CN113061032B - Metal acrylate resin derived composite wave-absorbing material and preparation method thereof - Google Patents

Metal acrylate resin derived composite wave-absorbing material and preparation method thereof Download PDF

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CN113061032B
CN113061032B CN202110361127.6A CN202110361127A CN113061032B CN 113061032 B CN113061032 B CN 113061032B CN 202110361127 A CN202110361127 A CN 202110361127A CN 113061032 B CN113061032 B CN 113061032B
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acid
metal
acrylate resin
absorbing material
methacrylate
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CN113061032A (en
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于良民
周文君
闫雪峰
刘宁
李昌诚
王言建
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Sanya Institute Of Oceanography Ocean University Of China
Ocean University of China
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Sanya Institute Of Oceanography Ocean University Of China
Ocean University of China
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/52—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite
    • C04B35/524—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite obtained from polymer precursors, e.g. glass-like carbon material
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    • C08F218/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
    • C08F218/02—Esters of monocarboxylic acids
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    • C08F218/08—Vinyl acetate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1802—C2-(meth)acrylate, e.g. ethyl (meth)acrylate
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    • 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
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
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    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6562—Heating rate
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6567—Treatment time

Abstract

The invention relates to a metal acrylate resin derived composite wave-absorbing material and a preparation method thereof. The composite wave-absorbing material derived from the metal acrylate resin prepared by the invention is simple to operate and low in preparation cost, the existing process conditions support large-scale production, and the composite wave-absorbing material of carbon materials and metal particles can be obtained directly by calcining the metal acrylate resin. Compared with the existing wave-absorbing material, the metal acrylate resin derived composite wave-absorbing material prepared by the embodiment has excellent wave-absorbing performance of small density and strong wave-absorbing performance, and when the addition amount is 25% and the thickness is 3.0mm, the minimum reflection loss energy reaches-43.15 dB.

Description

Metal acrylate resin derived composite wave-absorbing material and preparation method thereof
[ technical field ] A method for producing a semiconductor device
The invention belongs to the technical field of electromagnetic wave absorption materials. More specifically, the invention relates to a metal acrylate resin derived composite wave-absorbing material and a preparation method thereof.
[ background of the invention ]
In recent years, the development of electronic information technology and the wide application of various electronic devices bring great convenience to the life of people, but also bring a great deal of electromagnetic radiation pollution. Electromagnetic radiation not only affects the normal operation of electronic equipment, but has become an invisible killer that is harmful to animal and plant growth and human health. In the future, stealth technology applied to military weapons will become an important competitive means for improving military strength in all countries. Therefore, the development of an electromagnetic wave absorbing material with excellent wave absorbing performance has important research value and wide application prospect.
The ideal wave-absorbing material should have the characteristics of light weight, thin thickness, wide and strong effective absorption frequency, corrosion resistance, good thermal stability and the like, and the single type wave-absorbing material is difficult to meet the wave-absorbing requirement. Carbon materials have been widely reported to have the advantages of low density, good dielectric properties, thermal and chemical stability, abundant sources and easy preparation. However, they generally exhibit relatively high dielectric losses and are not suitable as wave absorbers alone. If metal ions are introduced into the carbon material wave absorbing agent to improve the magnetic loss performance and impedance matching of the carbon material, the wave absorbing performance of the material is improved to a great extent.
Carbon materials are widely available and include inorganic and organic carbon sources. Generally, a template is usually needed for preparing the wave-absorbing material by using an inorganic carbon source, the template is not needed by using an organic material as the carbon source, an organic polymer with a specific structure is synthesized by adjusting a synthesis process, and a functional group required by people can be obtained by a carbonization process, so that the wave-absorbing material becomes a relatively promising carbon material source. The acrylic resin is synthetic resin which is applied in the market at present, has low price, wide source, huge yield and stronger plasticity, and the metal ions are introduced into the acrylic resin to synthesize the acrylic acid metal salt resin, so that the acrylic resin is a mature synthesis process, and the carbon/metal particle composite wave-absorbing material can be directly obtained by taking the acrylic resin as a precursor through high-temperature carbonization, thereby being suitable for large-scale production.
[ summary of the invention ]
[ problem to be solved ]
The invention aims to provide a composite wave-absorbing material derived from metal acrylate resin.
The invention also aims to provide a preparation method of the metal acrylate resin derived composite wave-absorbing material.
[ solution ]
The invention is realized by the following technical scheme.
The invention relates to a preparation method of a composite wave-absorbing material derived from metal acrylate resin.
The preparation method comprises the following preparation steps:
A. preparation of monomer mixture
The vinyl monomer, acrylic acid, methacrylic acid, acrylate monomer and methacrylate monomer are mixed according to a molar ratio of 10-60: 10-20: 0 to 20: 20-40: 0-40 to obtain a monomer mixture;
then, adding an initiator accounting for 0.8-3.2% of the weight of the monomer mixture into the monomer mixture, and uniformly mixing to obtain a monomer mixture containing the initiator;
B. acrylic prepolymer synthesis
Respectively adding a solvent accounting for 50-100% of the weight of the monomer mixture, a chain transfer agent accounting for 0.3-2.0% of the total weight of reactants, a monomer mixture containing the initiator and obtained in the step A accounting for 10-20% of the weight of the monomer mixture, stirring, introducing nitrogen into the three-neck flask for 10-30 minutes, controlling the temperature of the reaction mixture to be 75-110 ℃ under the protection of nitrogen, dividing the rest monomer mixture containing the initiator into 9-19 parts, adding one part every 10-20 minutes, and reacting for 2-6 hours under the conditions to obtain a light yellow transparent viscous acrylic prepolymer;
C. synthesis of metal acrylate resin
Under the protection of nitrogen, cooling the acrylic prepolymer obtained in the step B to a temperature below 70 ℃, and then adding a metal oxide or hydroxide and an organic acid, wherein the adding amount of the metal oxide or hydroxide and the organic acid is 1-2 times of the total molar amount of acrylic acid and methacrylic acid, and the weight ratio of the metal oxide or hydroxide to the organic acid is 1: 0.5 to 2.0; then adding a mixed solvent which is equal to the total weight of the metal oxide or hydroxide and the organic acid, uniformly mixing, reacting for 2-6 hours at the temperature of 75-110 ℃, then heating to the azeotropic temperature for dehydration until no distilled water is discharged, thus obtaining the metal acrylate resin;
D. preparation of metal acrylate resin wave-absorbing material
And C, placing the metal acrylate resin obtained in the step C in a crucible, removing the solvent contained in the metal acrylate resin at the temperature of 120-130 ℃ under the vacuum condition, then placing the metal acrylate resin in a tubular furnace, heating to 250-350 ℃ under the condition of the heating rate of 2-5 ℃/min in the nitrogen protective atmosphere, preserving heat for 1-2 hours, continuing heating to 600-1000 ℃, preserving heat for 1-2 hours, then cooling to room temperature, and grinding to obtain the metal acrylate resin derived composite wave-absorbing material.
According to a preferred embodiment of the present invention, in step a, the acrylate monomer is one or more acrylates selected from the group consisting of methyl acrylate, ethyl acrylate, hydroxyethyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, hydroxybutyl acrylate, isooctyl acrylate, lauryl acrylate, and stearyl acrylate;
the methacrylate monomer is one or more of methacrylate selected from methyl methacrylate, ethyl methacrylate, hydroxyethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, hydroxybutyl methacrylate, isooctyl methacrylate, lauryl methacrylate or octadecyl methacrylate;
the vinyl monomer is one or more vinyl monomers selected from acrylonitrile, styrene, vinyl acetate or divinylbenzene.
According to another preferred embodiment of the present invention, in step A, the initiator is one or more initiators selected from the group consisting of azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate, benzoyl peroxide tert-butyl ester, methyl ethyl ketone peroxide, ammonium persulfate and potassium persulfate.
According to another preferred embodiment of the present invention, in step B, the chain transfer agent is n-dodecyl mercaptan, t-dodecyl mercaptan or an aliphatic mercaptan.
According to another preferred embodiment of the present invention, the solvent in step B and step C is one or more solvents selected from the group consisting of toluene, xylene, n-butanol, butyl acetate, ethyl acetate, cyclohexanone, or methyl isobutyl ketone.
According to another preferred embodiment of the present invention, in step C, the metal oxide is one or more metal oxides selected from zinc oxide, copper oxide, magnesium oxide or calcium oxide; the metal hydroxide is one or more metal hydroxides selected from zinc hydroxide, copper hydroxide, iron hydroxide, magnesium hydroxide or calcium hydroxide; the organic acid is one or more organic acids selected from benzoic acid, naphthenic acid, stearic acid, lauric acid, acetic acid, propionic acid, butyric acid, abietic acid, proline, leucine, phenylalanine, arginine, dimerized abietic acid, disproportionated abietic acid, salicylic acid, furoic acid or p-chlorobenzoic acid.
According to another preferred embodiment of the invention, in the step D, the metal acrylate resin obtained in the step C is heated to 600-1000 ℃ in a tubular furnace in a nitrogen protective atmosphere at a heating rate of 2-5 ℃/min, then is kept at the temperature for 1-2 hours, then is cooled to room temperature, and is ground, so as to obtain the metal acrylate resin derived composite wave-absorbing material.
According to another preferred embodiment of the present invention, in step C, the metal acrylate resin has the following structural formula:
Figure BDA0003005583090000041
in the formula:
R1is H or CH3；
R2Is CH3、CH2CH3、CH2CH2CH3、CH(CH3)2、CH2CH(CH3)2、C(CH3)3、CH2CH2OH、CH2CH(CH3)OH、(CH2)3CH3、(CH2)4CH3、(CH2)5CH3、(CH2)6CH3、(CH2)7CH3、(CH2)8CH3、(CH2)9CH3、(CH2)10CH3、(CH2)11CH3、(CH2)17CH3；
R3Is H, CH3Or CH2COO-X-R4；
X is Zn, Cu, Fe, Ca or Mg metal ion;
R4is acid radical of benzoic acid, naphthenic acid, stearic acid, lauric acid, acetic acid, propionic acid, butyric acid, abietic acid, proline, leucine, phenylalanine or arginine, dimerized abietic acid, disproportionated abietic acid, salicylic acid and p-chlorobenzoic acid;
R5is OOCCH3、C6H5、C6H4-(CH-CH2)xOr CN;
the number average molecular weight of the metal acrylate resin is 2000-60000, and the molecular weight distribution is 1-2.5.
The invention also relates to the metal acrylate resin derived composite wave-absorbing material prepared by the preparation method, which has excellent wave-absorbing performance within the wavelength of 2-40 GHz.
According to a preferred embodiment of the present invention, the composite wave-absorbing material is composed of a carbon matrix and metal particles, and the metal particles are embedded in the carbon material in a random manner.
The present invention will be described in more detail below.
The invention relates to a preparation method of a composite wave-absorbing material derived from metal acrylate resin.
The preparation method comprises the following preparation steps:
A. preparation of monomer mixture
The vinyl monomer, acrylic acid, methacrylic acid, acrylate monomer and methacrylate monomer are mixed according to a molar ratio of 10-60: 10-20: 0 to 20: 20-40: 0-40 to obtain a monomer mixture;
then, adding an initiator accounting for 0.8-3.2% of the weight of the monomer mixture into the monomer mixture, and uniformly mixing to obtain a monomer mixture containing the initiator;
in the invention, the main function of the vinyl monomer in preparing the metal acrylate derivative composite wave-absorbing material is to influence the structure and chemical properties of the wave-absorbing material, for example, the acrylonitrile monomer changes the electronegativity of the material by adding N atoms, and the dielectric loss is improved; the vinyl monomer used in the present invention is one or more vinyl monomers selected from acrylonitrile, styrene, vinyl acetate or divinylbenzene, which are currently commercially available products such as vinyl acetate under the trade name of national chemical agents, ltd.
The main function of the acrylic acid in the preparation of the acrylic acid prepolymer is to polymerize to form the main chain of the acrylic acid prepolymer and participate in the later dehydration condensation reaction with metal oxide or hydroxide; the acrylic acid used in the present invention is a product currently marketed, for example, by the Datang chemical Co., Ltd under the trade name acrylic acid.
The main function of methacrylic acid in the preparation of acrylic acid prepolymer is to adjust the hardness of the resin material; methacrylic acid used in the present invention is a product currently marketed, for example, by Datang chemical Co., Ltd under the trade name methacrylic acid.
The main function of the acrylate monomer in the preparation of the acrylic prepolymer is to change the length of a side chain and improve the foundation for constructing different carbon material structures in the later period; the acrylate monomer used in the present invention is one or more acrylates selected from the group consisting of methyl acrylate, ethyl acrylate, hydroxyethyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, hydroxybutyl acrylate, isooctyl acrylate, lauryl acrylate, and stearyl acrylate, which are currently commercially available products, such as ethyl acrylate sold under the trade name ethyl acrylate by down chemical limited, hydroxyethyl acrylate sold under the trade name hydroxyethyl acrylate by national chemical limited;
the main function of the methacrylate monomer in preparing the acrylic prepolymer is to change the hardness of the material and the length of a side chain; the methacrylate ester monomer used in the present invention is one or more methacrylate esters selected from the group consisting of methyl methacrylate, ethyl methacrylate, hydroxyethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, hydroxybutyl methacrylate, isooctyl methacrylate, lauryl methacrylate and stearyl methacrylate, which are currently commercially available products, such as methyl methacrylate sold under the trade name methyl methacrylate by national chemical Co., Ltd, butyl methacrylate sold under the trade name butyl methacrylate by Meditol chemical Co., Ltd;
the main function of the initiator in preparing the acrylic prepolymer is to decompose the initiator into active species to initiate the polymerization of monomers; the initiator used in the present invention is one or more initiators selected from azobisisobutyronitrile, azobisisoheptonitrile, azobisisobutyric acid dimethyl ester, benzoyl peroxide tert-butyl peroxide, methyl ethyl ketone peroxide, ammonium persulfate or potassium persulfate, all of which are currently marketed products, such as azobisisobutyronitrile sold under the trade name azobisisobutyronitrile by the majestic chemical plant of Tianjin, potassium persulfate sold under the trade name potassium persulfate by the Hedong redrock reagent plant of Tianjin;
in the present invention, when the amount of acrylic acid, methacrylic acid, acrylate ester monomer and methacrylate ester monomer is within the above range, if the amount of vinyl monomer is less than 10, the effect of improving the wave absorbing performance is not obtained; if the dosage of the vinyl monomer is higher than 60, the chemical property and the wave absorbing property of the material are affected, for example, the dielectric loss caused by overhigh electronegativity is overhigh; therefore, the use amount of the vinyl monomer is 10-60 reasonably;
when the dosage of the vinyl monomer, the methacrylic acid, the acrylate monomer and the methacrylate monomer is in the range, if the dosage of the acrylic acid is less than 10, the metal ions introduced in the later period are too little, and the wave absorbing performance of the composite material is reduced; if the dosage of the acrylic acid is higher than 20, the contents of metal and organic acid participating in the dehydration condensation reaction are too high, the viscosity is too high, the agglomeration phenomenon occurs, and the reaction cannot be normally carried out; therefore, the amount of acrylic acid is preferably 10 to 20;
when the vinyl monomer, acrylic acid, acrylate monomer and methacrylate monomer are used in the above-mentioned ranges, methacrylic acid may not be used because the effects of methacrylic acid and acrylic acid are largely similar and methacrylic acid is harder than acrylic acid; of course, the use of a small amount of methacrylic acid is advantageous for adjusting the hardness of the resin material; if the amount of the methacrylic acid is more than 20, the viscosity of the polymer is too high, and agglomeration is caused, which is not favorable for normal reaction; therefore, the amount of acrylic acid is preferably 0 to 20;
when the amount of the vinyl monomer, the acrylic acid, the methacrylic acid and the methacrylate monomer is in the range, if the amount of the acrylate monomer is less than 20, the length and the flexibility of a molecular chain cannot be well adjusted; if the dosage of the acrylate monomer is higher than 40, the content of other components can be reduced, which is not beneficial to later construction of the composite wave-absorbing material with reasonable structure; therefore, the amount of the acrylate monomer is preferably 20 to 40;
when the vinyl monomer, acrylic acid, methacrylic acid and acrylate monomer are used in the above-mentioned ranges, the methacrylate monomer may not be used because the methacrylate monomer has a great similarity in action with the acrylate monomer and is harder than the acrylate monomer; of course, the use of a small amount of methacrylate monomer is advantageous for adjusting the material hardness and the side chain length; if the dosage of the methacrylate monomer is higher than 40, the content of other components can be reduced, which is not beneficial to coordinating the wave-absorbing performance of the material; therefore, the amount of the methacrylate monomer is preferably 0 to 40;
in the present invention, the amount of the initiator exceeding the range is not preferable, because too small amount of the initiator results in incomplete polymerization of the acrylic resin, and too large amount of the initiator results in low viscosity and short molecular chain of the acrylic resin, which is not favorable for the construction of the carbon material in the later stage.
B. Acrylic prepolymer synthesis
Respectively adding a solvent accounting for 50-100% of the weight of the monomer mixture into a three-neck flask, adding a chain transfer agent accounting for 0.3-2.0% of the total weight of reactants, adding the monomer mixture containing the initiator obtained in the step A accounting for 10-20% of the weight of the monomer mixture, stirring, introducing nitrogen into the three-neck flask for 10-30 minutes, controlling the temperature of the reaction mixture to be 75-110 ℃ under the protection of nitrogen, dividing the rest monomer mixture containing the initiator into 7-10 parts, adding one part every 10-20 minutes, and reacting for 2-6 hours under the conditions to obtain a light yellow transparent viscous acrylic prepolymer;
the acrylic prepolymer synthesis step is mainly aimed at synthesizing the carbon skeleton of the composite material precursor by means of free radical polymerization.
According to the invention, the chain transfer agent has the main function of enabling chain-extending free radicals to generate free radical transfer in the synthesis of the acrylic prepolymer and adjusting the molecular weight of the polymer.
The chain transfer agent used in the present invention is a chain transfer agent of n-dodecyl mercaptan, t-dodecyl mercaptan or aliphatic mercaptan, which are currently commercially available products, such as n-dodecyl mercaptan sold under the trade name of n-dodecyl mercaptan by national chemical Co.
In the present invention, if the amount of the chain transfer agent is less than 0.3%, it may result in difficulty in terminating the radical polymerization; if the amount of the chain transfer agent is more than 2.0%, the viscosity of the polymer is lowered and the molecular chain is too short; therefore, the amount of the chain transfer agent is suitably 0.3 to 2.0%, preferably 0.6 to 1.6%, more preferably 0.9 to 1.4%;
the solvent used in the present invention is one or more solvents selected from the group consisting of toluene, xylene, n-butanol, butyl acetate, ethyl acetate, cyclohexanone or methyl isobutyl ketone, which are currently commercially available products such as n-butanol sold under the name of n-butanol by national chemical agents co.
In the present invention, it is not preferable to use the solvent in an amount exceeding the range, because too much solvent not only causes air pollution but also causes waste of the solvent.
In the step, the temperature of the reaction mixture is controlled to be 75-110 ℃, and if the temperature of the reaction mixture is lower than 75 ℃, the initiation of monomer polymerization is not facilitated; if the temperature of the reaction mixture is above 110 ℃, the reactive species may be rendered ineffective; therefore, the temperature of the reaction mixture is suitably 75 to 110 ℃, preferably 85 to 100 ℃, more preferably 88 to 96 ℃;
in the invention, the residual monomer mixture containing the initiator is divided into 9-19 parts and put into reaction, and the main purpose is to avoid agglomeration caused by excessive single addition or explosion caused by excessive local temperature;
the product obtained in this preparation step is an acrylic prepolymer which the inventors wished to obtain, as measured by conventional fourier transform infrared analysis detection method.
The three-necked flask used in this step is a three-necked flask equipped with a stirrer and a condenser tube, which is commonly used in the art.
C. Synthesis of metal acrylate resin
Under the protection of nitrogen, cooling the acrylic prepolymer obtained in the step B to a temperature below 70 ℃, and then adding a metal oxide or hydroxide and an organic acid, wherein the adding amount of the metal oxide or hydroxide and the organic acid is 1-2 times of the total molar amount of acrylic acid and methacrylic acid, and the weight ratio of the metal oxide or hydroxide to the organic acid is 1: 0.5 to 2.0; then adding a mixed solvent which is equal to the total weight of the metal oxide or hydroxide and the organic acid, uniformly mixing, reacting for 2-6 hours at the temperature of 75-110 ℃, then heating to the azeotropic temperature for dehydration until no distilled water is discharged, thus obtaining the metal acrylate resin;
in this step, the acrylic prepolymer, metal oxide or hydroxide and organic acid are reacted as follows:
-COOH+X-OH+-COOH＝-COO-X-OOC-+H2O；
the metal oxide is one or more metal oxides selected from zinc oxide, copper oxide, magnesium oxide or calcium oxide; the metal hydroxide is one or more metal hydroxides selected from zinc hydroxide, copper hydroxide, iron hydroxide, magnesium hydroxide or calcium hydroxide.
The organic acid is one or more organic acids selected from benzoic acid, naphthenic acid, stearic acid, lauric acid, acetic acid, propionic acid, butyric acid, abietic acid, proline, leucine, phenylalanine, arginine, dimerized abietic acid, disproportionated abietic acid, salicylic acid, furoic acid, or p-chlorobenzoic acid, which are currently commercially available products, such as stearic acid sold under the trade name stearic acid by national chemical agents ltd, and benzoic acid sold under the trade name benzoic acid by shanghai chemical agents ltd.
In the invention, the addition amount of the metal oxide or hydroxide and the organic acid is 1-2 times of the total molar amount of the acrylic acid and the methacrylic acid, which is to ensure the full progress of the dehydration condensation reaction;
the weight ratio of metal oxide or hydroxide to organic acid is 1: 0.5-2.0, if the weight ratio exceeds the range, the weight ratio is not allowed, because the full reaction of the two is ensured as much as possible, and the excessive content can cause a large amount of organic acid monomer substances to remain in the polymer solution;
in this step, the essential role of cooling the acrylic prepolymer obtained in step B to a temperature of 70 ℃ or lower is to prevent the temperature from being so high that a vigorous reaction occurs when other substances are added thereto;
the product obtained in the preparation step is metal acrylate resin detected by a conventional Fourier transform infrared analysis detection method.
The structural formula of the metal acrylate resin is as follows:
Figure BDA0003005583090000101
in the formula:
R1is H or CH3；
R2Is CH3、CH2CH3、CH2CH2CH3、CH(CH3)2、CH2CH(CH3)2、C(CH3)3、CH2CH2OH、CH2CH(CH3)OH、(CH2)3CH3、(CH2)4CH3、(CH2)5CH3、(CH2)6CH3、(CH2)7CH3、(CH2)8CH3、(CH2)9CH3、(CH2)10CH3、(CH2)11CH3、(CH2)17CH3；
R3Is H, CH3Or CH2COO-X-R4；
X is a metal ion, such as Zn, Cu, Fe, Ca, Mg;
R4is acid radical of benzoic acid, naphthenic acid, stearic acid, lauric acid, acetic acid, propionic acid, butyric acid, abietic acid, proline, leucine, phenylalanine or arginine, dimerized abietic acid, disproportionated abietic acid, salicylic acid and p-chlorobenzoic acid;
R5is OOCCH3、C6H5、C6H4-(CH-CH2)xOr CN;
the number average molecular weight of the metal acrylate resin is 2000-60000 and the molecular weight distribution is 1-2.5 according to the detection of a conventional gel permeation chromatography standard method.
D. Preparation of metal acrylate resin wave-absorbing material
And C, placing the metal acrylate resin obtained in the step C in a crucible, removing the solvent contained in the metal acrylate resin at the temperature of 120-130 ℃ under the vacuum condition, then placing the metal acrylate resin in a tubular furnace, heating to 250-350 ℃ under the condition of the heating rate of 2-5 ℃/min in the nitrogen protective atmosphere, preserving heat for 1-2 hours, continuing heating to 600-1000 ℃, preserving heat for 1-2 hours, then cooling to room temperature, and grinding to obtain the metal acrylate resin derived composite wave-absorbing material.
Or, heating the metal acrylate resin obtained in the step C to 600-1000 ℃ in a tubular furnace in a nitrogen protective atmosphere at a heating rate of 2-5 ℃/min, preserving the heat for 1-2 hours, cooling to room temperature, and grinding to obtain the metal acrylate resin derived composite wave-absorbing material.
In the step, before the metal acrylate resin obtained in the step C enters a tube furnace for high-temperature calcination, the metal acrylate resin must be dried in a vacuum drying oven at 120-130 ℃ under vacuum to remove volatile gas, so as to avoid danger in the high-temperature calcination process;
the invention adopts a carbonization mode of firstly carrying out low temperature of 250-350 ℃ and then carrying out high temperature of 600-1000 ℃ to slowly carbonize the material and reserve the basic structure of the carbon skeleton as far as possible.
The tube furnace used in the present invention is a tube furnace generally used in the art, for example, a tube furnace sold under the trade name of open vacuum/atmosphere tube electric furnace by Tianjin medium-ring electric furnace Co.
The product obtained by the production method of the present invention was analyzed under conventional analysis conditions by a conventional fourier transform infrared analysis method using an apparatus sold under the trade name fourier transform infrared spectrometer by bruker, germany, and as a result, it was confirmed that the obtained product satisfied the structural conditions of the metal acrylate resin, thereby confirming that it was a metal acrylate resin which the present inventors designed to synthesize.
The invention also relates to the composite wave-absorbing material derived from the metal acrylate resin prepared by the preparation method.
According to a coaxial method or a waveguide method and a transmission line theory, an Agilent E5224APNA vector network analyzer is used for detecting, and the wave absorbing performance of the wave absorbing material in the wavelength of 2-40 GHz is that the minimum reflection loss is-20.35 dB to-43.15 dB and the effective absorption bandwidth is 2.65-4.26 GHz when the addition amount of the wave absorbing material is 14.3-25% and the matching thickness is 3.0 mm.
The product obtained by the production method of the present invention was analyzed under conventional analysis conditions by scanning electron microscope analysis using an apparatus sold by Hitachi under the trade name of S-4800 scanning electron microscope, and the result is shown in fig. 2, whereby it was confirmed to be a composite material having no fixed morphology, consisting of a carbon matrix and metal particles which were embedded in the carbon material in a random manner.
[ advantageous effects ]
The invention has the beneficial effects that:
compared with the prior art, the precursor used in the invention is metal acrylate resin, and the raw materials are easy to obtain, the price is low and the synthesis process is mature; the composite wave-absorbing material derived from the metal acrylate resin prepared by the invention is simple to operate and low in preparation cost, the existing process conditions support large-scale production, and the composite wave-absorbing material of carbon materials and metal particles can be obtained directly by calcining the metal acrylate resin. Compared with the existing wave-absorbing material, the metal acrylate resin derived composite wave-absorbing material prepared by the embodiment has excellent wave-absorbing performance of small density and strong wave-absorbing performance, and when the addition amount is 25% and the thickness is 3.0mm, the minimum reflection loss energy reaches-43.15 dB. In addition, the wave absorbing performance of the product can be controlled by simply adjusting the proportions and types of the monomer, the initiator, the chain transfer agent and the metal ions. The preparation method provided by the invention provides a new idea for preparing the high-performance and large-scale carbon-based composite wave-absorbing material containing the metal particles.
[ description of the drawings ]
FIG. 1 is an infrared spectrum of the zinc acrylate resin and the derivative composite wave-absorbing material thereof prepared in example 1;
FIG. 2 is an SEM topography of the metal acrylate resin derived composite wave-absorbing material prepared in examples 1-4;
FIG. 3 is an SEM topography and a corresponding element mapping of the zinc acrylate resin derived composite wave-absorbing material prepared in example 1;
FIG. 4 is a reflection loss chart of the metal acrylate resin derived composite wave-absorbing material prepared in example 1;
FIG. 5 is a reflection loss chart of the metal acrylate resin derived composite wave-absorbing material prepared in example 2;
FIG. 6 is a reflection loss chart of the metal acrylate resin derived composite wave-absorbing material prepared in example 3;
FIG. 7 is a reflection loss chart of the metal acrylate resin derived composite wave-absorbing material prepared in example 4;
in fig. 7:
a is a reflection loss chart of the composite wave-absorbing material prepared in the embodiment 4 and paraffin in the mixing ratio of 1: 3;
b is a reflection loss chart of the composite wave-absorbing material prepared in the embodiment 4 and paraffin in the mixing ratio of 1: 6.
[ detailed description ] embodiments
The invention will be better understood from the following examples.
Example 1: preparation of metal acrylate resin derived composite wave-absorbing material
The implementation steps of this example are as follows:
A. preparation of monomer mixture
Vinyl acetate, acrylic acid, methacrylic acid and butyl acrylate monomers in a molar ratio of 40: 20: 0: 40 to obtain a monomer mixture;
then, adding 2.6 percent of azodiisoheptanonitrile initiator based on the weight of the monomer mixture into the monomer mixture, and uniformly mixing to obtain a monomer mixture containing the initiator;
B. acrylic prepolymer synthesis
Adding a xylene solvent into a three-neck flask according to 50 percent of the weight of the monomer mixture, adding an n-dodecyl mercaptan chain transfer agent into the three-neck flask according to 0.3 percent of the total weight of reactants, adding the monomer mixture containing the initiator obtained in the step A according to 10 percent of the weight of the monomer mixture, stirring, introducing nitrogen into the three-neck flask for 25 minutes, controlling the temperature of the reaction mixture to be 75 ℃ under the protection of nitrogen, dividing the rest monomer mixture containing the initiator into 7 parts, adding the parts every 15 minutes, and reacting for 5 hours under the conditions to obtain a light yellow transparent viscous acrylic prepolymer;
C. synthesis of metal acrylate resin
Under the protection of nitrogen, cooling the acrylic prepolymer obtained in the step B to a temperature below 70 ℃, and then adding zinc oxide and benzoic acid organic acid, wherein the adding amount of the zinc oxide and the benzoic acid organic acid is 1.6 times of the total molar amount of acrylic acid and methacrylic acid, and the weight ratio of the metal oxide to the organic acid is 1: 1; then adding a mixed solvent of toluene and xylene (volume ratio is 1: 2) which is equal to the total weight of the metal oxide and the organic acid, uniformly mixing, reacting for 6 hours at the temperature of 85 ℃, then heating to an azeotropic temperature for dehydration until no distilled water is discharged, thus obtaining the metal acrylate resin;
D. preparation of metal acrylate resin wave-absorbing material
And C, placing the metal acrylate resin obtained in the step C in a crucible, removing the solvent contained in the metal acrylate resin under the conditions of 125 ℃ and vacuum, then placing the metal acrylate resin in a tube furnace, heating the metal acrylate resin to 300 ℃ under the condition of a heating rate of 4 ℃/min in a nitrogen protective atmosphere, preserving the heat for 1.0 hour, continuing to heat to 600 ℃, preserving the heat for 2.0 hours, then cooling to room temperature, and grinding, wherein the product prepared in the embodiment is the metal acrylate resin derived composite wave-absorbing material, the analysis result of the composite wave-absorbing material is shown in the attached figure 1, the SEM appearance diagram of the composite wave-absorbing material is shown in the attached figure 2a, and the SEM appearance diagram of the composite wave-absorbing material and the corresponding element mapping diagram are shown in the attached figure 3.
The metal acrylate resin derived composite wave-absorbing material prepared in the embodiment is uniformly mixed with paraffin according to the weight ratio of 1:5 (the addition amount of the wave-absorbing material is 16.7 percent), a coaxial ring shape with the inner diameter of 3.04mm and the outer diameter of 7.00mm is prepared, then an Agilent E5224APNA vector network analyzer is utilized to test the complex dielectric constant and the magnetic permeability value in the frequency range of 2-18GHz by adopting a coaxial method, the reflection loss graph of the metal acrylate resin derived composite wave-absorbing material is calculated according to the transmission line theory, and the result is shown in figure 4. As can be seen from FIG. 4, under the conditions of matching thickness of 3.0mm and frequency of 10.32GHz, the minimum reflection loss is-34.66 dB, and the effective bandwidth is 2.65GHz (9.08-11.73 GHz).
Example 2: preparation of metal acrylate resin derived composite wave-absorbing material
The implementation steps of this example are as follows:
A. preparation of monomer mixture
Acrylonitrile, acrylic acid, methacrylic acid, ethyl acrylate and butyl methacrylate acrylate monomers in a molar ratio of 30: 14: 0: 35: 21 mixing to obtain a monomer mixture;
then, adding benzoyl peroxide initiator accounting for 1.2 percent of the weight of the monomer mixture into the monomer mixture, and uniformly mixing to obtain a monomer mixture containing the initiator;
B. acrylic prepolymer synthesis
Respectively adding an n-butyl alcohol solvent accounting for 66 percent of the weight of the monomer mixture, a tert-dodecyl mercaptan chain transfer agent accounting for 0.9 percent of the total weight of reactants, adding the monomer mixture containing the initiator obtained in the step A accounting for 14 percent of the weight of the monomer mixture, stirring, introducing nitrogen into the three-neck flask for 20 minutes, controlling the temperature of the reaction mixture to be 85 ℃ under the protection of nitrogen, dividing the rest monomer mixture containing the initiator into 8 parts, adding the parts every 20 minutes, and reacting for 2 hours under the conditions to obtain a light yellow transparent viscous acrylic prepolymer;
C. synthesis of metal acrylate resin
Under the protection of nitrogen, cooling the acrylic prepolymer obtained in the step B to a temperature below 70 ℃, and then adding zinc oxide metal oxide and benzoic acid organic acid, wherein the adding amount of the zinc oxide metal oxide and the benzoic acid organic acid is 1.0 time of the total molar amount of acrylic acid and methacrylic acid, and the weight ratio of the metal oxide to the organic acid is 1: 2; then adding a mixed solvent of a mixture of xylene and n-butanol (the volume ratio is 1: 3) which is equal to the total weight of the metal oxide and the organic acid, uniformly mixing, reacting for 4 hours at the temperature of 80 ℃, then heating to the azeotropic temperature for dehydration until no distilled water is discharged, thus obtaining the metal acrylate resin;
D. preparation of metal acrylate resin wave-absorbing material
And C, placing the metal acrylate resin obtained in the step C in a crucible, removing the solvent contained in the metal acrylate resin under the conditions of 125 ℃ and vacuum, then placing the metal acrylate resin in a tube furnace, heating to 250 ℃ under the condition of a heating rate of 2 ℃/min in the nitrogen protection atmosphere, preserving heat for 2.0 hours, continuing to heat to 800 ℃, preserving heat for 1.6 hours, then cooling to room temperature, grinding, and detecting according to the method described in the specification of the application, wherein the product prepared in the embodiment is the metal acrylate resin derived composite wave-absorbing material, and the SEM appearance of the product is shown in the attached figure 2 b.
The metal acrylate resin derived composite wave-absorbing material prepared in the embodiment is uniformly mixed with paraffin according to the weight ratio of 1:3 (the adding amount of the composite material is 25 percent), a coaxial ring shape with the inner diameter of 3.04mm and the outer diameter of 7.00mm is prepared, then an Agilent E5224A PNA vector network analyzer is utilized, the complex dielectric constant and the magnetic permeability value of the composite wave-absorbing material in the frequency range of 2-18GHz are tested by adopting a coaxial method, the reflection loss graph of the metal acrylate resin derived composite wave-absorbing material is calculated according to the transmission line theory, and the result is shown in figure 5. As can be seen from FIG. 5, the minimum reflection loss is-43.15 dB and the effective bandwidth is 2.83GHz (8.56-11.39GHz) under the conditions of matching thickness of 3.0mm and frequency of 9.68 GHz.
Example 3: preparation of metal acrylate resin derived composite wave-absorbing material
The implementation steps of this example are as follows:
A. preparation of monomer mixture
Acrylonitrile, acrylic acid, methacrylic acid, ethyl acrylate and butyl acrylate monomers in a molar ratio of 20: 10: 10: 40: 20 to obtain a monomer mixture;
then, adding a methyl ethyl ketone peroxide initiator accounting for 0.4 percent of the weight of the monomer mixture into the monomer mixture, and uniformly mixing to obtain a monomer mixture containing the initiator;
B. acrylic prepolymer synthesis
Adding an ethyl acetate solvent according to 82 percent of the weight of the monomer mixture, adding an aliphatic thiol chain transfer agent according to 1.4 percent of the total weight of reactants, adding the monomer mixture containing the initiator obtained in the step A according to 17 percent of the weight of the monomer mixture, stirring, introducing nitrogen into the three-neck flask for 30 minutes, controlling the temperature of the reaction mixture at 110 ℃ under the protection of nitrogen, dividing the rest monomer mixture containing the initiator into 10 parts, adding the parts every 14 minutes, and reacting for 3 hours under the conditions to obtain a light yellow transparent viscous acrylic prepolymer;
C. synthesis of metal acrylate resin
Under the protection of nitrogen, cooling the acrylic prepolymer obtained in the step B to a temperature below 70 ℃, and then adding a zinc hydroxide metal hydroxide mixture and benzoic acid organic acid, wherein the adding amount of the zinc hydroxide metal hydroxide mixture and the benzoic acid organic acid is 1.2 times of the total molar amount of acrylic acid and methacrylic acid, and the weight ratio of the metal hydroxide to the organic acid is 1: 1.5; then adding a mixed solvent of ethyl acetate and cyclohexanone mixture (volume ratio is 3: 1) which is equal to the total weight of the metal hydroxide and the organic acid, uniformly mixing, reacting for 3 hours at the temperature of 98 ℃, then heating to the azeotropic temperature for dehydration until no distilled water is discharged, thus obtaining the metal acrylate resin;
D. preparation of metal acrylate resin wave-absorbing material
And C, placing the metal acrylate resin obtained in the step C in a crucible, removing the solvent contained in the metal acrylate resin under the conditions of 124 ℃ and vacuum, then placing the metal acrylate resin in a tube furnace, heating to 280 ℃ under the condition of a heating rate of 3 ℃/min in a nitrogen protective atmosphere, preserving heat for 1.8 hours, continuing to heat to 900 ℃, preserving heat for 1.3 hours, then cooling to room temperature, grinding, detecting according to the method described in the specification of the application, wherein the product prepared in the embodiment is the metal acrylate resin derived composite wave-absorbing material, and the SEM appearance of the product is shown in an attached figure 2C.
The metal acrylate resin derived composite wave-absorbing material prepared in the embodiment is uniformly mixed with paraffin according to the weight ratio of 1:3 (the adding amount of the composite material is 25%), a coaxial ring shape with the inner diameter of 3.04mm and the outer diameter of 7.00mm is prepared, then an Agilent E5224A PNA vector network analyzer is utilized, the complex dielectric constant and the magnetic permeability value of the metal acrylate resin derived composite wave-absorbing material in the frequency range of 2-18GHz are tested by a coaxial method, and the reflection loss graph of the metal acrylate resin derived composite wave-absorbing material is calculated according to the transmission line theory, and the result is shown in figure 6. As can be seen from FIG. 6, under the conditions of matching thickness of 2.5mm and frequency of 8.72GHz, the minimum reflection loss is-33.70 dB, and the effective bandwidth is 2.38GHz (8.03-10.41 GHz).
Example 4: preparation of metal acrylate resin derived composite wave-absorbing material
The implementation steps of this example are as follows:
A. preparation of monomer mixture
Acrylonitrile monomer, acrylic acid, methacrylic acid, octadecyl acrylate monomer and hydroxyethyl methacrylate monomer according to a molar ratio of 20: 16: 0: 40: 24 to obtain a monomer mixture;
then, adding 3.2% of ammonium persulfate initiator by weight of the monomer mixture into the monomer mixture, and uniformly mixing to obtain a monomer mixture containing the initiator;
B. acrylic prepolymer synthesis
Adding cyclohexanone solvent into a three-neck flask according to 100 percent of the weight of the monomer mixture, adding n-dodecyl mercaptan chain transfer agent into the three-neck flask according to 2.0 percent of the total weight of reactants, adding the monomer mixture containing the initiator obtained in the step A according to 20 percent of the weight of the monomer mixture, stirring, introducing nitrogen into the three-neck flask for 18 minutes, controlling the temperature of the reaction mixture to be 100 ℃ under the protection of nitrogen, dividing the rest monomer mixture containing the initiator into 9 parts, adding the parts every 16 minutes, and reacting for 6 hours under the conditions to obtain a light yellow transparent viscous acrylic prepolymer;
C. synthesis of metal acrylate resin
Under the protection of nitrogen, cooling the acrylic prepolymer obtained in the step B to a temperature below 70 ℃, and then adding zinc hydroxide, a mixture of iron hydroxide metal hydroxides and dimerized abietic acid organic acid, wherein the adding amount of the zinc hydroxide, the iron hydroxide metal hydroxides and the dimerized abietic acid organic acid is 2.0 times of the total molar amount of acrylic acid and methacrylic acid, and the weight ratio of the metal hydroxides to the organic acid is 1: 2; then adding a mixed solvent of toluene and methyl isobutyl ketone mixture (volume ratio is 2: 1) which is equal to the total weight of the metal hydroxide and the organic acid, uniformly mixing, reacting for 2 hours at the temperature of 110 ℃, and then heating to the azeotropic temperature for dehydration until no distilled water is discharged, thus obtaining the metal acrylate resin;
D. preparation of metal acrylate resin wave-absorbing material
And C, placing the metal acrylate resin obtained in the step C in a crucible, removing the solvent contained in the metal acrylate resin under the conditions of 130 ℃ and vacuum, then placing the metal acrylate resin in a tube furnace, heating to 310 ℃ under the condition of a heating rate of 5 ℃/min in a nitrogen protective atmosphere, preserving heat for 1.5 hours, continuing to heat to 1000 ℃, preserving heat for 1.0 hour, then cooling to room temperature, grinding, detecting according to the method described in the specification of the application, wherein the product prepared in the embodiment is the metal acrylate resin derived composite wave-absorbing material, and the SEM appearance of the product is shown in an attached figure 2 d.
The metal acrylate resin derived composite wave-absorbing material prepared in the embodiment and paraffin are mixed according to the weight ratio of 1:6 and 1:3 (the addition amount of the composite material is 14.3 percent and 25 percent) are uniformly mixed to prepare a coaxial ring shape with the inner diameter of 3.04mm and the outer diameter of 7.00mm, then an Agilent E5224A PNA vector network analyzer is utilized to test the complex dielectric constant and the magnetic permeability value of the composite wave-absorbing material in the frequency range of 2-18GHz by a coaxial method, and the reflection loss graph of the metal acrylate resin derived composite wave-absorbing material is calculated according to the transmission line theory, and the result is shown in figure 7. As shown in FIG. 7a, under the conditions of matching thickness of 2.0mm and frequency of 14.16GHz, the minimum reflection loss is-32.60 dB, and the effective bandwidth is 4.26GHz (12.09-16.35 GHz). As shown in FIG. 7b, under the conditions of matching thickness of 2.5mm and frequency of 10.00GHz, the minimum reflection loss is-37.24 dB, and the effective bandwidth is 3.00GHz (8.74-11.74 GHz).
At present, the carbon/metal composite wave-absorbing material synthesized by the above process is not found, and the same analysis method is adopted for the carbon nano tube/TiO2The composite wave-absorbing material (documents Mo Z, Yang R, Lu D, Yang L, Hu Q, Li H, et al Lightweight, and three-dimensional carbon Nanotube @ TiO2 span with enhanced microwave absorption performance. CARBON.2019; 144:433-9.) is compared at 2-18GHz, and the result is that the minimum reflection loss is-31.8 dB and the effective bandwidth is 2.76GHz (9.24-12.0GHz) under the conditions of the optimal component ratio (30 percent of the added wave-absorbing material), the thickness is 2.0mm and the frequency is 10.35 GHz.
The metal acrylate resin derived composite wave-absorbing material prepared by the embodiment has excellent wave-absorbing performance, and the minimum reflection loss energy reaches-43.15 dB when the addition amount is 25% and the thickness is 3.0 mm.

Claims (9)

1. A preparation method of a composite wave-absorbing material derived from metal acrylate resin is characterized by comprising the following preparation steps:
A. preparation of monomer mixture
The vinyl monomer, acrylic acid, methacrylic acid, acrylate monomer and methacrylate monomer are mixed according to a molar ratio of 10-60: 10-20: 0 to 20: 20-40: 0-40 to obtain a monomer mixture;
then, adding an initiator accounting for 0.8-3.2% of the weight of the monomer mixture into the monomer mixture, and uniformly mixing to obtain a monomer mixture containing the initiator;
B. acrylic prepolymer synthesis
Respectively adding a solvent accounting for 50-100% of the weight of the monomer mixture, a chain transfer agent accounting for 0.3-2.0% of the total weight of reactants, a monomer mixture containing the initiator and obtained in the step A accounting for 10-20% of the weight of the monomer mixture, stirring, introducing nitrogen into the three-neck flask for 10-30 minutes, controlling the temperature of the reaction mixture to be 75-110 ℃ under the protection of nitrogen, dividing the rest monomer mixture containing the initiator into 9-19 parts, adding one part every 10-20 minutes, and reacting for 2-6 hours under the conditions to obtain a light yellow transparent viscous acrylic prepolymer;
C. synthesis of metal acrylate resin
Under the protection of nitrogen, cooling the acrylic prepolymer obtained in the step B to a temperature below 70 ℃, and then adding a metal oxide or hydroxide and an organic acid, wherein the addition amount of the metal oxide or hydroxide and the organic acid is 1-2 times of the total molar amount of acrylic acid and methacrylic acid, and the weight ratio of the metal oxide or hydroxide to the organic acid is 1: 0.5 to 2.0; then adding a mixed solvent which is equal to the total weight of the metal oxide or hydroxide and the organic acid, uniformly mixing, reacting for 2-6 hours at the temperature of 75-110 ℃, then heating to the azeotropic temperature for dehydration until no distilled water is discharged, thus obtaining the metal acrylate resin;
the structural formula of the metal acrylate resin is as follows:
Figure FDA0003589590930000021
in the formula:
R1is H or CH3；
R2Is CH3、CH2CH3、CH2CH2CH3、CH(CH3)2、CH2CH(CH3)2、C(CH3)3、CH2CH2OH、CH2CH(CH3)OH、(CH2)3CH3、(CH2)4CH3、(CH2)5CH3、(CH2)6CH3、(CH2)7CH3、(CH2)8CH3、(CH2)9CH3、(CH2)10CH3、(CH2)11CH3、(CH2)17CH3；
R3Is H, CH3Or CH2COO-X-R4；
X is Zn, Cu, Fe, Ca or Mg metal ion;
R4is acid radical of benzoic acid, naphthenic acid, stearic acid, lauric acid, acetic acid, propionic acid, butyric acid, abietic acid, proline, leucine, phenylalanine or arginine, dimerized abietic acid, disproportionated abietic acid, salicylic acid or p-chlorobenzoic acid;
R5is OOCCH3、C6H5、C6H4-(CH-CH2) x or CN;
the number average molecular weight of the metal acrylate resin is 2000-60000, and the molecular weight distribution is 1-2.5;
D. preparation of metal acrylate resin wave-absorbing material
And C, placing the metal acrylate resin obtained in the step C in a crucible, removing the solvent contained in the metal acrylate resin at the temperature of 120-130 ℃ under the vacuum condition, then placing the metal acrylate resin in a tubular furnace, heating to 250-350 ℃ under the condition of the heating rate of 2-5 ℃/min in the nitrogen protective atmosphere, preserving heat for 1-2 hours, continuing heating to 600-1000 ℃, preserving heat for 1-2 hours, then cooling to room temperature, and grinding to obtain the metal acrylate resin derived composite wave-absorbing material.
2. The method according to claim 1, wherein in the step A, the acrylate monomer is one or more acrylates selected from the group consisting of methyl acrylate, ethyl acrylate, hydroxyethyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, hydroxybutyl acrylate, isooctyl acrylate, lauryl acrylate and stearyl acrylate;
the methacrylate monomer is one or more of methacrylate selected from methyl methacrylate, ethyl methacrylate, hydroxyethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, hydroxybutyl methacrylate, isooctyl methacrylate, lauryl methacrylate or octadecyl methacrylate;
the vinyl monomer is one or more vinyl monomers selected from acrylonitrile, styrene, vinyl acetate or divinylbenzene.
3. The method according to claim 1, wherein in step A, the initiator is one or more initiators selected from the group consisting of azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate, benzoyl peroxide t-butyl ester, methyl ethyl ketone peroxide, ammonium persulfate and potassium persulfate.
4. The method according to claim 1, wherein in the step B, the chain transfer agent is n-dodecyl mercaptan, t-dodecyl mercaptan or an aliphatic mercaptan.
5. The method of claim 1, wherein the solvent used in the step B and the step C is one or more solvents selected from the group consisting of toluene, xylene, n-butanol, butyl acetate, ethyl acetate, cyclohexanone and methyl isobutyl ketone.
6. The method according to claim 1, wherein in step C, the metal oxide is one or more metal oxides selected from the group consisting of zinc oxide, copper oxide, magnesium oxide and calcium oxide; the metal hydroxide is one or more metal hydroxides selected from zinc hydroxide, copper hydroxide, iron hydroxide, magnesium hydroxide or calcium hydroxide; the organic acid is one or more organic acids selected from benzoic acid, naphthenic acid, stearic acid, lauric acid, acetic acid, propionic acid, butyric acid, abietic acid, proline, leucine, phenylalanine, arginine, dimerized abietic acid, disproportionated abietic acid, salicylic acid, furoic acid or p-chlorobenzoic acid.
7. The preparation method according to claim 1, wherein in the step D, the metal acrylate resin obtained in the step C is heated to 600-1000 ℃ in a tubular furnace in a nitrogen protective atmosphere at a heating rate of 2-5 ℃/min, then is kept at the temperature for 1-2 hours, then is cooled to room temperature, and is ground to obtain the metal acrylate resin derived composite wave-absorbing material.
8. The metal acrylate resin derived composite wave-absorbing material prepared by the preparation method according to any one of claims 1 to 7, which is characterized by having excellent wave-absorbing performance within a wavelength of 2-40 GHz.
9. The metal acrylate resin derived composite wave-absorbing material according to claim 8, wherein the composite wave-absorbing material is composed of carbon matrix and metal particles, and the metal particles are randomly embedded in the carbon matrix.
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