WO2020114092A1 - Epoxy rubber radiation-absorbing coating and preparation method therefor - Google Patents

Epoxy rubber radiation-absorbing coating and preparation method therefor Download PDF

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Publication number
WO2020114092A1
WO2020114092A1 PCT/CN2019/111290 CN2019111290W WO2020114092A1 WO 2020114092 A1 WO2020114092 A1 WO 2020114092A1 CN 2019111290 W CN2019111290 W CN 2019111290W WO 2020114092 A1 WO2020114092 A1 WO 2020114092A1
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Prior art keywords
ferrite
wave
rubber
absorbing
epoxy
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PCT/CN2019/111290
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French (fr)
Chinese (zh)
Inventor
刘若鹏
赵治亚
王佳佳
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洛阳尖端技术研究院
洛阳尖端装备技术有限公司
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Publication of WO2020114092A1 publication Critical patent/WO2020114092A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D109/00—Coating compositions based on homopolymers or copolymers of conjugated diene hydrocarbons
    • C09D109/02—Copolymers with acrylonitrile
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D115/00—Coating compositions based on rubber derivatives
    • C09D115/02—Rubber derivatives containing halogen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D181/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur, with or without nitrogen, oxygen, or carbon only; Coating compositions based on polysulfones; Coating compositions based on derivatives of such polymers
    • C09D181/04—Polysulfides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/32—Radiation-absorbing paints
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2265—Oxides; Hydroxides of metals of iron

Definitions

  • the invention relates to the field of composite materials, in particular, to an epoxy rubber wave-absorbing coating and a preparation method thereof.
  • Absorbing paint also known as microwave absorbing paint or radar wave absorbing paint, is a functional material that covers the target with a coating layer to achieve radar stealth. It can convert incident radar wave energy into heat energy to dissipate or through resonance effects. Make it eliminated or weakened to achieve the purpose of effective absorption or attenuation. Absorbing materials are widely used in the fields of anti-electromagnetic interference and stealth technology in communications. In order to obtain an excellent wave absorbing effect, the wave absorbing material needs to have both excellent electromagnetic impedance matching characteristics and electromagnetic loss performance.
  • Ferrite materials are a class of wave absorbing materials that have been studied and developed more maturely. Ferrite materials have good impedance matching and electromagnetic loss characteristics, making it easy to absorb electromagnetic waves and quickly lose electromagnetic waves. Therefore, it is widely used in the field of radar absorbing materials. However, due to the poor oxidation resistance and dispersibility of ferrite materials, it is difficult to meet the requirements of high-performance radar wave absorbing materials.
  • the absorber will be compounded with other matrix materials to prepare a wave-absorbing material.
  • the choice of matrix material should focus on minimizing the impact on the absorber in the wave-absorbing material, give full play to the performance of the absorber, and should comprehensively consider the structural requirements, adhesion, abrasion resistance, aging resistance, and resistance of the wave-absorbing composite material Flushing performance and other factors.
  • Epoxy resins have high strength and excellent bonding properties, and can be used as matrix coatings, electrical insulation materials, reinforcement materials, adhesives, etc.
  • epoxy resin wave-absorbing coatings have been found to have high brittleness in epoxy coatings during long-term use. Temperature resistance, easy aging, short service life and other issues.
  • the main purpose of the present invention is to provide an epoxy rubber wave-absorbing coating and a preparation method thereof to solve the problems of poor wave-absorbing performance and temperature resistance of the composite wave-absorbing material in the prior art.
  • an epoxy rubber wave absorbing coating includes a toughened modified epoxy resin and an oxidation modified ferrite Absorber.
  • the anti-oxidation modified ferrite wave absorber is a ferrite wave absorber coated with a coupling agent on the surface, and the mass ratio of the coupling agent to the ferrite wave absorber is preferably 0.05 to 0.1: 1; preferably ferrite absorbing agent is selected from magnetoplumbite type ferrite, more preferably, magnetoplumbite type ferrite is selected from M type ferrite, Z type ferrite and W type ferrite One or more of them; preferably the coupling agent is selected from silane coupling agents, more preferably the silane coupling agent is selected from ⁇ -aminopropyltriethoxysilane, 3-(2,3-epoxypropoxy)propane One or more of trimethoxysilane, ⁇ -(methacryloyloxy)propyltrimethoxysilane and ⁇ -propyltriethoxysilane.
  • the toughened modified epoxy resin is an epoxy resin mixed with liquid rubber, preferably one or more epoxy resins selected from EP815, EP828, EP827 and EP834; preferably the liquid rubber is selected from chlorinated One or more of rubber, nitrile rubber, or polysulfide rubber.
  • the epoxy rubber wave-absorbing coating includes 10 to 20 parts of liquid rubber, 60 to 80 parts of epoxy resin, and 10 to 75 parts of anti-oxidation-modified ferrite wave-absorbing agent.
  • the epoxy rubber wave-absorbing coating further includes a thinner selected from one or more of methyl acetate, ethyl acetate, amyl acetate, and butyl acetate; preferably, by weight, the thinner
  • the agent is 12 to 18 parts; preferably, the epoxy rubber wave-absorbing coating further includes a dispersant and a defoamer; more preferably, by weight, the dispersant is 3 to 5 parts and the defoamer is 3 to 5 parts .
  • the present application provides a method for preparing an epoxy rubber wave-absorbing coating.
  • the preparation method includes the following steps: diluting a toughened and modified epoxy resin to obtain a diluted resin;
  • the diluted resin is mixed with a ferrite absorber modified by oxidation resistance to obtain an epoxy rubber absorber coating.
  • the above preparation method further includes the step of toughening and modifying the epoxy resin
  • the step of toughening and modifying the epoxy resin includes: mixing and stirring the liquid rubber and the epoxy resin to obtain a toughened and modified ring Oxygen resin; preferably, in terms of parts by weight, the liquid rubber is 10-20 parts and the epoxy resin is 60-80 parts; preferably the epoxy resin is selected from one or more of EP815, EP828, EP827 and EP834; preferably The liquid rubber is selected from one or more of chlorinated rubber, nitrile rubber and polysulfide rubber.
  • the above-mentioned dilution treatment step includes: mixing and agitating the diluent with the toughened and modified epoxy resin to obtain a dilute resin; wherein the diluent is selected from methyl acetate, ethyl acetate, amyl acetate, and butyl acetate One or more of them; preferably, the diluent is 12-18 parts by weight.
  • the above preparation method further includes the step of performing anti-oxidation modification on the ferrite wave absorber, and the step of performing anti-oxidation modification on the ferrite wave absorber includes: absorbing the ferrite with a particle size of less than 400 mesh Mix the particles with the organic solvent to obtain a ferrite absorbing agent particle dispersion; mix the ferrite absorbing agent particle dispersion with the coupling agent and perform ball milling to obtain a suspension; dry the suspension To obtain ferrite absorber modified by oxidation resistance; preferably ferrite absorber is selected from magnetoplumbite type ferrite, more preferably, magnetoplumbite type ferrite is selected from M type ferrite , One or more of Z type ferrite and W type ferrite; preferably the organic solvent is selected from ethanol and/or propanol; preferably the coupling agent is selected from silane coupling agent, more preferably the silane coupling agent is selected From ⁇ -aminopropyltriethoxysilane, 3-(2,
  • the step of mixing the diluted resin with the anti-oxidation-modified ferrite wave absorber includes: mixing the diluted resin with the anti-oxidation-modified ferrite wave absorber using ultrasound to obtain an epoxy rubber absorber Wave coating; preferably, by weight, the antioxidant-modified ferrite wave absorber is 10 to 75 parts; preferably the step of mixing the diluted resin with the antioxidant-modified ferrite wave absorber includes :Using ultrasound to mix dilute resin, anti-oxidation modified ferrite absorbing agent, dispersant and defoaming agent to obtain epoxy rubber absorbing coating; the preferred ultrasonic treatment time is 5 ⁇ 7h and the ultrasonic frequency is 25 -30KHz.
  • the epoxy resin undergoes toughening modification, so that the modified epoxy resin has a polymer network structure, which makes the epoxy resin heat resistance, adhesion, wear resistance, impact resistance
  • the performance and product processing performance have been improved, and at the same time, the modified epoxy resin is more easily compounded with the ferrite wave absorber; the ferrite wave absorber modified by oxidation resistance improves the resistance of the wave absorber Oxidizing ability and dispersibility broaden the absorption band of the absorbing material.
  • the coating formed after compounding not only combines the performance of the above two materials, but also makes the processing and use performance of the ferrite wave absorber more superior, so that the epoxy rubber wave absorbing coating can effectively improve the wave absorbing effect and temperature resistance.
  • the compounded epoxy rubber wave-absorbing coating has a wider low-frequency absorption frequency band, more stable wave-absorbing performance, and more outstanding temperature resistance effect.
  • the composite wave absorbing materials in the prior art have poor wave absorbing performance and temperature resistance.
  • this application provides an epoxy rubber wave-absorbing coating and a preparation method thereof.
  • an epoxy rubber wave-absorbing coating which includes a toughened modified epoxy resin and an oxidation-resistant modified ferrite Wave agent.
  • the epoxy resin undergoes toughening modification, so that the modified epoxy resin has a polymer network structure, which makes the epoxy resin heat resistance, adhesion, and wear resistance.
  • the resistance, impact resistance and product processing performance have been improved, and at the same time, the modified epoxy resin is easier to compound with the ferrite wave absorber; the ferrite wave absorber modified by oxidation resistance improves the absorption The anti-oxidation ability and dispersion of the wave agent broaden the wave absorption band of the wave absorbing material.
  • the coating formed after compounding not only has the performance of the above two materials, but also makes the processing and use performance of the ferrite wave absorber more superior, so that the epoxy rubber wave absorbing coating can effectively improve the wave absorbing effect and temperature resistance, and finally
  • the compounded epoxy rubber wave-absorbing coating has a wider low-frequency absorption frequency band, more stable wave-absorbing performance, and more outstanding temperature resistance effect.
  • the above-mentioned toughened and modified epoxy resins are mixed Epoxy resin with liquid rubber.
  • the rubber will react with the epoxy resin to form a polymer rubber-plastic network structure to achieve toughening and modification of the epoxy resin.
  • This structure can significantly improve the resistance of the epoxy resin.
  • Heat, adhesion and abrasion resistance are also beneficial to promote the compounding of epoxy resin and ferrite wave absorber, and significantly improve the wave absorbing performance of the compound wave absorbing coating.
  • the epoxy resin is selected from one or more of EP815, EP828, EP827 and EP834, preferably the liquid rubber is selected from one or more of chlorinated rubber, nitrile rubber and polysulfide rubber, but the epoxy resin and The choice of liquid rubber includes but is not limited to the range provided above, as long as the epoxy resin can react with the liquid rubber to achieve toughening and produce a more stable structure.
  • the anti-oxidation modified ferrite wave absorber is ferrite coated with a coupling agent on the surface Body absorbing agent.
  • a coupling agent on the surface Body absorbing agent By coating the coupling agent on the surface of the ferrite wave absorber, the contact between the ferrite wave absorber and the air is effectively prevented, so that the anti-oxidation performance of the ferrite wave absorber can be improved.
  • the structure of the coupling agent on the surface of the ferrite makes the ferrite absorber easier to compound with the epoxy resin.
  • the mass ratio of the coupling agent to the ferrite wave absorber is 0.05 ⁇ 0.1:1, the mass ratio of the coupling agent to the ferrite wave absorber and the coating of the ferrite wave absorber surface coupling agent
  • the thickness is related, and it also affects the antioxidant modification effect of the ferrite wave absorber and the composite effect with the epoxy resin. It is preferable that the mass ratio of the coupling agent to the ferrite wave absorber in the above ratio is not only conducive to achieving
  • the anti-oxidation performance of the ferrite wave absorbing agent is also beneficial to promote the compounding of the ferrite wave absorbing agent and the epoxy resin, and thus to improve the wave absorbing performance of the composite wave absorbing coating.
  • the ferrite wave absorber is selected from magnetoplumbite type ferrite, and more preferably, the magnetoplumbite type ferrite is selected from M type ferrite (such as BaFe 12 O 19 , SrFe 12 O 19 ), Z type One or more of ferrite (such as Ba 3 Me 2 Fe 24 O 41 ) and W-type ferrite (such as BaMe 2 Fe 16 O 27 ).
  • M type ferrite such as BaFe 12 O 19 , SrFe 12 O 19
  • Z type One or more of ferrite such as Ba 3 Me 2 Fe 24 O 41
  • W-type ferrite such as BaMe 2 Fe 16 O 27 .
  • the coupling agent is selected from silane coupling agents, more preferably the silane coupling agent is selected from ⁇ -aminopropyltriethoxysilane (coupling agent KH-550), 3-(2,3-epoxypropoxy) Propyltrimethoxysilane (coupling agent KH-560), ⁇ -(methacryloyloxy)propyltrimethoxysilane (coupling agent KH-570) and ⁇ -propyltriethoxysilane (coupling One or more of the joint agent KH-580).
  • the silane coupling agent is selected from ⁇ -aminopropyltriethoxysilane (coupling agent KH-550), 3-(2,3-epoxypropoxy) Propyltrimethoxysilane (coupling agent KH-560), ⁇ -(methacryloyloxy)propyltrimethoxysilane (coupling agent KH-570) and ⁇ -propyltriethoxysilane (coupling
  • the choice of ferrite wave absorber and coupling agent includes but is not limited to the range provided above, as long as the coupling agent can be coated with the ferrite wave absorber to isolate the air, while the coupling agent can be combined with the epoxy resin Just combine them.
  • the organic solvent such as ethanol and propanol can be used to dilute the silane coupling agent or to dissolve the ferrite A silane coupling agent is added to the alcohol organic solvent.
  • the above-mentioned epoxy rubber absorbing coating includes 10-20 parts of liquid rubber, 60-80 parts of epoxy resin and 10-75 parts of antioxidant-modified ferrite Body absorbing agent.
  • the different ratios of liquid rubber and epoxy resin directly affect the improvement of the temperature and wear resistance of the absorbing material
  • the different ratios of epoxy resin and ferrite absorbing agent modified by oxidation directly affect the absorption
  • the change of the absorption band of the wave material and the change of the low-frequency absorption band control the mixing ratio of the liquid rubber, epoxy resin and ferrite absorber modified by oxidation resistance within the range provided above, which is conducive to further improve the compounding
  • the absorbing performance, temperature resistance and the width of the low-frequency absorption band of the absorbing coating are examples of antioxidant-modified ferrite Body absorbing agent.
  • the epoxy rubber wave-absorbing coating further includes a diluent, wherein the diluent is selected from methyl acetate, ethyl acetate, and amyl acetate One or more of butyl acetate; preferably, the diluent is 12 to 18 parts by weight.
  • a diluent is selected from methyl acetate, ethyl acetate, and amyl acetate
  • the diluent is 12 to 18 parts by weight.
  • the epoxy rubber wave-absorbing coating further includes a dispersant and a defoamer; more preferably, the dispersant is 3 to 5 parts by weight, and the defoamer is 3 to 5 parts by weight.
  • the defoamer is helpful to remove the bubbles generated during the mixing of the above materials, to avoid the presence of bubbles affecting the curing effect of the composite wave-absorbing coating;
  • the dispersant is helpful to promote the distribution of the ferrite wave-absorbing agent in the epoxy resin It is more uniform to ensure that the entire coating layer formed by the composite wave-absorbing coating has excellent wave-absorbing effect when it is used.
  • the dispersant is selected from one or more of polypropylene sodium carbonate, polyethylene glycol, and polyvinyl alcohol; preferably, the defoamer is selected from polydimethylsiloxane and/or tributyl phosphate.
  • a method for preparing an epoxy rubber wave-absorbing coating includes: first diluting a toughened and modified epoxy resin to obtain a diluted resin; Then, the obtained diluted resin is mixed with an anti-oxidation modified ferrite wave-absorbing agent to obtain an epoxy rubber wave-absorbing paint.
  • the toughened and modified epoxy resin is first diluted to make the epoxy resin easier to compound with other materials, and then the diluted resin is mixed with the anti-oxidation modified ferrite wave absorber.
  • a composite epoxy rubber wave-absorbing coating is obtained, which has the performance of both toughened modified epoxy resin and anti-oxidation-modified ferrite wave-absorbing agent, and realizes the ferrite wave-absorbing The wave-absorbing performance of the agent is fully exerted, and at the same time, the oxidation resistance, temperature resistance and low-frequency absorption band width of the wave-absorbing material are improved.
  • the above preparation method is simple, and the epoxy rubber composite wave absorbing coating obtained by the above preparation method can improve the electromagnetic wave matching performance, so that the low frequency absorption frequency band of the composite wave absorbing coating is wider and the wave absorbing performance is more remarkable.
  • the temperature resistance effect is more prominent. It can be seen that the above-mentioned preparation method is used to prepare the composite wave-absorbing coating.
  • the process is simple, easy to operate, and the cost is low. It can realize large-scale production.
  • the obtained composite wave-absorbing coating has more remarkable wave-absorbing performance and more outstanding temperature resistance.
  • the stealth field has good application prospects.
  • the above preparation method further includes toughening and modifying epoxy resins.
  • the step of toughening and modifying the epoxy resin includes: mixing and stirring the liquid rubber with the epoxy resin to obtain a toughened and modified epoxy resin; preferably, the liquid rubber is 10 ⁇ by weight 20 parts, epoxy resin is 60 ⁇ 80 parts; preferably epoxy resin is selected from one or more of EP815, EP828, EP827 and EP834, preferably liquid rubber is selected from chlorinated rubber, nitrile rubber and polysulfide rubber One or more.
  • the rubber By adding liquid rubber to the epoxy resin, the rubber will react with the epoxy resin to form a polymer rubber-plastic network structure to achieve toughening and modification of the epoxy resin.
  • This structure can significantly improve the resistance of the epoxy resin.
  • Heat, adhesion and abrasion resistance are also beneficial to promote the compounding of epoxy resin and ferrite wave absorber, and significantly improve the wave absorbing performance of the compound wave absorbing coating.
  • the above-mentioned dilution treatment step includes: mixing and agitating the diluent with the toughened modified epoxy resin to obtain a diluted resin; wherein, the dilution The agent is selected from one or more of methyl acetate, ethyl acetate, amyl acetate, and butyl acetate; preferably, the diluent is 12-18 parts by weight. Adding a diluent to the epoxy resin is helpful to promote the combination of the epoxy resin and the ferrite absorber. By controlling the type and amount of the diluent within the above range, it is beneficial to further promote the epoxy resin and ferrite The combination of body absorbers shortens the compounding time.
  • the above preparation method further includes the step of performing anti-oxidation modification on the ferrite wave absorber.
  • the steps of the anti-oxidation modification of the wave absorber include: first mixing the ferrite wave absorber particles with a particle size of less than 400 mesh and an organic solvent to obtain a dispersion liquid of the ferrite wave absorber particles; then the ferrite wave absorber The particle dispersion is mixed with the coupling agent and then ball milled to obtain a suspension.
  • the suspension is dried to obtain an anti-oxidation modified ferrite wave absorber; preferably the ferrite wave absorber is selected from Magnetoplumbite type ferrite, more preferably magnetoplumbite type ferrite is selected from M-type ferrite (BaFe 12 O 19 , SrFe 12 O 19 ), Z-type ferrite (Ba 3 Me 2 Fe 24 O 41 ) And one or more of W-type ferrite (BaMe 2 Fe 16 O 27 ); preferably the organic solvent is selected from ethanol and/or propanol; preferably the coupling agent is selected from silane coupling agents, more preferably silane coupling The coupling agent is selected from ⁇ -aminopropyltriethoxysilane, 3-(2,3-glycidoxy)propyltrimethoxysilane, ⁇ -(methacryloyloxy)propyltrimethoxysilane and One or more of ⁇ -propyltriethoxysilane; more preferably
  • the ball mill performs ball milling on the ferrite wave-absorbing agent, and then sieves with a 400-mesh screen to obtain uniform ferrite wave-absorbing agent particles with a particle size of less than 400 mesh, and then Disperse the ferrite absorbing agent particles in an organic solvent, and then mix with the coupling agent for ball milling.
  • the ball milling process is beneficial for the coupling agent to coat the surface of the ferrite absorbing agent to realize the absorption of ferrite. Antioxidant modification of the agent.
  • the coupling agent By coating the coupling agent on the surface of the ferrite wave absorber, the contact between the ferrite wave absorber and the air is effectively prevented, so that the anti-oxidation performance of the ferrite wave absorber is improved.
  • the structure of the coupling agent on the surface of the ferrite makes the ferrite absorber easier to compound with the epoxy resin.
  • the mass ratio of the coupling agent and the ferrite wave absorber is related to the antioxidant performance of the modified ferrite wave absorber.
  • Controlling the mass ratio within the above range is conducive to improving the wave absorption of the modified ferrite
  • the antioxidant performance of the agent, and the choice of ferrite wave absorber and coupling agent include but are not limited to the range provided above, as long as the coupling agent can be coated with the ferrite wave absorber to isolate the air, while coupling
  • the joint agent can be combined with the epoxy resin.
  • the step of mixing the diluted resin with the anti-oxidation modified ferrite wave absorber includes: mixing the diluted resin with the anti-oxidation modified ferrite wave absorber using ultrasound, To obtain an epoxy rubber wave-absorbing coating, preferably, by weight, the antioxidant-modified ferrite wave-absorbing agent is 10 to 75 parts; it is preferable to dilute the diluted resin with the oxidation-resistant modified ferrite wave-absorbing agent
  • the mixing steps of the agent include: mixing the diluted resin, the ferrite absorber modified with oxidation resistance, the dispersant and the defoaming agent by ultrasound to obtain the epoxy rubber absorber coating, preferably the ultrasonic treatment time is 5 ⁇ 7h , Ultrasonic frequency is 25 ⁇ 30KHz; diluent is selected from one or more of methyl acetate, ethyl acetate, amyl acetate, butyl acetate; preferably, the diluent is 12-18 parts by weight ;
  • the epoxy rubber wave-absorbing coating preferably, by weight
  • the dispersant is selected from one or more of polypropylene sodium carbonate, polyethylene glycol, and polyvinyl alcohol; preferably, the defoamer is selected from polydimethylsiloxane and/or tributyl phosphate.
  • the Z-type ferrite (Ba 3 Me 2 Fe 24 O 41 ) was ball-milled for 60 h, and then sieved with a 400-mesh screen to obtain sieve ferrite absorbing agent particles, and the ferrite absorbing agent particles were dispersed in To ethanol, add a silane coupling agent (KH-550) which accounts for 5% of the ferrite absorber mass, and after ball milling for 30 minutes, dry the resulting suspension to obtain an anti-oxidation modified ferrite absorber. Agent, save for future use.
  • KH-550 silane coupling agent
  • nitrile rubber type 170
  • epoxy resin EP8248
  • methyl acetate was added for dilution and stirring to obtain a diluted resin.
  • M-type ferrite absorbing agent modified by coupling agent KH-560 into the diluted resin, add 4 parts of polypropylene sodium carbonate dispersant, 4 parts of polydimethylsiloxane defoamer, Disperse with an ultrasonic disperser for 6h, where the ultrasonic frequency is 25KHz to obtain epoxy rubber wave-absorbing coating.
  • nitrile rubber type 170
  • epoxy resin EP834
  • ethyl acetate was added for dilution and stirring to obtain a diluted resin.
  • the mass ratio of the coupling agent to the ferrite wave absorber is 10%.
  • Example 1 The difference from Example 1 is that the added ferrite wave absorber does not undergo high-temperature anti-oxidation modification without a coupling agent.
  • Example 1 The difference from Example 1 is that no liquid rubber is added during the preparation process, that is, the epoxy resin is not toughened and modified.
  • Example 1 The difference from Example 1 is that no liquid rubber is added during the preparation process, and the added ferrite absorbing agent is not subjected to anti-oxidation modification through the coupling agent.
  • Wave absorption performance test method add 12 parts of epoxy resin curing agent modified alicyclic amine to the epoxy rubber wave absorbing coating prepared above, mix and evenly inject it into a mold of 300 ⁇ 300 ⁇ 2mm, and cure at room temperature Obtain epoxy resin wave-absorbing coating with a cured layer of 2mm. After bonding the cured layer with a standard metal sheet (size 300 ⁇ 300 ⁇ 2mm), place it in a microwave dark room to formulate the receiving plane. The electromagnetic absorption parameters of the layered absorbing material are tested in the microwave dark room. The test results are shown in Table 1.
  • High temperature oxidation resistance test method oxidation resistance is reflected in a specific environment, generally in high temperature.
  • the cured coating prepared above was placed in a constant temperature oven at 200°C. After 24 hours, check whether there was peeling or peeling, and test the material's wave absorption performance.
  • Flexibility test method the thickness of the cured coating prepared above is 2 mm, and the test is performed according to the GBT1731 paint film flexibility test method.
  • the modified epoxy resin has a polymer network structure, so that the heat resistance, adhesion, wear resistance and impact resistance of the epoxy resin are processed and used.
  • the modified epoxy resin easier to compound with the ferrite wave absorber; the ferrite wave absorber modified by anti-oxidation improves the antioxidant capacity and dispersibility of the wave absorber, as shown in the table As shown in Example 1 to Example 4 in 1, as the content of anti-oxidation-modified ferrite increases, the peak position shifts to a low frequency, and at 15.4 GHz, the bandwidth of absorption rate ⁇ 90% can reach 6.4 GHz, still having Better absorbing performance and bandwidth.
  • the coating formed after compounding not only has the performance of the above two materials, but also makes the processing and use performance of the ferrite wave absorber more superior, so that the epoxy rubber wave absorbing coating can effectively improve the wave absorbing effect and temperature resistance, and finally
  • the compounded epoxy rubber wave-absorbing coating has a wider low-frequency absorption frequency band, more stable wave-absorbing performance, and more outstanding temperature resistance effect.

Abstract

Provided in the present invention are an epoxy rubber radiation-absorbing material and a preparation method therefor. The epoxy rubber radiation-absorbing material comprises an epoxy resin that has undergone toughening modification, and an a ferrite radiation-absorbing agent that has undergone anti-oxidation modification. The epoxy rubber radiation-absorbing coating obtained by means of the preparation method provided in the present application features a wider low-frequency absorption band, more stable absorption performance, and a more pronounced thermal resistance effect.

Description

环氧橡胶吸波涂料及其制备方法Epoxy rubber wave-absorbing paint and preparation method thereof 技术领域Technical field
本发明涉及复合材料领域，具体而言，涉及一种环氧橡胶吸波涂料及其制备方法。The invention relates to the field of composite materials, in particular, to an epoxy rubber wave-absorbing coating and a preparation method thereof.
背景技术Background technique
吸波涂料又称微波吸收涂料或雷达波吸收涂料，是用涂覆层形式覆盖在目标上实现雷达隐身的一种功能材料，能将入射的雷达波能量转换成热能而耗散或通过谐振效应使之消除或减弱，达到有效吸收或衰减的目的。吸波材料广泛应用于通讯抗电磁干扰和隐身技术等领域。为了获得性能优良的吸波效果，吸波材料需要同时具备优异的电磁阻抗匹配特性和电磁损耗性能。Absorbing paint, also known as microwave absorbing paint or radar wave absorbing paint, is a functional material that covers the target with a coating layer to achieve radar stealth. It can convert incident radar wave energy into heat energy to dissipate or through resonance effects. Make it eliminated or weakened to achieve the purpose of effective absorption or attenuation. Absorbing materials are widely used in the fields of anti-electromagnetic interference and stealth technology in communications. In order to obtain an excellent wave absorbing effect, the wave absorbing material needs to have both excellent electromagnetic impedance matching characteristics and electromagnetic loss performance.
铁氧体材料是目前研究较多且发展较为成熟的一类吸波材料。铁氧体材料具有良好的阻抗匹配及电磁损耗特性，使其易于吸收电磁波并快速将电磁波损耗。因此被广泛地应用于雷达吸波材料领域。但由于铁氧体材料的抗氧化能力和分散性较差，又导致以铁氧体材料为主的涂层难以满足高性能的雷达波吸收材料。Ferrite materials are a class of wave absorbing materials that have been studied and developed more maturely. Ferrite materials have good impedance matching and electromagnetic loss characteristics, making it easy to absorb electromagnetic waves and quickly lose electromagnetic waves. Therefore, it is widely used in the field of radar absorbing materials. However, due to the poor oxidation resistance and dispersibility of ferrite materials, it is difficult to meet the requirements of high-performance radar wave absorbing materials.
技术问题technical problem
在实际应用过程中，吸收剂都将与其他基体材料复合，制备成吸波材料。基体材料的选择应着眼于尽量减少对吸波材料中吸收剂的影响，充分发挥吸收剂的性能，并且应综合考虑吸波复合材料的结构要求、附着力、抗磨损性、耐老化性能、耐冲刷性能等因素。环氧树脂具有高强度和优良的粘接性能，可用作基体涂料、电绝缘材料、增强材料和胶粘剂等，但环氧树脂吸波涂料在长期使用中发现，存在环氧涂层脆性大，耐温差，易老化，使用寿命短等问题。In the actual application process, the absorber will be compounded with other matrix materials to prepare a wave-absorbing material. The choice of matrix material should focus on minimizing the impact on the absorber in the wave-absorbing material, give full play to the performance of the absorber, and should comprehensively consider the structural requirements, adhesion, abrasion resistance, aging resistance, and resistance of the wave-absorbing composite material Flushing performance and other factors. Epoxy resins have high strength and excellent bonding properties, and can be used as matrix coatings, electrical insulation materials, reinforcement materials, adhesives, etc. However, epoxy resin wave-absorbing coatings have been found to have high brittleness in epoxy coatings during long-term use. Temperature resistance, easy aging, short service life and other issues.
技术解决方案Technical solution
本发明的主要目的在于提供一种环氧橡胶吸波涂料及其制备方法，以解决现有技术中复合吸波材料吸波性能差、耐温差的问题。The main purpose of the present invention is to provide an epoxy rubber wave-absorbing coating and a preparation method thereof to solve the problems of poor wave-absorbing performance and temperature resistance of the composite wave-absorbing material in the prior art.
为了实现上述目的，根据本发明的一个方面，提供了一种环氧橡胶吸波涂料，该环氧橡胶吸波涂料包括经过增韧改性的环氧树脂和经过抗氧化改性的铁氧体吸波剂。In order to achieve the above object, according to an aspect of the present invention, there is provided an epoxy rubber wave absorbing coating, the epoxy rubber wave absorbing coating includes a toughened modified epoxy resin and an oxidation modified ferrite Absorber.
进一步地，经过抗氧化改性的铁氧体吸波剂为表面包覆有偶联剂的铁氧体吸波剂，优选偶联剂与铁氧体吸波剂的质量比为0.05~0.1:1；优选铁氧体吸波剂选自磁铅石型铁氧体，更优选地，磁铅石型铁氧体选自M型铁氧体、Z型铁氧体和W型铁氧体中的一种或多种；优选偶联剂选自硅烷偶联剂，更优选硅烷偶联剂选自γ-氨丙基三乙氧基硅烷、3-(2,3-环氧丙氧)丙基三甲氧基硅烷、γ-（甲基丙烯酰氧）丙基三甲氧基硅烷和γ-丙基三乙氧基硅烷中的一种或多种。Further, the anti-oxidation modified ferrite wave absorber is a ferrite wave absorber coated with a coupling agent on the surface, and the mass ratio of the coupling agent to the ferrite wave absorber is preferably 0.05 to 0.1: 1; preferably ferrite absorbing agent is selected from magnetoplumbite type ferrite, more preferably, magnetoplumbite type ferrite is selected from M type ferrite, Z type ferrite and W type ferrite One or more of them; preferably the coupling agent is selected from silane coupling agents, more preferably the silane coupling agent is selected from γ-aminopropyltriethoxysilane, 3-(2,3-epoxypropoxy)propane One or more of trimethoxysilane, γ-(methacryloyloxy)propyltrimethoxysilane and γ-propyltriethoxysilane.
进一步地，经过增韧改性的环氧树脂为混合有液态橡胶的环氧树脂，优选环氧树脂选自EP815、EP828、EP827和EP834中的一种或多种；优选液态橡胶选自氯化橡胶、丁腈橡胶、或聚硫橡胶中的一种或多种。Further, the toughened modified epoxy resin is an epoxy resin mixed with liquid rubber, preferably one or more epoxy resins selected from EP815, EP828, EP827 and EP834; preferably the liquid rubber is selected from chlorinated One or more of rubber, nitrile rubber, or polysulfide rubber.
进一步地，按重量份计，环氧橡胶吸波涂料中包括10~20份液态橡胶、60~80份环氧树脂与10~75份经过抗氧化改性的铁氧体吸波剂。Further, in terms of parts by weight, the epoxy rubber wave-absorbing coating includes 10 to 20 parts of liquid rubber, 60 to 80 parts of epoxy resin, and 10 to 75 parts of anti-oxidation-modified ferrite wave-absorbing agent.
进一步地，环氧橡胶吸波涂料还包括稀释剂，稀释剂选自醋酸甲酯、醋酸乙酯、醋酸戊酯、醋酸丁酯中的一种或多种；优选地，按重量份计，稀释剂为12~18份；优选地，环氧橡胶吸波涂料还包括分散剂和消泡剂；更优选地，按重量份计，分散剂为3~5份，消泡剂为3~5份。Further, the epoxy rubber wave-absorbing coating further includes a thinner selected from one or more of methyl acetate, ethyl acetate, amyl acetate, and butyl acetate; preferably, by weight, the thinner The agent is 12 to 18 parts; preferably, the epoxy rubber wave-absorbing coating further includes a dispersant and a defoamer; more preferably, by weight, the dispersant is 3 to 5 parts and the defoamer is 3 to 5 parts .
根据本申请的另一个方面，本申请提供了一种环氧橡胶吸波涂料的制备方法，该制备方法包括以下步骤：将经过增韧改性的环氧树脂进行稀释处理，得到稀释树脂；将稀释树脂与经过抗氧化改性的铁氧体吸波剂混合，得到环氧橡胶吸波涂料。According to another aspect of the present application, the present application provides a method for preparing an epoxy rubber wave-absorbing coating. The preparation method includes the following steps: diluting a toughened and modified epoxy resin to obtain a diluted resin; The diluted resin is mixed with a ferrite absorber modified by oxidation resistance to obtain an epoxy rubber absorber coating.
进一步地，上述制备方法还包括对环氧树脂增韧改性的步骤，对环氧树脂进行增韧改性的步骤包括：将液态橡胶与环氧树脂混合搅拌，得到经过增韧改性的环氧树脂；优选地，按重量份计，液态橡胶为10~20份，环氧树脂为60~80份；优选环氧树脂选自EP815、EP828、EP827和EP834中的一种或多种；优选液态橡胶选自氯化橡胶、丁腈橡胶和聚硫橡胶中的一种或多种。Further, the above preparation method further includes the step of toughening and modifying the epoxy resin, and the step of toughening and modifying the epoxy resin includes: mixing and stirring the liquid rubber and the epoxy resin to obtain a toughened and modified ring Oxygen resin; preferably, in terms of parts by weight, the liquid rubber is 10-20 parts and the epoxy resin is 60-80 parts; preferably the epoxy resin is selected from one or more of EP815, EP828, EP827 and EP834; preferably The liquid rubber is selected from one or more of chlorinated rubber, nitrile rubber and polysulfide rubber.
进一步地，上述稀释处理步骤包括：将稀释剂与经过增韧改性的环氧树脂混合搅拌，得到稀释树脂；其中，稀释剂选自醋酸甲酯、醋酸乙酯、醋酸戊酯、醋酸丁酯中的一种或多种；优选地，按重量份计，稀释剂为12~18份。Further, the above-mentioned dilution treatment step includes: mixing and agitating the diluent with the toughened and modified epoxy resin to obtain a dilute resin; wherein the diluent is selected from methyl acetate, ethyl acetate, amyl acetate, and butyl acetate One or more of them; preferably, the diluent is 12-18 parts by weight.
进一步地，上述制备方法还包括对铁氧体吸波剂进行抗氧化改性的步骤，对铁氧体吸波剂进行抗氧化改性的步骤包括：将粒径小于400目的铁氧体吸波剂颗粒与有机溶剂混合，得到铁氧体吸波剂颗粒分散液；将铁氧体吸波剂颗粒分散液与偶联剂混合后进行球磨处理，得到悬浊液；将悬浊液进行干燥处理，得到经过抗氧化改性的铁氧体吸波剂；优选铁氧体吸波剂选自磁铅石型铁氧体，更优选地，磁铅石型铁氧体选自M型铁氧体、Z型铁氧体和W型铁氧体中的一种或多种；优选有机溶剂选自乙醇和/或丙醇；优选偶联剂选自硅烷偶联剂，更优选硅烷偶联剂选自γ-氨丙基三乙氧基硅烷、3-(2,3-环氧丙氧)丙基三甲氧基硅烷、γ-（甲基丙烯酰氧）丙基三甲氧基硅烷和γ-丙基三乙氧基硅烷中的一种或多种；更优选偶联剂与铁氧体吸波剂的质量比为0.05~0.1:1。Further, the above preparation method further includes the step of performing anti-oxidation modification on the ferrite wave absorber, and the step of performing anti-oxidation modification on the ferrite wave absorber includes: absorbing the ferrite with a particle size of less than 400 mesh Mix the particles with the organic solvent to obtain a ferrite absorbing agent particle dispersion; mix the ferrite absorbing agent particle dispersion with the coupling agent and perform ball milling to obtain a suspension; dry the suspension To obtain ferrite absorber modified by oxidation resistance; preferably ferrite absorber is selected from magnetoplumbite type ferrite, more preferably, magnetoplumbite type ferrite is selected from M type ferrite , One or more of Z type ferrite and W type ferrite; preferably the organic solvent is selected from ethanol and/or propanol; preferably the coupling agent is selected from silane coupling agent, more preferably the silane coupling agent is selected From γ-aminopropyltriethoxysilane, 3-(2,3-epoxypropyloxy)propyltrimethoxysilane, γ-(methacryloyloxy)propyltrimethoxysilane and γ-propylene One or more of triethoxysilane; more preferably the mass ratio of coupling agent to ferrite wave absorber is 0.05~0.1:1.
进一步地，将稀释树脂与经过抗氧化改性的铁氧体吸波剂混合的步骤包括：利用超声将稀释树脂与经过抗氧化改性的铁氧体吸波剂的混合，得到环氧橡胶吸波涂料；优选地，按重量份计，经过抗氧化改性的铁氧体吸波剂为10~75份；优选将稀释树脂与经过抗氧化改性的铁氧体吸波剂混合的步骤包括：利用超声将稀释树脂、经过抗氧化改性的铁氧体吸波剂、分散剂和消泡剂混合，得到环氧橡胶吸波涂料；优选超声的处理时间为5~7h，超声频率为25-30KHz。Further, the step of mixing the diluted resin with the anti-oxidation-modified ferrite wave absorber includes: mixing the diluted resin with the anti-oxidation-modified ferrite wave absorber using ultrasound to obtain an epoxy rubber absorber Wave coating; preferably, by weight, the antioxidant-modified ferrite wave absorber is 10 to 75 parts; preferably the step of mixing the diluted resin with the antioxidant-modified ferrite wave absorber includes ：Using ultrasound to mix dilute resin, anti-oxidation modified ferrite absorbing agent, dispersant and defoaming agent to obtain epoxy rubber absorbing coating; the preferred ultrasonic treatment time is 5~7h and the ultrasonic frequency is 25 -30KHz.
有益效果Beneficial effect
应用本发明的技术方案，由于环氧树脂经过增韧改性，使得改性后的环氧树脂具备高分子网络结构，使得环氧树脂的耐热性、粘结性、耐磨性、抗冲击性、产品加工使用性能均得到提高，同时使得改性后的环氧树脂更易与铁氧体吸波剂进行复合；经过抗氧化改性的铁氧体吸波剂，提高了吸波剂的抗氧化能力和分散性，拓宽了吸波材料的吸波频带。复合后形成的涂料不但兼具了上述两种材料的性能，还使得铁氧体吸波剂的加工使用性能更加优越，使得环氧橡胶吸波涂料能够有效改善吸波效果和耐温性能，最终复合得到的环氧橡胶吸波涂料的低频吸收频带更宽、吸波性能更稳定、耐温效果更突出。Applying the technical solution of the present invention, the epoxy resin undergoes toughening modification, so that the modified epoxy resin has a polymer network structure, which makes the epoxy resin heat resistance, adhesion, wear resistance, impact resistance The performance and product processing performance have been improved, and at the same time, the modified epoxy resin is more easily compounded with the ferrite wave absorber; the ferrite wave absorber modified by oxidation resistance improves the resistance of the wave absorber Oxidizing ability and dispersibility broaden the absorption band of the absorbing material. The coating formed after compounding not only combines the performance of the above two materials, but also makes the processing and use performance of the ferrite wave absorber more superior, so that the epoxy rubber wave absorbing coating can effectively improve the wave absorbing effect and temperature resistance. The compounded epoxy rubber wave-absorbing coating has a wider low-frequency absorption frequency band, more stable wave-absorbing performance, and more outstanding temperature resistance effect.
本发明的实施方式Embodiments of the invention
需要说明的是，在不冲突的情况下，本申请中的实施例及实施例中的特征可以相互组合。下面将结合实施例来详细说明本发明。It should be noted that the embodiments in the present application and the features in the embodiments can be combined with each other if there is no conflict. The present invention will be described in detail below in conjunction with embodiments.
正如背景技术中所描述的，现有技术中的复合吸波材料吸波性能差、耐温差等问题。为了解决这一问题，本申请提供了一种环氧橡胶吸波涂料及其制备方法。As described in the background art, the composite wave absorbing materials in the prior art have poor wave absorbing performance and temperature resistance. In order to solve this problem, this application provides an epoxy rubber wave-absorbing coating and a preparation method thereof.
在本申请一种典型的实施方式中，提供了一种环氧橡胶吸波涂料，该环氧橡胶吸波涂料包括经过增韧改性的环氧树脂和经过抗氧化改性的铁氧体吸波剂。In a typical embodiment of the present application, there is provided an epoxy rubber wave-absorbing coating, which includes a toughened modified epoxy resin and an oxidation-resistant modified ferrite Wave agent.
本申请的环氧橡胶吸波涂料中，由于环氧树脂经过增韧改性，使得改性后的环氧树脂具备高分子网络结构，使得环氧树脂的耐热性、粘结性、耐磨性、抗冲击性、产品加工使用性能均得到提高，同时使得改性后的环氧树脂更易与铁氧体吸波剂进行复合；经过抗氧化改性的铁氧体吸波剂，提高了吸波剂的抗氧化能力和分散性，拓宽了吸波材料的吸波频带。复合后形成的涂料不但兼具了上述两种材料的性能，还使得铁氧体吸波剂的加工使用性能更加优越，使得环氧橡胶吸波涂料能够有效改善吸波效果和耐温性能，最终复合得到的环氧橡胶吸波涂料的低频吸收频带更宽、吸波性能更稳定、耐温效果更突出。In the epoxy rubber wave-absorbing coating of the present application, the epoxy resin undergoes toughening modification, so that the modified epoxy resin has a polymer network structure, which makes the epoxy resin heat resistance, adhesion, and wear resistance. The resistance, impact resistance and product processing performance have been improved, and at the same time, the modified epoxy resin is easier to compound with the ferrite wave absorber; the ferrite wave absorber modified by oxidation resistance improves the absorption The anti-oxidation ability and dispersion of the wave agent broaden the wave absorption band of the wave absorbing material. The coating formed after compounding not only has the performance of the above two materials, but also makes the processing and use performance of the ferrite wave absorber more superior, so that the epoxy rubber wave absorbing coating can effectively improve the wave absorbing effect and temperature resistance, and finally The compounded epoxy rubber wave-absorbing coating has a wider low-frequency absorption frequency band, more stable wave-absorbing performance, and more outstanding temperature resistance effect.
对环氧树脂进行增韧改性的方法有多种，为了简化本申请的环氧橡胶吸波涂料的制备，在一种优选的实施例中，上述经过增韧改性的环氧树脂为混合有液态橡胶的环氧树脂。通过向环氧树脂中添加液态橡胶，橡胶会与环氧树脂发生发应，形成高分子橡塑网络结构，实现对环氧树脂的增韧改性，该结构不但能够显著提高环氧树脂的耐热性、粘结性以及耐磨性，还有利于促进环氧树脂与铁氧体吸波剂的复合，显著提高复合吸波涂料的吸波性能。优选环氧树脂选自EP815、EP828、EP827和EP834中的一种或多种，优选液态橡胶选自氯化橡胶、丁腈橡胶和聚硫橡胶中的一种或多种，但是环氧树脂和液态橡胶的选择包括但并不仅限于上述提供的范围，只要环氧树脂能够与液态橡胶进行反应实现增韧，产生更稳定的结构即可。There are various methods of toughening and modifying epoxy resins. In order to simplify the preparation of the epoxy rubber wave-absorbing coating of the present application, in a preferred embodiment, the above-mentioned toughened and modified epoxy resins are mixed Epoxy resin with liquid rubber. By adding liquid rubber to the epoxy resin, the rubber will react with the epoxy resin to form a polymer rubber-plastic network structure to achieve toughening and modification of the epoxy resin. This structure can significantly improve the resistance of the epoxy resin. Heat, adhesion and abrasion resistance are also beneficial to promote the compounding of epoxy resin and ferrite wave absorber, and significantly improve the wave absorbing performance of the compound wave absorbing coating. Preferably the epoxy resin is selected from one or more of EP815, EP828, EP827 and EP834, preferably the liquid rubber is selected from one or more of chlorinated rubber, nitrile rubber and polysulfide rubber, but the epoxy resin and The choice of liquid rubber includes but is not limited to the range provided above, as long as the epoxy resin can react with the liquid rubber to achieve toughening and produce a more stable structure.
对铁氧体进行抗氧化改性的方法可以参考现有技术，在一种优选的实施例中，上述经过抗氧化改性的铁氧体吸波剂为表面包覆有偶联剂的铁氧体吸波剂。通过将偶联剂包覆在铁氧体吸波剂的表面，有效阻止了铁氧体吸波剂与空气的接触，使得铁氧体吸波剂的抗氧化性能得以提升，同时由于包覆在铁氧体表面的偶联剂的结构，使得铁氧体吸波剂更易与环氧树脂进行复合。优选地，偶联剂与铁氧体吸波剂的质量比为0.05~0.1:1，偶联剂与铁氧体吸波剂的质量比与铁氧体吸波剂表面偶联剂的包覆厚度存在关联，也影响着铁氧体吸波剂的抗氧化改性效果以及与环氧树脂的复合效果，优选上述比例的偶联剂与铁氧体吸波剂的质量比，不仅有利于实现铁氧体吸波剂的抗氧化性能，还有利于促进铁氧体吸波剂与环氧树脂的复合，进而有利于提高复合吸波涂料的吸波性能。优选铁氧体吸波剂选自磁铅石型铁氧体，更优选地，磁铅石型铁氧体选自M型铁氧体（如BaFe 12O 19，SrFe 12O 19）、Z型铁氧体（如Ba 3Me 2Fe 24O 41）和W型铁氧体（如BaMe 2Fe 16O 27）中的一种或多种。优选偶联剂选自硅烷偶联剂，更优选硅烷偶联剂选自γ-氨丙基三乙氧基硅烷（偶联剂KH-550）、3-（2,3-环氧丙氧）丙基三甲氧基硅烷（偶联剂KH-560）、γ-（甲基丙烯酰氧）丙基三甲氧基硅烷（偶联剂KH-570）和γ-丙基三乙氧基硅烷（偶联剂KH-580）中的一种或多种。铁氧体吸波剂和偶联剂的选择包括但并不仅限于上述提供的范围，只要偶联剂能够与铁氧体吸波剂进行包覆以隔绝空气，同时偶联剂能够与环氧树脂结合即可。为了便于硅烷偶联剂与铁氧体的包覆，以进一步提高铁氧体的改性效果，可以用乙醇、丙醇等醇类有机溶剂对硅烷偶联剂进行稀释，或将铁氧体溶于上述醇类有机溶剂中，再添加硅烷偶联剂。 For the method of performing anti-oxidation modification on the ferrite, reference may be made to the prior art. In a preferred embodiment, the anti-oxidation modified ferrite wave absorber is ferrite coated with a coupling agent on the surface Body absorbing agent. By coating the coupling agent on the surface of the ferrite wave absorber, the contact between the ferrite wave absorber and the air is effectively prevented, so that the anti-oxidation performance of the ferrite wave absorber can be improved. The structure of the coupling agent on the surface of the ferrite makes the ferrite absorber easier to compound with the epoxy resin. Preferably, the mass ratio of the coupling agent to the ferrite wave absorber is 0.05~0.1:1, the mass ratio of the coupling agent to the ferrite wave absorber and the coating of the ferrite wave absorber surface coupling agent The thickness is related, and it also affects the antioxidant modification effect of the ferrite wave absorber and the composite effect with the epoxy resin. It is preferable that the mass ratio of the coupling agent to the ferrite wave absorber in the above ratio is not only conducive to achieving The anti-oxidation performance of the ferrite wave absorbing agent is also beneficial to promote the compounding of the ferrite wave absorbing agent and the epoxy resin, and thus to improve the wave absorbing performance of the composite wave absorbing coating. Preferably, the ferrite wave absorber is selected from magnetoplumbite type ferrite, and more preferably, the magnetoplumbite type ferrite is selected from M type ferrite (such as BaFe 12 O 19 , SrFe 12 O 19 ), Z type One or more of ferrite (such as Ba 3 Me 2 Fe 24 O 41 ) and W-type ferrite (such as BaMe 2 Fe 16 O 27 ). Preferably, the coupling agent is selected from silane coupling agents, more preferably the silane coupling agent is selected from γ-aminopropyltriethoxysilane (coupling agent KH-550), 3-(2,3-epoxypropoxy) Propyltrimethoxysilane (coupling agent KH-560), γ-(methacryloyloxy)propyltrimethoxysilane (coupling agent KH-570) and γ-propyltriethoxysilane (coupling One or more of the joint agent KH-580). The choice of ferrite wave absorber and coupling agent includes but is not limited to the range provided above, as long as the coupling agent can be coated with the ferrite wave absorber to isolate the air, while the coupling agent can be combined with the epoxy resin Just combine them. In order to facilitate the coating of the silane coupling agent and the ferrite to further improve the modification effect of the ferrite, the organic solvent such as ethanol and propanol can be used to dilute the silane coupling agent or to dissolve the ferrite A silane coupling agent is added to the alcohol organic solvent.
在一种优选的实施例中，按重量份计，上述环氧橡胶吸波涂料中包括10~20份液态橡胶、60~80份环氧树脂与10~75份经过抗氧化改性的铁氧体吸波剂。其中，液态橡胶与环氧树脂的不同比例直接影响着吸波材料的耐温耐磨性能的改善程度，环氧树脂与经过抗氧化改性的铁氧体吸波剂的不同比例直接影响着吸波材料的吸波波段变化和低频吸收频带的变化，将液态橡胶、环氧树脂与经过抗氧化改性的铁氧体吸波剂的混合比例控制在上述提供的范围内，有利于进一步提高复合吸波涂料的吸波性能、耐温性以及低频吸收频带的宽度。In a preferred embodiment, in terms of parts by weight, the above-mentioned epoxy rubber absorbing coating includes 10-20 parts of liquid rubber, 60-80 parts of epoxy resin and 10-75 parts of antioxidant-modified ferrite Body absorbing agent. Among them, the different ratios of liquid rubber and epoxy resin directly affect the improvement of the temperature and wear resistance of the absorbing material, and the different ratios of epoxy resin and ferrite absorbing agent modified by oxidation directly affect the absorption The change of the absorption band of the wave material and the change of the low-frequency absorption band control the mixing ratio of the liquid rubber, epoxy resin and ferrite absorber modified by oxidation resistance within the range provided above, which is conducive to further improve the compounding The absorbing performance, temperature resistance and the width of the low-frequency absorption band of the absorbing coating.
为了便于上述环氧橡胶吸波涂料的制备，在一种优选的实施例中，上述环氧橡胶吸波涂料还包括稀释剂，其中，稀释剂选自醋酸甲酯、醋酸乙酯、醋酸戊酯、醋酸丁酯中的一种或多种；优选地，按重量份计，稀释剂为12~18份。在上述环氧树脂中添加稀释剂，有利于促进环氧树脂与铁氧体吸波剂的结合，通过将稀释剂的种类和添加量控制在上述范围内，有利于进一步促进环氧树脂与铁氧体吸波剂的结合，缩短复合时间。优选地，环氧橡胶吸波涂料还包括分散剂和消泡剂；更优选地，按重量份计，分散剂为3~5份，消泡剂为3~5份。其中，消泡剂有利于去除上述材料混合过程中产生的气泡，避免气泡的存在影响复合吸波涂料的固化使用效果；分散剂则有利于促进铁氧体吸波剂在环氧树脂中分布的更为均匀，保证该复合吸波涂料在使用时，所形成的整个涂覆层均具备优良的吸波效果。优选分散剂选自聚丙烯碳酸钠盐、聚乙二醇和聚乙烯醇中的一种或多种；优选消泡剂选自聚二甲基硅氧烷和/或磷酸三丁酯。In order to facilitate the preparation of the epoxy rubber wave-absorbing coating, in a preferred embodiment, the epoxy rubber wave-absorbing coating further includes a diluent, wherein the diluent is selected from methyl acetate, ethyl acetate, and amyl acetate One or more of butyl acetate; preferably, the diluent is 12 to 18 parts by weight. Adding diluent to the above epoxy resin is helpful to promote the combination of epoxy resin and ferrite absorber. By controlling the type and amount of diluent within the above range, it is conducive to further promote the epoxy resin and iron The combination of oxygen absorbing agent shortens the compounding time. Preferably, the epoxy rubber wave-absorbing coating further includes a dispersant and a defoamer; more preferably, the dispersant is 3 to 5 parts by weight, and the defoamer is 3 to 5 parts by weight. Among them, the defoamer is helpful to remove the bubbles generated during the mixing of the above materials, to avoid the presence of bubbles affecting the curing effect of the composite wave-absorbing coating; the dispersant is helpful to promote the distribution of the ferrite wave-absorbing agent in the epoxy resin It is more uniform to ensure that the entire coating layer formed by the composite wave-absorbing coating has excellent wave-absorbing effect when it is used. Preferably, the dispersant is selected from one or more of polypropylene sodium carbonate, polyethylene glycol, and polyvinyl alcohol; preferably, the defoamer is selected from polydimethylsiloxane and/or tributyl phosphate.
在另一种典型的实施方式中，还提供了一种环氧橡胶吸波涂料的制备方法，该制备方法包括：先将经过增韧改性的环氧树脂进行稀释处理，以得到稀释树脂；然后将得到的稀释树脂与经过抗氧化改性的铁氧体吸波剂混合，得到环氧橡胶吸波涂料。In another typical embodiment, a method for preparing an epoxy rubber wave-absorbing coating is also provided. The preparation method includes: first diluting a toughened and modified epoxy resin to obtain a diluted resin; Then, the obtained diluted resin is mixed with an anti-oxidation modified ferrite wave-absorbing agent to obtain an epoxy rubber wave-absorbing paint.
本申请首先将经过增韧改性后的环氧树脂进行稀释处理，使得环氧树脂利于与其他材料进行复合，然后将稀释后树脂与经过抗氧化改性的铁氧体吸波剂进行混合，得到一种复合环氧橡胶吸波涂料，该复合涂料兼具经过增韧改性的环氧树脂和经过抗氧化改性的铁氧体吸波剂两者的性能，实现了铁氧体吸波剂吸波性能的充分发挥，同时使得吸波材料的抗氧化性、耐温性以及低频吸收频带宽度得以提升。上述制备方法简单，且通过上述制备方法得到的环氧橡胶复合吸波涂料能够改善电磁波匹配性能，使得复合吸波涂料的低频吸收频带更宽、吸波性能更显著。耐温效果更突出。由此可见采用上述制备方法制备复合吸波涂料，工艺简单、易于操作、成本低，可实现规模化生产，同时得到的复合吸波涂料吸波性能更显著、耐温效果更突出，在实现雷达隐身领域有良好的应用前景。In this application, the toughened and modified epoxy resin is first diluted to make the epoxy resin easier to compound with other materials, and then the diluted resin is mixed with the anti-oxidation modified ferrite wave absorber. A composite epoxy rubber wave-absorbing coating is obtained, which has the performance of both toughened modified epoxy resin and anti-oxidation-modified ferrite wave-absorbing agent, and realizes the ferrite wave-absorbing The wave-absorbing performance of the agent is fully exerted, and at the same time, the oxidation resistance, temperature resistance and low-frequency absorption band width of the wave-absorbing material are improved. The above preparation method is simple, and the epoxy rubber composite wave absorbing coating obtained by the above preparation method can improve the electromagnetic wave matching performance, so that the low frequency absorption frequency band of the composite wave absorbing coating is wider and the wave absorbing performance is more remarkable. The temperature resistance effect is more prominent. It can be seen that the above-mentioned preparation method is used to prepare the composite wave-absorbing coating. The process is simple, easy to operate, and the cost is low. It can realize large-scale production. At the same time, the obtained composite wave-absorbing coating has more remarkable wave-absorbing performance and more outstanding temperature resistance. The stealth field has good application prospects.
对环氧树脂进行增韧改性的方法有多种，为了简化本申请的环氧橡胶吸波涂料的制备，在一种优选的实施例中，上述制备方法还包括对环氧树脂增韧改性的步骤，上述环氧树脂的增韧改性步骤包括：将液态橡胶与环氧树脂混合搅拌，得到经过增韧改性的环氧树脂；优选地，按重量份计，液态橡胶为10~20份，环氧树脂为60~80份；优选环氧树脂选自EP815、EP828、EP827和EP834中的一种或多种，优选液态橡胶选自氯化橡胶、丁腈橡胶和聚硫橡胶中的一种或多种。通过向环氧树脂中添加液态橡胶，橡胶会与环氧树脂发生发应，形成高分子橡塑网络结构，实现对环氧树脂的增韧改性，该结构不但能够显著提高环氧树脂的耐热性、粘结性以及耐磨性，还有利于促进环氧树脂与铁氧体吸波剂的复合，显著提高复合吸波涂料的吸波性能。There are various methods for toughening and modifying epoxy resins. In order to simplify the preparation of the epoxy rubber wave-absorbing coating of the present application, in a preferred embodiment, the above preparation method further includes toughening and modifying epoxy resins. The step of toughening and modifying the epoxy resin includes: mixing and stirring the liquid rubber with the epoxy resin to obtain a toughened and modified epoxy resin; preferably, the liquid rubber is 10~ by weight 20 parts, epoxy resin is 60~80 parts; preferably epoxy resin is selected from one or more of EP815, EP828, EP827 and EP834, preferably liquid rubber is selected from chlorinated rubber, nitrile rubber and polysulfide rubber One or more. By adding liquid rubber to the epoxy resin, the rubber will react with the epoxy resin to form a polymer rubber-plastic network structure to achieve toughening and modification of the epoxy resin. This structure can significantly improve the resistance of the epoxy resin. Heat, adhesion and abrasion resistance are also beneficial to promote the compounding of epoxy resin and ferrite wave absorber, and significantly improve the wave absorbing performance of the compound wave absorbing coating.
为了便于上述环氧橡胶吸波涂料的制备，在一种优选的实施例中，上述稀释处理步骤包括：将稀释剂与经过增韧改性的环氧树脂混合搅拌，得到稀释树脂；其中，稀释剂选自醋酸甲酯、醋酸乙酯、醋酸戊酯、醋酸丁酯中的一种或多种；优选地，按重量份计，稀释剂为12~18份。在环氧树脂中添加稀释剂，有利于促进环氧树脂与铁氧体吸波剂的结合，通过将稀释剂的种类和添加量控制在上述范围内，有利于进一步促进环氧树脂与铁氧体吸波剂的结合，缩短复合时间。In order to facilitate the preparation of the above-mentioned epoxy rubber wave-absorbing coating, in a preferred embodiment, the above-mentioned dilution treatment step includes: mixing and agitating the diluent with the toughened modified epoxy resin to obtain a diluted resin; wherein, the dilution The agent is selected from one or more of methyl acetate, ethyl acetate, amyl acetate, and butyl acetate; preferably, the diluent is 12-18 parts by weight. Adding a diluent to the epoxy resin is helpful to promote the combination of the epoxy resin and the ferrite absorber. By controlling the type and amount of the diluent within the above range, it is beneficial to further promote the epoxy resin and ferrite The combination of body absorbers shortens the compounding time.
对铁氧体进行抗氧化改性的方法可以参考现有技术，在一种优选的实施例中，上述制备方法还包括对铁氧体吸波剂进行抗氧化改性的步骤，上述铁氧体吸波剂的抗氧化改性的步骤包括：首先将粒径小于400目的铁氧体吸波剂颗粒与有机溶剂混合，得到铁氧体吸波剂颗粒分散液；然后将铁氧体吸波剂颗粒分散液与偶联剂混合后进行球磨处理，得到悬浊液；最后将悬浊液进行干燥处理，得到经过抗氧化改性的铁氧体吸波剂；优选铁氧体吸波剂选自磁铅石型铁氧体，更优选磁铅石型铁氧体选自M型铁氧体（BaFe 12O 19，SrFe 12O 19）、Z型铁氧体（Ba 3Me 2Fe 24O 41）和W型铁氧体（BaMe 2Fe 16O 27）中的一种或多种；优选有机溶剂选自乙醇和/或丙醇；优选偶联剂选自硅烷偶联剂，更优选硅烷偶联剂选自γ-氨丙基三乙氧基硅烷、3-(2,3-环氧丙氧)丙基三甲氧基硅烷、γ-（甲基丙烯酰氧）丙基三甲氧基硅烷和γ-丙基三乙氧基硅烷中的一种或多种；更优选偶联剂与铁氧体吸波剂的质量比为0.05~0.1:1。 For the method of performing anti-oxidation modification on the ferrite, reference may be made to the prior art. In a preferred embodiment, the above preparation method further includes the step of performing anti-oxidation modification on the ferrite wave absorber. The steps of the anti-oxidation modification of the wave absorber include: first mixing the ferrite wave absorber particles with a particle size of less than 400 mesh and an organic solvent to obtain a dispersion liquid of the ferrite wave absorber particles; then the ferrite wave absorber The particle dispersion is mixed with the coupling agent and then ball milled to obtain a suspension. Finally, the suspension is dried to obtain an anti-oxidation modified ferrite wave absorber; preferably the ferrite wave absorber is selected from Magnetoplumbite type ferrite, more preferably magnetoplumbite type ferrite is selected from M-type ferrite (BaFe 12 O 19 , SrFe 12 O 19 ), Z-type ferrite (Ba 3 Me 2 Fe 24 O 41 ) And one or more of W-type ferrite (BaMe 2 Fe 16 O 27 ); preferably the organic solvent is selected from ethanol and/or propanol; preferably the coupling agent is selected from silane coupling agents, more preferably silane coupling The coupling agent is selected from γ-aminopropyltriethoxysilane, 3-(2,3-glycidoxy)propyltrimethoxysilane, γ-(methacryloyloxy)propyltrimethoxysilane and One or more of γ-propyltriethoxysilane; more preferably, the mass ratio of the coupling agent to the ferrite wave absorber is 0.05 to 0.1:1.
为了便于最终得到的复合吸波涂料的使用，优选球磨机对铁氧体吸波剂进行球磨处理，然后用400目筛网过筛，得到粒径小于400目的均匀铁氧体吸波剂颗粒，然后将铁氧体吸波剂颗粒分散在有机溶剂中，再与偶联剂混合进行球磨处理，球磨过程有利于偶联剂包覆在铁氧体吸波剂的表面，实现对铁氧体吸波剂的抗氧化改性。通过将偶联剂包覆在铁氧体吸波剂的表面，有效阻止了铁氧体吸波剂与空气的接触，使得铁氧体吸波剂的抗氧化性能得以提升，同时由于包覆在铁氧体表面的偶联剂的结构，使得铁氧体吸波剂更易与环氧树脂进行复合。偶联剂和铁氧体吸波剂的质量比与改性后铁氧体吸波剂的抗氧化性能存在关联，将质量比控制在上述范围内，有利于提升改性后铁氧体吸波剂的抗氧化性能，同时铁氧体吸波剂和偶联剂的选择包括但并不仅限于上述提供的范围，只要偶联剂能够与铁氧体吸波剂进行包覆以隔绝空气，同时偶联剂能够与环氧树脂结合即可。In order to facilitate the use of the finally obtained composite wave-absorbing coating, it is preferred that the ball mill performs ball milling on the ferrite wave-absorbing agent, and then sieves with a 400-mesh screen to obtain uniform ferrite wave-absorbing agent particles with a particle size of less than 400 mesh, and then Disperse the ferrite absorbing agent particles in an organic solvent, and then mix with the coupling agent for ball milling. The ball milling process is beneficial for the coupling agent to coat the surface of the ferrite absorbing agent to realize the absorption of ferrite. Antioxidant modification of the agent. By coating the coupling agent on the surface of the ferrite wave absorber, the contact between the ferrite wave absorber and the air is effectively prevented, so that the anti-oxidation performance of the ferrite wave absorber is improved. The structure of the coupling agent on the surface of the ferrite makes the ferrite absorber easier to compound with the epoxy resin. The mass ratio of the coupling agent and the ferrite wave absorber is related to the antioxidant performance of the modified ferrite wave absorber. Controlling the mass ratio within the above range is conducive to improving the wave absorption of the modified ferrite The antioxidant performance of the agent, and the choice of ferrite wave absorber and coupling agent include but are not limited to the range provided above, as long as the coupling agent can be coated with the ferrite wave absorber to isolate the air, while coupling The joint agent can be combined with the epoxy resin.
在一种优选的实施例中，稀释树脂与经过抗氧化改性的铁氧体吸波剂混合的步骤包括：利用超声将稀释树脂与经过抗氧化改性的铁氧体吸波剂的混合，得到环氧橡胶吸波涂料，优选地，按重量份计，经过抗氧化改性的铁氧体吸波剂为10~75份；优选将稀释树脂与经过抗氧化改性的铁氧体吸波剂混合的步骤包括：利用超声将稀释树脂、经过抗氧化改性的铁氧体吸波剂、分散剂和消泡剂混合，得到环氧橡胶吸波涂料，优选超声处理的时间为5~7h，超声频率为25~30KHz；稀释剂选自醋酸甲酯、醋酸乙酯、醋酸戊酯、醋酸丁酯中的一种或多种；优选地，按重量份计，稀释剂为12~18份；优选地，环氧橡胶吸波涂料还包括分散剂和消泡剂；更优选地，按重量份计，分散剂为3~5份，消泡剂为3~5份。优选分散剂选自聚丙烯碳酸钠盐、聚乙二醇和聚乙烯醇中的一种或多种；优选消泡剂选自聚二甲基硅氧烷和/或磷酸三丁酯。In a preferred embodiment, the step of mixing the diluted resin with the anti-oxidation modified ferrite wave absorber includes: mixing the diluted resin with the anti-oxidation modified ferrite wave absorber using ultrasound, To obtain an epoxy rubber wave-absorbing coating, preferably, by weight, the antioxidant-modified ferrite wave-absorbing agent is 10 to 75 parts; it is preferable to dilute the diluted resin with the oxidation-resistant modified ferrite wave-absorbing agent The mixing steps of the agent include: mixing the diluted resin, the ferrite absorber modified with oxidation resistance, the dispersant and the defoaming agent by ultrasound to obtain the epoxy rubber absorber coating, preferably the ultrasonic treatment time is 5~7h , Ultrasonic frequency is 25~30KHz; diluent is selected from one or more of methyl acetate, ethyl acetate, amyl acetate, butyl acetate; preferably, the diluent is 12-18 parts by weight ; Preferably, the epoxy rubber wave-absorbing coating further includes a dispersant and a defoamer; more preferably, by weight, the dispersant is 3 to 5 parts, and the defoamer is 3 to 5 parts. Preferably, the dispersant is selected from one or more of polypropylene sodium carbonate, polyethylene glycol, and polyvinyl alcohol; preferably, the defoamer is selected from polydimethylsiloxane and/or tributyl phosphate.
通过超声分散仪对稀释树脂与经过抗氧化改性的铁氧体吸波剂进行分散处理，使得经过增韧改性的环氧树脂与经过抗氧化改性的铁氧体吸波剂的充分混合，使得复合得到的环氧橡胶吸波涂料中两种材料均与分布，有利于吸波涂料的吸波性能稳定性。环氧树脂与经过抗氧化改性的铁氧体吸波剂的不同比例直接影响着吸波材料的吸波和低频吸收频带，将经过抗氧化改性的铁氧体吸波剂的添加比例控制在上述提供的范围内，有利于进一步提高复合吸波涂料的吸波性能、耐温性以及低频吸收频带的宽度。Disperse the diluted resin and the anti-oxidation-modified ferrite absorber with an ultrasonic disperser, so that the toughened modified epoxy resin and the anti-oxidation-modified ferrite absorber are fully mixed , So that the two materials in the epoxy rubber wave-absorbing coating compounded are both distributed, which is conducive to the stability of the wave-absorbing coating's wave-absorbing performance. The different proportions of epoxy resin and anti-oxidation-modified ferrite absorber directly affect the absorption and low-frequency absorption bands of the absorber, and the addition ratio of anti-oxidation-modified ferrite absorber is controlled Within the range provided above, it is beneficial to further improve the wave absorbing performance, temperature resistance and the width of the low frequency absorption band of the composite wave absorbing coating.
以下结合具体实施例对本申请作进一步详细描述，这些实施例不能理解为限制本申请所要求保护的范围。The present application will be described in further detail below with reference to specific embodiments, which cannot be understood as limiting the scope of protection claimed by the present application.
实施例1Example 1
首先将Z型铁氧体（Ba 3Me 2Fe 24O 41）球磨60h，然后用400目筛网过筛，得到筛下铁氧体吸波剂颗粒，将铁氧体吸波剂颗粒分散于乙醇中，加入占铁氧体吸波剂质量5%的硅烷偶联剂（KH-550），继续球磨30min后，将得到的悬浊液烘干得到经过抗氧化改性的铁氧体吸波剂，保存备用。 First, the Z-type ferrite (Ba 3 Me 2 Fe 24 O 41 ) was ball-milled for 60 h, and then sieved with a 400-mesh screen to obtain sieve ferrite absorbing agent particles, and the ferrite absorbing agent particles were dispersed in To ethanol, add a silane coupling agent (KH-550) which accounts for 5% of the ferrite absorber mass, and after ball milling for 30 minutes, dry the resulting suspension to obtain an anti-oxidation modified ferrite absorber. Agent, save for future use.
按重量份计，称取10份氯化橡胶（型号CR20）添加到60份环氧树脂（EP815）中，同时加入15份醋酸乙酯进行稀释搅拌，得到稀释树脂。称取10份上述经过改性的铁氧体吸波剂加入稀释树脂中，添加3份聚乙二醇（分散剂）、3份磷酸三丁酯（消泡剂），用超声分散仪分散5h，其中超声频率为25KHz，得到环氧橡胶吸波涂料。Based on parts by weight, 10 parts of chlorinated rubber (model CR20) was weighed out and added to 60 parts of epoxy resin (EP815). At the same time, 15 parts of ethyl acetate was added for dilution and stirring to obtain a diluted resin. Weigh 10 parts of the above-mentioned modified ferrite wave absorber into the diluted resin, add 3 parts of polyethylene glycol (dispersant), 3 parts of tributyl phosphate (defoamer), and disperse with an ultrasonic disperser for 5 hours , Where the ultrasonic frequency is 25KHz, to obtain epoxy rubber wave-absorbing coating.
实施例2Example 2
按重量份计，称取15份丁腈橡胶（170型）添加到70份环氧树脂（EP828）中，同时加入12份醋酸甲酯进行稀释搅拌，得到稀释树脂。称取20份经过偶联剂KH-560改性的M型铁氧体吸波剂加入稀释树脂中，添加4份聚丙烯碳酸钠盐分散剂、4份聚二甲基硅氧烷消泡剂，用超声分散仪分散6h，其中超声频率为25KHz，得到环氧橡胶吸波涂料。Based on parts by weight, 15 parts of nitrile rubber (type 170) was weighed and added to 70 parts of epoxy resin (EP828), and 12 parts of methyl acetate was added for dilution and stirring to obtain a diluted resin. Weigh 20 parts of M-type ferrite absorbing agent modified by coupling agent KH-560 into the diluted resin, add 4 parts of polypropylene sodium carbonate dispersant, 4 parts of polydimethylsiloxane defoamer, Disperse with an ultrasonic disperser for 6h, where the ultrasonic frequency is 25KHz to obtain epoxy rubber wave-absorbing coating.
实施例3Example 3
按重量份计，称取20份聚硫橡胶（型号LP-2）添加到80份环氧树脂（EP827）中，同时加入18份醋酸戊酯进行稀释搅拌，得到稀释树脂。称取40份经过偶联剂KH-570改性的W型铁氧体吸波剂加入稀释树脂中，添加5份聚乙二醇分散剂、5份磷酸三丁酯消泡剂，用超声分散仪分散7h，其中超声频率为30KHz，得到环氧橡胶吸波涂料。Based on parts by weight, 20 parts of polysulfide rubber (model LP-2) was weighed and added to 80 parts of epoxy resin (EP827), and 18 parts of amyl acetate was added for dilution and stirring to obtain a diluted resin. Weigh 40 parts of W-type ferrite absorbing agent modified by coupling agent KH-570 into the diluted resin, add 5 parts of polyethylene glycol dispersant, 5 parts of tributyl phosphate defoamer, and disperse with ultrasound The instrument was dispersed for 7h, and the ultrasonic frequency was 30KHz to obtain epoxy rubber wave-absorbing coating.
实施例4Example 4
按重量份计，称取20份丁腈橡胶（170型）添加到80份环氧树脂（EP834）中，同时加入18份醋酸乙酯进行稀释搅拌，得到稀释树脂。称取75份上述经过改性偶联剂KH-580改性的W型铁氧体吸波剂加入稀释树脂中，添加5份聚乙烯醇分散剂、5份磷酸三丁酯消泡剂，用超声分散仪分散7h，其中超声频率为30KHz，得到环氧橡胶吸波涂料。Based on parts by weight, 20 parts of nitrile rubber (type 170) was weighed and added to 80 parts of epoxy resin (EP834), while 18 parts of ethyl acetate was added for dilution and stirring to obtain a diluted resin. Weigh 75 parts of the W-type ferrite absorber modified by the modified coupling agent KH-580 into the diluted resin, add 5 parts of polyvinyl alcohol dispersant, 5 parts of tributyl phosphate defoamer, use The ultrasonic disperser disperses for 7h, the ultrasonic frequency is 30KHz, and the epoxy rubber wave-absorbing coating is obtained.
实施例5Example 5
与实施例1不同的是，偶联剂占铁氧体吸波剂的质量比为10%。Different from Example 1, the mass ratio of the coupling agent to the ferrite wave absorber is 10%.
对比例1Comparative Example 1
与实施例1不同的是，所添加的铁氧体吸波剂不经过偶联剂进行高温抗氧化改性。The difference from Example 1 is that the added ferrite wave absorber does not undergo high-temperature anti-oxidation modification without a coupling agent.
对比例2Comparative Example 2
与实施例1不同的是，制备过程中不添加液态橡胶，即不对环氧树脂进行增韧改性。The difference from Example 1 is that no liquid rubber is added during the preparation process, that is, the epoxy resin is not toughened and modified.
对比例3Comparative Example 3
与实施例1不同的是，制备过程中不添加液态橡胶，且所添加的铁氧体吸波剂不经过偶联剂进行抗氧化改性。The difference from Example 1 is that no liquid rubber is added during the preparation process, and the added ferrite absorbing agent is not subjected to anti-oxidation modification through the coupling agent.
吸波性能测试方式：向上述制备得到的环氧橡胶吸波涂料中加入12份环氧树脂固化剂改性脂环胺混合搅拌均匀后注入规格为300×300×2mm的模具中，常温固化成型，得到固化层为2mm的环氧橡胶吸波涂料，将固化层与标准金属板材（尺寸300×300×2mm）粘结后，放入微波暗室制定接收平面，采用弓形反射法按照GJB2038标准对双层平板吸波材料在微波暗室内进行电磁性能参数测试，测试结果见表1。Wave absorption performance test method: add 12 parts of epoxy resin curing agent modified alicyclic amine to the epoxy rubber wave absorbing coating prepared above, mix and evenly inject it into a mold of 300×300×2mm, and cure at room temperature Obtain epoxy resin wave-absorbing coating with a cured layer of 2mm. After bonding the cured layer with a standard metal sheet (size 300×300×2mm), place it in a microwave dark room to formulate the receiving plane. The electromagnetic absorption parameters of the layered absorbing material are tested in the microwave dark room. The test results are shown in Table 1.
高温抗氧化性能测试方法：抗氧化是在特定的环境中体现出来的，一般是高温中。将上述制备的固化涂层放在200℃恒温烘箱中，24h后查看是否有起皮、脱落现象，并测试材料的吸波性能。High temperature oxidation resistance test method: oxidation resistance is reflected in a specific environment, generally in high temperature. The cured coating prepared above was placed in a constant temperature oven at 200°C. After 24 hours, check whether there was peeling or peeling, and test the material's wave absorption performance.
柔韧性测试方法：将上述制备的固化涂层厚度为2mm，参照GBT1731漆膜柔韧性测试方法进行测试。Flexibility test method: the thickness of the cured coating prepared above is 2 mm, and the test is performed according to the GBT1731 paint film flexibility test method.
Figure dest_path_image001
Figure dest_path_image001
从以上的描述中，可以看出，本发明上述的实施例实现了如下技术效果：From the above description, it can be seen that the above embodiments of the present invention achieve the following technical effects:
由于环氧树脂经过增韧改性，使得改性后的环氧树脂具备高分子网络结构，使得环氧树脂的耐热性、粘结性、耐磨性、抗冲击性产品加工使用性能均得到提高，同时使得改性后的环氧树脂更易与铁氧体吸波剂进行复合；经过抗氧化改性的铁氧体吸波剂，提高了吸波剂的抗氧化能力和分散性，如表1中实施例1至实施例4所示，随着抗氧化改性的铁氧体含量增加，峰位向低频移动，且在15.4GHz，吸收率≥90%的带宽可达6.4GHz，仍具有较好的吸波性能和频宽。复合后形成的涂料不但兼具了上述两种材料的性能，还使得铁氧体吸波剂的加工使用性能更加优越，使得环氧橡胶吸波涂料能够有效改善吸波效果和耐温性能，最终复合得到的环氧橡胶吸波涂料的低频吸收频带更宽、吸波性能更稳定、耐温效果更突出。Because the epoxy resin is toughened and modified, the modified epoxy resin has a polymer network structure, so that the heat resistance, adhesion, wear resistance and impact resistance of the epoxy resin are processed and used. Improve, at the same time make the modified epoxy resin easier to compound with the ferrite wave absorber; the ferrite wave absorber modified by anti-oxidation improves the antioxidant capacity and dispersibility of the wave absorber, as shown in the table As shown in Example 1 to Example 4 in 1, as the content of anti-oxidation-modified ferrite increases, the peak position shifts to a low frequency, and at 15.4 GHz, the bandwidth of absorption rate ≥ 90% can reach 6.4 GHz, still having Better absorbing performance and bandwidth. The coating formed after compounding not only has the performance of the above two materials, but also makes the processing and use performance of the ferrite wave absorber more superior, so that the epoxy rubber wave absorbing coating can effectively improve the wave absorbing effect and temperature resistance, and finally The compounded epoxy rubber wave-absorbing coating has a wider low-frequency absorption frequency band, more stable wave-absorbing performance, and more outstanding temperature resistance effect.
工业实用性Industrial applicability
以上所述仅为本发明的优选实施例而已，并不用于限制本发明，对于本领域的技术人员来说，本发明可以有各种更改和变化。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内97。The above is only the preferred embodiments of the present invention and is not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and changes. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention97.

Claims (10)

  1. 一种环氧橡胶吸波涂料，其特征在于，所述环氧橡胶吸波涂料包括经过增韧改性的环氧树脂和经过抗氧化改性的铁氧体吸波剂。An epoxy rubber wave-absorbing coating, characterized in that the epoxy rubber wave-absorbing coating includes a toughened and modified epoxy resin and an anti-oxidation modified ferrite wave-absorbing agent.
  2. 根据权利要求1所述的环氧橡胶吸波涂料，其特征在于，所述经过抗氧化改性的铁氧体吸波剂为表面包覆有偶联剂的铁氧体吸波剂，优选所述偶联剂与所述铁氧体吸波剂的质量比为0.05~0.1:1；优选所述铁氧体吸波剂选自磁铅石型铁氧体，更优选地，所述磁铅石型铁氧体选自M型铁氧体、Z型铁氧体和W型铁氧体中的一种或多种；优选所述偶联剂选自硅烷偶联剂，更优选所述硅烷偶联剂选自γ-氨丙基三乙氧基硅烷、3-(2,3-环氧丙氧)丙基三甲氧基硅烷、γ-（甲基丙烯酰氧）丙基三甲氧基硅烷和γ-丙基三乙氧基硅烷中的一种或多种。The epoxy rubber wave-absorbing paint according to claim 1, wherein the anti-oxidation modified ferrite wave-absorbing agent is a ferrite wave-absorbing agent coated with a coupling agent on the surface, preferably The mass ratio of the coupling agent to the ferrite wave absorber is 0.05~0.1:1; preferably, the ferrite wave absorber is selected from magnetoplumbite type ferrite, more preferably, the magnetic lead Stone type ferrite is selected from one or more of M type ferrite, Z type ferrite and W type ferrite; preferably the coupling agent is selected from silane coupling agents, more preferably the silane The coupling agent is selected from γ-aminopropyltriethoxysilane, 3-(2,3-glycidoxy)propyltrimethoxysilane, γ-(methacryloyloxy)propyltrimethoxysilane And one or more of γ-propyltriethoxysilane.
  3. 根据权利要求1所述的环氧橡胶吸波涂料，其特征在于，所述经过增韧改性的环氧树脂为混合有液态橡胶的环氧树脂，优选所述环氧树脂选自EP815、EP828、EP827和EP834中的一种或多种；优选所述液态橡胶选自氯化橡胶、丁腈橡胶和聚硫橡胶中的一种或多种。The epoxy rubber wave-absorbing coating according to claim 1, wherein the toughened modified epoxy resin is an epoxy resin mixed with liquid rubber, preferably the epoxy resin is selected from EP815 and EP828 , EP827 and EP834 one or more; preferably the liquid rubber is selected from one or more of chlorinated rubber, nitrile rubber and polysulfide rubber.
  4. 根据权利要求3所述的环氧橡胶吸波涂料，其特征在于，按重量份计，所述环氧橡胶吸波涂料中包括10~20份所述液态橡胶、60~80份所述环氧树脂与10~75份所述经过抗氧化改性的铁氧体吸波剂。The epoxy rubber wave-absorbing paint according to claim 3, wherein the epoxy rubber wave-absorbing paint includes 10 to 20 parts of the liquid rubber and 60 to 80 parts of the epoxy by weight parts Resin and 10~75 parts of the anti-oxidation modified ferrite wave absorber.
  5. 根据权利要求4所述的环氧橡胶吸波涂料，其特征在于，所述环氧橡胶吸波涂料还包括稀释剂，所述稀释剂选自醋酸甲酯、醋酸乙酯、醋酸戊酯、醋酸丁酯中的一种或多种；优选地，按重量份计，所述稀释剂为12~18份；优选地，所述环氧橡胶吸波涂料还包括分散剂和消泡剂；更优选地，按重量份计，所述分散剂为3~5份，所述消泡剂为3~5份。The epoxy rubber wave-absorbing paint according to claim 4, wherein the epoxy rubber wave-absorbing paint further comprises a diluent selected from methyl acetate, ethyl acetate, amyl acetate, and acetic acid One or more of butyl ester; preferably, the diluent is 12 to 18 parts by weight; preferably, the epoxy rubber wave-absorbing coating further includes a dispersant and a defoamer; more preferably In terms of parts by weight, the dispersant is 3 to 5 parts, and the defoamer is 3 to 5 parts.
  6. 一种环氧橡胶吸波涂料的制备方法，其特征在于，所述制备方法包括以下步骤：A preparation method of epoxy rubber wave-absorbing paint, characterized in that the preparation method comprises the following steps:
    将经过增韧改性的环氧树脂进行稀释处理，得到稀释树脂；Dilute the toughened modified epoxy resin to obtain diluted resin;
    将所述稀释树脂与经过抗氧化改性的铁氧体吸波剂混合，得到所述环氧橡胶吸波涂料。The diluted resin is mixed with an anti-oxidation-modified ferrite wave-absorbing agent to obtain the epoxy rubber wave-absorbing paint.
  7. 根据权利要求6所述的制备方法，其特征在于，所述制备方法还包括对所述环氧树脂增韧改性的步骤，所述对环氧树脂进行增韧改性的步骤包括：The preparation method according to claim 6, wherein the preparation method further comprises a step of toughening and modifying the epoxy resin, and the step of toughening and modifying the epoxy resin comprises:
    将液态橡胶与所述环氧树脂混合搅拌，得到所述经过增韧改性的环氧树脂；优选地，按重量份计，所述液态橡胶为10~20份，所述环氧树脂为60~80份；Mixing and stirring the liquid rubber with the epoxy resin to obtain the toughened modified epoxy resin; preferably, the liquid rubber is 10-20 parts by weight, and the epoxy resin is 60 ~80 copies;
    优选所述环氧树脂选自EP815、EP828、EP827和EP834中的一种或多种；优选所述液态橡胶选自氯化橡胶、丁腈橡胶和聚硫橡胶中的一种或多种。Preferably, the epoxy resin is selected from one or more of EP815, EP828, EP827, and EP834; preferably, the liquid rubber is selected from one or more of chlorinated rubber, nitrile rubber, and polysulfide rubber.
  8. 根据权利要求6所述的制备方法，其特征在于，所述稀释处理步骤包括：The preparation method according to claim 6, wherein the dilution treatment step comprises:
    将稀释剂与所述经过增韧改性的环氧树脂混合搅拌，得到所述稀释树脂；Mixing and stirring the diluent with the toughened and modified epoxy resin to obtain the diluted resin;
    其中，所述稀释剂选自醋酸甲酯、醋酸乙酯、醋酸戊酯、醋酸丁酯中的一种或多种；优选地，按重量份计，所述稀释剂为12~18份。Wherein, the diluent is selected from one or more of methyl acetate, ethyl acetate, amyl acetate, and butyl acetate; preferably, the diluent is 12-18 parts by weight.
  9. 根据权利要求6所述的制备方法，其特征在于，所述制备方法还包括对所述铁氧体吸波剂进行抗氧化改性的步骤，所述对铁氧体吸波剂进行抗氧化改性的步骤包括：The preparation method according to claim 6, characterized in that the preparation method further comprises the step of carrying out anti-oxidation modification on the ferrite wave absorber, and the anti-oxidation modification on the ferrite wave absorber The sexual steps include:
    将粒径小于400目的铁氧体吸波剂颗粒与有机溶剂混合，得到铁氧体吸波剂颗粒分散液；Mixing ferrite absorbing agent particles with a particle size of less than 400 mesh and an organic solvent to obtain a ferrite absorbing agent particle dispersion;
    将所述铁氧体吸波剂颗粒分散液与偶联剂混合后进行球磨处理，得到悬浊液；Mixing the ferrite wave absorbing agent particle dispersion with the coupling agent and performing ball milling treatment to obtain a suspension;
    将所述悬浊液进行干燥处理，得到所述经过抗氧化改性的铁氧体吸波剂；Drying the suspension to obtain the anti-oxidation modified ferrite wave absorber;
    优选所述铁氧体吸波剂选自磁铅石型铁氧体，更优选地，所述磁铅石型铁氧体选自M型铁氧体、Z型铁氧体和W型铁氧体中的一种或多种；优选所述有机溶剂选自乙醇和/或丙醇；优选所述偶联剂选自硅烷偶联剂，更优选所述硅烷偶联剂选自γ-氨丙基三乙氧基硅烷、3-(2,3-环氧丙氧)丙基三甲氧基硅烷、γ-（甲基丙烯酰氧）丙基三甲氧基硅烷和γ-丙基三乙氧基硅烷中的一种或多种；更优选所述偶联剂与所述铁氧体吸波剂的质量比为0.05~0.1:1。Preferably, the ferrite absorbing agent is selected from magnetoplumbite type ferrite, and more preferably, the magnetoplumbite type ferrite is selected from M type ferrite, Z type ferrite and W type ferrite One or more of the compounds; preferably the organic solvent is selected from ethanol and/or propanol; preferably the coupling agent is selected from a silane coupling agent, more preferably the silane coupling agent is selected from γ-aminopropyl Triethoxysilane, 3-(2,3-glycidoxy)propyltrimethoxysilane, γ-(methacryloyloxy)propyltrimethoxysilane and γ-propyltriethoxy One or more of silanes; more preferably, the mass ratio of the coupling agent to the ferrite wave absorber is 0.05 to 0.1:1.
  10. 根据权利要求6所述的制备方法，其特征在于，将所述稀释树脂与所述经过抗氧化改性的铁氧体吸波剂混合的步骤包括：The preparation method according to claim 6, characterized in that the step of mixing the diluted resin with the anti-oxidation modified ferrite wave absorber comprises:
    利用超声将所述稀释树脂与所述经过抗氧化改性的铁氧体吸波剂的混合，得到所述环氧橡胶吸波涂料；优选地，按重量份计，所述经过抗氧化改性的铁氧体吸波剂为10~75份；Mixing the diluted resin with the anti-oxidation-modified ferrite wave-absorbing agent by ultrasound to obtain the epoxy rubber absorbing coating; preferably, the anti-oxidation-modified by weight parts The ferrite wave absorber is 10~75 parts;
    优选将所述稀释树脂与经过抗氧化改性的铁氧体吸波剂混合的步骤包括：Preferably, the step of mixing the diluted resin with the ferrite absorber modified by oxidation resistance includes:
    利用超声将所述稀释树脂、所述经过抗氧化改性的铁氧体吸波剂、分散剂和消泡剂混合，得到所述环氧橡胶吸波涂料；优选所述超声的处理时间为5~7h，所述超声频率为25~30KHz。Mixing the diluted resin, the anti-oxidation-modified ferrite wave absorber, dispersant, and defoamer with ultrasound to obtain the epoxy rubber wave-absorbing coating; preferably, the ultrasound treatment time is 5 ~7h, the ultrasonic frequency is 25~30KHz.
PCT/CN2019/111290 2018-12-06 2019-10-15 Epoxy rubber radiation-absorbing coating and preparation method therefor WO2020114092A1 (en)

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