybdenum-1 vanadophosphoric acid, 10-molybdenum-2-vanadophosphoric acid, 9-molybdenum-3-vanadophosphoric acid and 18-tungstodiphosphoric acid; more preferably silicotungstic acid.
In the present invention, the particle size of the nano heteropoly acid particles is preferably 0.5 to 6nm, and more preferably 0.5 to 2 nm.
In the composite material, the ratio of the molar quantity of the nano heteropoly acid particles to n in the polymer shown in the formula (1) is preferably (0.5-1): 1; in some embodiments of the invention, the ratio is 0.5: 1 or 1: 1. Specifically, after the polymer shown in the formula (1) is obtained, the molar weight of the vinyl heterocyclic structure on a high molecular chain of the polymer is tested, and then nano heteropoly acid particles are introduced according to the proportion.
In the composite material, the polymer molecular chain of the formula (1) and the nano heteropoly acid particles are combined through physical association-ion interaction, the structural schematic diagram is shown in figure 1, and figure 1 is the structural schematic diagram between the polymer molecular chain of the formula (1) and the nano heteropoly acid particles in the composite damping material; wherein, the lines represent polymer molecular chains, the spheres represent nano heteropoly acid particles, and the round dots represent association points between the polymer molecular chains and the nano heteropoly acid particles. Specifically, a vinyl heterocyclic structure in a polymer molecular chain provides an association site, and after the nano heteropoly acid particles are introduced, the association site is combined with the heteropoly acid particles to form the association site. It can be seen that a plurality of association points exist between the polymer molecular chains and the heteropoly acid particles, and when the composite material receives external stimulation under a high-temperature condition, energy can be dissipated through the dissociation between the polymer chains, so that an excellent damping effect is achieved.
In the invention, the r value represents the ratio of the charge carried by the heteropoly acid to the molecular chain association point, when r is more than 0.5, the molecular chain has the coupling effect of multi-point disassociation, namely the molecular chain must break two or more association points at the same time, and the condition can only occur at high temperature, so that the composite material provided by the invention has the dissociation of the association points in the range from low temperature to high temperature, the energy dissipation is realized, and the effective damping temperature range is effectively widened. The invention preferably controls the ratio of the molar quantity of the nano heteropoly acid particles to n in the polymer shown in the formula (1) to be preferably (0.5-1) to 1; the high-temperature damping effect of the composite material can be further improved in the proportion.
The invention also provides a preparation method of the composite damping material in the technical scheme, which comprises the following steps:
a) under the action of an initiator, carrying out polymerization reaction on an acrylate monomer, a vinyl heterocyclic compound and a chain transfer agent to obtain a polymer matrix;
b) mixing the polymer matrix with nano heteropoly acid particles to obtain a composite damping material;
the acrylate monomer is one or more of acrylate and methacrylate;
the ester group in the acrylate monomer is an ester group of C1-C8;
the vinyl heterocyclic compound is selected from one or more of vinyl imidazole, 2-vinyl pyridine and 4-vinyl pyridine;
the chain transfer agent is 1- (O-ethylsulfonic acid group) ethylbenzene.
According to the invention, under the action of an initiator, an acrylate monomer, a vinyl heterocyclic compound and a chain transfer agent are subjected to polymerization reaction to obtain a polymer matrix.
In the present invention, the initiator is preferably azobisisobutyronitrile. The molar ratio of the initiator to the acrylate monomer is preferably 0.2 to (100-3000), and more preferably 0.2 to (100-1000).
In the invention, the acrylate monomer is one or more of acrylate and methacrylate; wherein the ester group in the acrylate monomer is an ester group of C1-C8. Preferably, the acrylate monomer is selected from one or more of methyl acrylate, ethyl acrylate, butyl acrylate, octyl acrylate, butyl methacrylate and hexyl methacrylate. The butyl acrylate is selected from one or more of n-butyl acrylate, tert-butyl acrylate and isobutyl acrylate. The octyl acrylate is preferably n-octyl acrylate. According to the invention, the acrylate monomer is adopted, the damping performance is exhibited by virtue of glass transition at low temperature, and a large amount of energy is absorbed by virtue of the dissociation of a molecular chain and polyacid at high temperature, so that the wider application temperature range of the damping material is realized.
In the invention, the vinyl heterocyclic compound is selected from one or more of vinyl imidazole, 2-vinyl pyridine and 4-vinyl pyridine. The vinyl heterocyclic compound is combined with the acrylate monomer to provide an association site for the polymer,
in the invention, the molar ratio of the acrylate monomer to the vinyl heterocyclic compound is preferably (7-30) to 1; more preferably (7-10) to 1.
In the present invention, it is preferable that the reaction raw materials are subjected to a polymerization inhibitor removal treatment before the acrylic monomer and the vinyl heterocyclic compound are introduced. In some embodiments of the invention, the above reaction raw materials are separately passed through a neutral alumina column to remove the polymerization inhibitor.
In the invention, the chain transfer agent is 1- (O-ethylsulfonic acid group) ethylbenzene, namely a basic molecular chain of the polymer shown in the formula (1), and free radical polymerization reaction is realized in the presence of the chain transfer agent, so that the acrylate structure and the vinyl heterocyclic structure are combined.
In the invention, the 1- (O-ethylsulfonic acid group) ethylbenzene can be prepared by reacting (1-bromoethyl) benzene with potassium ethylxanthate, and the reaction route is as follows:
in the invention, the molar ratio of the chain transfer agent to the acrylate monomer is 1: 100-3000; preferably 1 to (100-1000).
In the present invention, butyl acrylate and vinyl imidazole are taken as examples, and the reaction route of the butyl acrylate and vinyl imidazole in the presence of a chain transfer agent to form the polymer shown in formula (1) is as follows:
in the present invention, the above reaction is carried out in a solvent medium. The solvent preferably comprises one or more of dioxane and N, N-dimethylformamide. In the invention, the preferable dosage ratio of the solvent to the acrylate monomer is (5-30) mL: 10 g; more preferably (5 to 10) mL: 10g, and the monodispersity after polymerization is good in the above range.
In the present invention, the mixed system is preferably subjected to freeze-pumping circulation before the reaction. The freezing and pumping cycle refers to freezing, vacuumizing and unfreezing. The number of freeze pumping cycles is preferably three. The water and oxygen in the reactor were removed by the freeze-pumping treatment described above.
In the present invention, the polymerization reaction is started after the freeze-pumping treatment. The temperature of the polymerization reaction is preferably 70-80 ℃. The time of the polymerization reaction is preferably 8-24 h; generally, the reaction time is 12 hours, and the monomer reaction rate can reach about 60%.
In the present invention, the reaction is preferably carried out under a protective gas atmosphere. The present invention is not particularly limited in the kind of the protective agent, and may be any conventional inert gas known to those skilled in the art, such as nitrogen, argon, helium, etc., and in some embodiments of the present invention, nitrogen is used.
In the present invention, after the reaction, it is preferable to add a solvent to the reaction solution obtained by the reaction to perform precipitation treatment. In the present invention, the solvent preferably includes one or more of methanol and water. Adding a solvent, precipitating, and removing the solvent to obtain the polymer shown in the formula (1).
After obtaining the polymer represented by the formula (1), the following characterization can be performed: (1) determining the molecular weight of the molecular chain by Gel Permeation Chromatography (GPC); specifically, TFH was used as an eluent, and the flow rate was 1 mL/min. (2) The ratio between the acrylate structure and the vinyl hybrid structure is determined by nuclear magnetic resonance, so that the number of association sites contained on each molecular chain can be calculated.
According to the invention, after the polymer shown in the formula (1) is obtained, the polymer matrix is mixed with the nano heteropoly acid particles to obtain the composite damping material.
The types, the usage amount, the particle diameters and the like of the polymer matrix and the nano heteropoly acid particles are consistent with those in the technical scheme, and are not repeated.
In the present invention, the mixing process preferably specifically includes:
b1) dissolving the polymer matrix in a solvent to obtain a polymer solution;
b2) dispersing the nano heteropoly acid particles in a solvent to obtain a heteropoly acid solution;
b3) mixing the polymer solution with a heteropoly acid solution, and drying to obtain a composite damping material;
the step b1) and the step b2) are not limited in order.
With respect to step b 1): the solvent preferably comprises one or more of Tetrahydrofuran (THF), methanol, ethanol and NN Dimethylformamide (DMF). The concentration of the polymer matrix in the solvent is preferably 5-30 mg/mL; in some embodiments of the invention, the concentration is controlled to be 10mg/mL in order to achieve uniform dispersion.
With respect to step b 2): the solvent preferably comprises one or more of Tetrahydrofuran (THF), methanol, ethanol and NN Dimethylformamide (DMF). The concentration of the nano heteropoly acid particles in the solvent is preferably 5-30 mg/mL; in some embodiments of the invention, the concentration is controlled to be 10mg/mL in order to achieve uniform dispersion.
With respect to step b 3): the mixing is preferably ultrasonic dispersion mixing and then stirring mixing. The temperature of the mixing is not particularly limited, and may be carried out at room temperature. The frequency of ultrasonic dispersion is preferably 60-90 Hz, and the time is preferably 5-10 min. The stirring speed is preferably 100-400 rpm, and the time is preferably 3-5 h. The drying temperature is preferably 50-80 ℃. After the drying treatment, the composite material of the polymer matrix and the nano heteropoly acid particles is obtained, the structure of which is shown in figure 1, and the nano heteropoly acid particles are dispersed in the polymer matrix and form physical association with association sites on polymer molecular chains.
The preparation method provided by the invention is simple and feasible, mild in condition, simple in equipment and convenient for large-scale production and application.
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims. In the following examples, the chain transfer agent was 1- (O-ethylsulfonic acid) ethylbenzene and the initiator was azobisisobutyronitrile. The particle size of the silicotungstic acid nano particles is 1 nm.
Example 1
1.1 preparation of the Material
S1, passing the vinyl imidazole and the butyl acrylate through a neutral alumina column to remove the polymerization inhibitor. Mixing butyl acrylate and vinyl imidazole according to the molar ratio of 9: 1, and adding a chain transfer agent and an initiator according to the molar ratio of butyl acrylate monomer, the chain transfer agent and the initiator of 100: 1: 0.2; then, anhydrous dioxane solvent (butyl acrylate monomer: solvent: 10 g: 6mL) was added thereto, the mixture was freeze-extracted three times, and then reacted at 70 ℃ for 12 hours under nitrogen, the resulting reaction solution was precipitated in a mixed solution of methanol and water (methanol: water volume ratio: 85: 15), and vacuum-dried at 80 ℃ to obtain a polymer represented by formula (1).
The reaction route of the above reaction is as follows:
the molecular weight of the obtained polymer and the molar ratio of the butyl acrylate fragment to the vinyl imidazole fragment in the polymer chain were measured by GPC and NMR measurements, respectively, and it was found that the number average molecular weight was 25090g/mol, m was 186 and n was 13.6.
S2, controlling the molar ratio of the silicotungstic acid nano particles to the imidazole fragments to be 0.5: 1 according to the content of the imidazole fragments in the obtained polymer.
Dissolving the obtained polymer in THF, and mixing uniformly to obtain a polymer solution;
dissolving silicotungstic acid nano particles in methanol, and uniformly mixing to obtain a silicotungstic acid solution;
mixing the polymer solution with a silicotungstic acid solution, ultrasonically dispersing for 5min, and stirring for 12 h; and then, volatilizing the solvent in a blowing oven at 50 ℃, and then pumping the solvent in a vacuum oven at 80 ℃ to obtain the composite damping material.
1.2 testing of the materials
The obtained composite damping material was subjected to a dynamic temperature scan test, and the result is shown in fig. 2, fig. 2 is a dynamic temperature scan test analysis chart of the composite damping material obtained in example 1; where the symbols □, Δ and o are the storage modulus G', the loss modulus G "and the loss factor tan, respectively, and the abscissa is the temperature T.
It can be seen that the material prepared by doping polybutyl acrylate containing vinyl imidazole with silicotungstic acid with r being 0.5 has tan being more than 0.3 within the range of 20-120 ℃, and is suitable for the occasions of damping and absorbing vibration and noise near and above room temperature.
Example 2
1.1 preparation of the Material
S1, passing the 2-vinylpyridine and the hexyl methacrylate through a neutral alumina column to remove the polymerization inhibitor. Mixing according to the molar ratio of hexyl methacrylate to 2-vinylpyridine of 9: 1, and adding chain transfer agent and initiator according to the molar ratio of hexyl methacrylate monomer to chain transfer agent to initiator of 100: 1: 0.2; then, anhydrous dioxane solvent (10 g: 6mL of hexyl methacrylate monomer: solvent) was added, the mixture was freeze-extracted three times, and then reacted at 70 ℃ for 12 hours under nitrogen, the resulting reaction solution was precipitated in methanol, and the precipitate was vacuum-dried at 80 ℃ to obtain a polymer represented by formula (1).
The molecular weight of the obtained polymer and the molar ratio of the butyl acrylate fragment to the vinyl imidazole fragment in the polymer chain were measured by GPC and NMR detection, respectively, and it was found that the number average molecular weight was 162300g/mol, m was 914.2, and n was 61.2.
S2, controlling the molar ratio of the silicotungstic acid nano particles to the imidazole fragments to be 0.5: 1 according to the content of the pyridine fragments in the obtained polymer.
Dissolving the obtained polymer in THF, and mixing uniformly to obtain a polymer solution;
dissolving silicotungstic acid nano particles in methanol, and uniformly mixing to obtain a silicotungstic acid solution;
mixing the polymer solution with a silicotungstic acid solution, ultrasonically dispersing for 5min, and stirring for 12 h; and then, volatilizing the solvent in a blowing oven at 50 ℃, and then pumping the solvent in a vacuum oven at 80 ℃ to obtain the composite damping material.
1.2 testing of the materials
(1) Temperature domain testing
The obtained composite damping material was subjected to a dynamic temperature scan test, and the result is shown in fig. 3, fig. 3 is a dynamic temperature scan test analysis chart of the composite damping material obtained in example 2; where the symbols □, Δ and o are the storage modulus G', the loss modulus G "and the loss factor tan, respectively, and the abscissa is the temperature T.
It can be seen that, based on example 1, after the acrylate monomer and the vinyl hybrid monomer are replaced by hexyl methacrylate and 2-vinylpyridine, the lower limit of the service temperature of the obtained composite material is reduced to below 0 ℃, the upper limit temperature is increased to 250 ℃, and the damping effect is stronger (the purple dotted line represents the critical value of damping, and the higher the line is, the better the damping effect is), so that the composite material is suitable for occasions with requirements on vibration damping and noise absorption in a wider temperature range.
(2) Frequency testing
The obtained composite damping material was subjected to a frequency sweep test, and the result is shown in fig. 4, fig. 4 is a frequency sweep test analysis chart of the composite damping material obtained in example 2; the dynamic frequency is a main curve obtained by taking 60 ℃ as reference temperature through superposition; where the symbols □, Δ and o are the storage modulus G', the loss modulus G "and the loss factor tan, respectively, and the abscissa is the relevant parameter for the frequency ω (rad/s).
It can be seen that the effective damping frequency range of the composite material is up to 15 orders of magnitude, the composite material still has good damping effect under low frequency, and vibration and noise can be effectively reduced under a wider frequency range.
Example 3 and comparative example 1
The procedure of example 2 was followed except that, in step S2, the molar ratio of silicotungstic acid nanoparticles to imidazole fragments was controlled to 1: 1, i.e., r was controlled to 1: 1. As example 3.
The procedure of example 2 was followed except that silicotungstic acid nanoparticles were not introduced. This is denoted as comparative example 1.
According to the test method of the embodiment 2, the obtained materials are respectively subjected to dynamic temperature scanning test and compared with the dynamic temperature scanning curve of the product obtained in the embodiment 2, and the result is shown in fig. 5, wherein fig. 5 is a comparison graph of the dynamic temperature scanning curves of the materials in the embodiment 3; where the symbols □, Δ and diamond correspond to the loss factor tan of comparative example 1, example 2 with r-0.5 and example 3 with r-1, respectively, for undoped nano-heteropolyacid particles. Compared with the polymer material not doped with the nano heteropoly acid particles, the doped composite material has the advantages that the upper limit temperature of the use is increased by more than 100 ℃, the use temperature range of the material is greatly expanded, and the use occasions of the material are expanded.
According to the testing method of the embodiment 2, the composite material obtained in the embodiment 3 is subjected to a frequency scanning test, and the result is shown in fig. 6, and fig. 6 is a frequency scanning test analysis chart of the composite damping material obtained in the embodiment 3; the dynamic frequency is a main curve obtained by taking 60 ℃ as reference temperature through superposition; where the symbols □, Δ and o are the storage modulus G', the loss modulus G "and the loss factor tan, respectively, and the abscissa is the relevant parameter for the frequency ω (rad/s).
It can be seen that the effective damping frequency range of the composite material reaches up to 17 orders of magnitude, the composite material still has good damping effect under low frequency, and vibration and noise can be effectively reduced under a wider frequency range.
Example 4
1.1 preparation of the Material
S1, passing the 4-vinylpyridine and the hexyl methacrylate through a neutral alumina column to remove the polymerization inhibitor. Mixing according to the molar ratio of hexyl methacrylate to 4-vinylpyridine of 9: 1, and adding chain transfer agent and initiator according to the molar ratio of hexyl methacrylate monomer to chain transfer agent to initiator of 100: 1: 0.2; then, anhydrous dioxane solvent (10 g: 6mL of hexyl methacrylate monomer: solvent) was added, the mixture was freeze-extracted three times, and then reacted at 70 ℃ for 12 hours under nitrogen, the resulting reaction solution was precipitated in methanol, and the precipitate was vacuum-dried at 80 ℃ to obtain a polymer represented by formula (1).
The molecular weight of the obtained polymer and the molar ratio of the butyl acrylate fragment to the vinyl imidazole fragment in the polymer chain were measured by GPC and NMR detection, respectively, and it was found that the number average molecular weight was 100200g/mol, m was 563.7, and n was 38.1.
S2, controlling the molar ratio of the silicotungstic acid nano particles to the imidazole fragments to be 1: 1 according to the content of the pyridine fragments in the obtained polymer.
Dissolving the obtained polymer in THF, and mixing uniformly to obtain a polymer solution;
dissolving silicotungstic acid nano particles in methanol, and uniformly mixing to obtain a silicotungstic acid solution;
mixing the polymer solution with a silicotungstic acid solution, ultrasonically dispersing for 5min, and stirring for 12 h; and then, volatilizing the solvent in a blowing oven at 50 ℃, and then pumping the solvent in a vacuum oven at 80 ℃ to obtain the composite damping material.
1.2 testing of the materials
The dynamic temperature scan test of the obtained composite damping material is carried out, the result is shown in fig. 7, and fig. 7 is a dynamic temperature scan test analysis chart of the composite damping material obtained in example 4; where the symbols □, Δ and o are the storage modulus G', the loss modulus G "and the loss factor tan, respectively, and the abscissa is the temperature T.
It can be seen that, based on example 1, after the acrylate monomer and the vinyl hybrid monomer are replaced by the hexyl methacrylate monomer and 4-vinylpyridine, the lower limit of the use temperature of the obtained composite material is reduced to below 0 ℃, the upper limit temperature is increased to 250 ℃, the damping effect is stronger, and the composite material is suitable for occasions with requirements on vibration reduction and noise absorption in a wider temperature range.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A composite damping material, comprising a polymer matrix and nano heteropoly acid particles dispersed in the polymer matrix;
the polymer has a structure represented by formula (1):
wherein:
m is 100 to 3000, n is 3 to 420;
R1is H or methyl;
R2alkyl selected from C1-C8;
R3selected from the structures represented by formulas 3 a-3 c:
2. the composite damping material according to claim 1, wherein the heteropoly acid is selected from one or more of silicotungstic acid, phosphotungstic acid, molybdosilicic acid, molybdophosphoric acid, 11-molybdenum-1-vanadophosphoric acid, 10-molybdenum-2-vanadophosphoric acid, 9-molybdenum-3-vanadophosphoric acid and 18-tungstodiphosphoric acid.
3. The composite damping material as claimed in claim 1, wherein the ratio of the molar amount of the nano heteropoly acid particles to n in the polymer represented by the formula (1) is (0.5-1): 1.
4. The composite damping material of claim 1, wherein R is2Selected from methyl, ethyl, butyl, hexyl or octyl.
5. The composite damping material of claim 1, wherein the particle size of the nano heteropoly acid particles is 0.5-6 nm.
6. A preparation method of the composite damping material as claimed in any one of claims 1 to 5, characterized by comprising the following steps:
a) under the action of an initiator, carrying out polymerization reaction on an acrylate monomer, a vinyl heterocyclic compound and a chain transfer agent to obtain a polymer matrix;
b) mixing the polymer matrix with nano heteropoly acid particles to obtain a composite damping material;
the acrylate monomer is one or more of acrylate and methacrylate;
the ester group in the acrylate monomer is an ester group of C1-C8;
the vinyl heterocyclic compound is selected from one or more of vinyl imidazole, 2-vinyl pyridine and 4-vinyl pyridine;
the chain transfer agent is 1- (O-ethylsulfonic acid group) ethylbenzene;
the 1- (O-ethylsulfonic acid group) ethylbenzene has a structure shown in a formula (2):
7. the method of claim 6, wherein in step a):
the molar ratio of the chain transfer agent to the acrylate monomer is 1: 100-3000;
the molar ratio of the acrylate monomer to the vinyl heterocyclic compound is (7-30) to 1.
8. The method of manufacturing according to claim 6 or 7, wherein in step a):
the initiator is azobisisobutyronitrile;
the molar ratio of the initiator to the acrylate monomer is 0.2 to (100-3000).
9. The method of manufacturing according to claim 6 or 7, wherein in step a):
the temperature of the polymerization reaction is 70-80 ℃, and the time is 8-24 h.
10. The method according to claim 6, wherein step b) comprises in particular:
b1) dissolving the polymer matrix in a solvent to obtain a polymer solution;
b2) dispersing the nano heteropoly acid particles in a solvent to obtain a heteropoly acid solution;
b3) mixing the polymer solution with a heteropoly acid solution, and drying to obtain a composite damping material;
the step b1) and the step b2) are not limited in sequence;
the molar ratio of the nano heteropoly acid particles to the vinyl heterocyclic structure on the polymer molecular chain in the polymer matrix is (0.5-1) to 1.
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