CN114874481A - Polymethacrylimide foam with multi-layer wave-absorbing structure and preparation method thereof - Google Patents
Polymethacrylimide foam with multi-layer wave-absorbing structure and preparation method thereof Download PDFInfo
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- CN114874481A CN114874481A CN202210721310.7A CN202210721310A CN114874481A CN 114874481 A CN114874481 A CN 114874481A CN 202210721310 A CN202210721310 A CN 202210721310A CN 114874481 A CN114874481 A CN 114874481A
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- Prior art keywords
- wave
- absorbing
- foam
- polymethacrylimide foam
- agent
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- 229920007790 polymethacrylimide foam Polymers 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000011347 resin Substances 0.000 claims abstract description 33
- 229920005989 resin Polymers 0.000 claims abstract description 33
- 239000006096 absorbing agent Substances 0.000 claims abstract description 31
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000003063 flame retardant Substances 0.000 claims abstract description 28
- 238000004132 cross linking Methods 0.000 claims abstract description 25
- 230000005855 radiation Effects 0.000 claims abstract description 24
- 238000005187 foaming Methods 0.000 claims abstract description 23
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 16
- 239000002562 thickening agent Substances 0.000 claims abstract description 16
- 238000010521 absorption reaction Methods 0.000 claims abstract description 13
- 239000011159 matrix material Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims description 59
- 239000000835 fiber Substances 0.000 claims description 41
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 24
- 229910052799 carbon Inorganic materials 0.000 claims description 24
- 239000000843 powder Substances 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 17
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- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 16
- 230000002745 absorbent Effects 0.000 claims description 15
- 239000002250 absorbent Substances 0.000 claims description 15
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical class [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 claims description 15
- 230000000379 polymerizing effect Effects 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 12
- 239000003999 initiator Substances 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N 1,4-Benzenediol Natural products OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 10
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000004088 foaming agent Substances 0.000 claims description 8
- 238000007599 discharging Methods 0.000 claims description 7
- 239000003112 inhibitor Substances 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 7
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 7
- HGXJDMCMYLEZMJ-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOOC(=O)C(C)(C)C HGXJDMCMYLEZMJ-UHFFFAOYSA-N 0.000 claims description 6
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 239000011574 phosphorus Substances 0.000 claims description 5
- -1 phosphorus compound Chemical class 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 4
- 239000004925 Acrylic resin Substances 0.000 claims description 4
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- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- 239000003431 cross linking reagent Substances 0.000 claims description 4
- 239000006249 magnetic particle Substances 0.000 claims description 4
- 229920001490 poly(butyl methacrylate) polymer Polymers 0.000 claims description 3
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000292 calcium oxide Substances 0.000 claims description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 2
- 125000000687 hydroquinonyl group Chemical group C1(O)=C(C=C(O)C=C1)* 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 2
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 claims description 2
- QTECDUFMBMSHKR-UHFFFAOYSA-N prop-2-enyl prop-2-enoate Chemical compound C=CCOC(=O)C=C QTECDUFMBMSHKR-UHFFFAOYSA-N 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 239000006260 foam Substances 0.000 abstract description 23
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000010410 layer Substances 0.000 description 24
- 229920001577 copolymer Polymers 0.000 description 12
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 11
- 229910010271 silicon carbide Inorganic materials 0.000 description 11
- 229920000049 Carbon (fiber) Polymers 0.000 description 9
- 239000004917 carbon fiber Substances 0.000 description 9
- 239000011259 mixed solution Substances 0.000 description 9
- 239000004114 Ammonium polyphosphate Substances 0.000 description 7
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 7
- 229920001276 ammonium polyphosphate Polymers 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 5
- 229920000877 Melamine resin Polymers 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 description 4
- 239000011358 absorbing material Substances 0.000 description 4
- YLFBFPXKTIQSSY-UHFFFAOYSA-N dimethoxy(oxo)phosphanium Chemical compound CO[P+](=O)OC YLFBFPXKTIQSSY-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000002310 reflectometry Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000003892 spreading Methods 0.000 description 4
- 230000007480 spreading Effects 0.000 description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 229910052790 beryllium Inorganic materials 0.000 description 3
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000008098 formaldehyde solution Substances 0.000 description 3
- 150000002978 peroxides Chemical group 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- 239000004254 Ammonium phosphate Substances 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 2
- 235000019289 ammonium phosphates Nutrition 0.000 description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000006261 foam material Substances 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000004506 ultrasonic cleaning Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- NYYLZXREFNYPKB-UHFFFAOYSA-N 1-[ethoxy(methyl)phosphoryl]oxyethane Chemical compound CCOP(C)(=O)OCC NYYLZXREFNYPKB-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- RWIGWWBLTJLKMK-UHFFFAOYSA-N diethoxyphosphorylmethanol Chemical compound CCOP(=O)(CO)OCC RWIGWWBLTJLKMK-UHFFFAOYSA-N 0.000 description 1
- OIERWUPLBOKSRB-UHFFFAOYSA-N dimethoxyphosphorylmethanol Chemical compound COP(=O)(CO)OC OIERWUPLBOKSRB-UHFFFAOYSA-N 0.000 description 1
- VONWDASPFIQPDY-UHFFFAOYSA-N dimethyl methylphosphonate Chemical compound COP(C)(=O)OC VONWDASPFIQPDY-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
- B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
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- 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
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/322—Ammonium phosphate
- C08K2003/323—Ammonium polyphosphate
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Abstract
The invention discloses polymethacrylimide foam with a multilayer wave-absorbing structure and a preparation method thereof, the foam is prepared from components such as matrix resin, a thickening agent, a flame retardant, a wave-absorbing agent and the like through the working procedures of layering, polymerization, radiation crosslinking, high-temperature foaming and the like, the prepared wave-absorbing PMI foam can be designed, has the multilayer wave-absorbing structure without bonding, also has the advantages of short production period, good broadband wave-absorbing performance, high strength, good flame retardant property, uniform density and strength and the like, can be used for a sandwich structure, is used as a secondary bearing structural member, and is applied to the field with radar electromagnetic wave absorption and light weight requirements for all military uses.
Description
Technical Field
The invention relates to Polymethacrylimide (PMI) foam with a multi-layer wave-absorbing structure and a preparation method thereof, belonging to the technical field of wave-absorbing materials.
Background
Polymethacrylimide (PMI) foam is a high-strength high-temperature-resistant structural rigid foam with excellent performance, forms a plurality of varieties through continuous optimization for nearly 50 years, is widely applied to various fields of military use and civil use, and the existing commercially available PMI foam is a conventional variety and cannot meet special requirements of specific fields, such as the field of electromagnetic shielding.
In recent years, many researches have been made on structural wave-absorbing foam materials using rigid foam such as polyurethane as a base material, for example, patent CN101740143, patent CN102529229 and patent CN103923337, but the published reports on the research on the wave-absorbing performance of high-performance PMI foam are less. Patent CN106939110 of New Material Limited of Bohang in Hunan discloses a light, high-strength, high-temperature-resistant, broadband wave-absorbing PMI foam and a preparation method thereof, wherein an electromagnetic wave absorbent is added into monomer resin, and a two-step method is adopted to prepare uniform wave-absorbing PMI foam which has controllable density, excellent mechanical property and better radar wave absorption property at 2-40 GHz, but with the development of the structural wave-absorbing material towards the demand directions of ultra-wide band, super-strong absorption, thinning and the like, the existing single-layer wave-absorbing structural design can not meet the performance requirement of the structural wave-absorbing material which is improved continuously.
Disclosure of Invention
Aiming at the defects of the wave-absorbing foam material in the prior art, the invention aims to provide the Polymethacrylimide (PMI) foam which is light in weight, high in strength, more excellent in broadband wave-absorbing performance and provided with a multi-layer wave-absorbing structure.
The second purpose of the invention is to provide a method for preparing polymethacrylimide foam which has uniform density and a multilayer wave-absorbing structure and can be produced in large batch.
In order to realize the technical purpose, the following technical scheme is adopted:
the invention relates to polymethacrylimide foam with a multi-layer wave-absorbing structure, which is divided into n layers, wherein n is not less than 2, and the polymethacrylimide foam is prepared from the following raw materials in parts by mass through layering, radiation crosslinking, low-temperature polymerization and high-temperature foaming:
100 parts of matrix mixed resin; 0.1-3 parts of a third monomer; 0.2-30 parts of a broadband wave absorbing agent; 3-20 parts of a thickening agent; 20-100 parts of a flame retardant; 0.01-0.5 part of an initiator; 0.1-5 parts of a crosslinking agent; 3-12 parts of a foaming agent; 0.01-0.05 part of polymerization inhibitor;
the matrix mixed resin is a mixture consisting of a acrylonitrile resin monomer and an acrylic resin monomer;
the broadband wave absorbing agent is a mixture consisting of a magnetized fiber broadband wave absorbing agent and a granular absorbent;
the flame retardant is a mixture consisting of a liquid phosphorus compound and modified ammonium phosphate powder.
In the preferable scheme, the polymethacrylimide foam is divided into 3-20 layers, preferably 5-7 layers.
In a preferable scheme, the thickness of any layer of the polymethacrylimide foam is 1-20 mm.
In a preferable scheme, in two layers which are randomly contacted in the polymethacrylimide foam, the adding amount of the broadband wave absorber in the upper layer is 0.9-3 times, preferably 1-2 times of the mass of the broadband wave absorber in the lower layer.
The inventor finds that the polymethacrylimide foam with a multi-layer wave-absorbing structure and the broadband wave-absorbing agent in each layer arranged in the manner have the most excellent wave-absorbing performance.
In a preferable scheme, in the matrix mixed resin, the mass ratio of the acrylonitrile-based resin monomer to the acrylic resin monomer is 0.8-1.2: 1. more preferred acrylonitrile-based monomers are methacrylonitrile and/or acrylonitrile. More preferred acrylic monomers are methacrylic acid and/or acrylic acid.
In a preferred scheme, the broadband wave absorber comprises the following components in percentage by mass: 5-60% of magnetized fiber broadband wave absorbing agent and 40-95% of granular absorbent.
Further preferably, the broadband wave absorber comprises the following components in percentage by mass: 30-60% of magnetized fiber broadband wave absorbing agent and 40-70% of granular absorbent.
Further preferably, the magnetized fibrous broadband wave absorber is at least one selected from fibers and magnetized fibers, and is preferably magnetized fibers.
Still more preferably, the fibers are selected from at least one of carbon fibers, aluminum-containing silicon carbide fibers, zirconium-containing silicon carbide fibers, beryllium-containing silicon carbide fibers.
Still more preferably, the magnetized fiber broadband wave absorbing agent is at least one selected from the group consisting of magnetized carbon fibers, magnetized silicon carbide fibers, magnetized aluminum-containing silicon carbide fibers, magnetized zirconium-containing silicon carbide fibers, and magnetized beryllium-containing silicon carbide fibers. Preferably, the magnetized fiber broadband wave absorbing agent is formed by coating magnetic wave absorbing sol and/or particles on the surface of the fiber, wherein the total mass percentage content of the magnetic wave absorbing sol and the particles is 10-70%; the fiber is at least one of carbon fiber, silicon carbide fiber, beryllium-containing silicon carbide fiber, aluminum-containing silicon carbide fiber and zirconium-containing silicon carbide fiber.
Preferably, the diameter of the monofilament of the magnetized fiber broadband wave absorber is 1-50 μm, and the magnetized fiber broadband wave absorber is cut to 0.1-10 mm after ultrasonic cleaning and vacuum drying. The fibers of the present invention are all purchased from outsources.
Further preferably, the particulate absorbent is at least one of carbon particles and magnetic particles.
Further preferably, the carbon particles have a particle size of less than 15 μm and a specific resistance of less than 0.15 Ω. cm 2 It is used after ultrasonic cleaning and vacuum drying. Therefore, the carbon particles provided by the invention are high-conductivity carbon particles.
Further preferably, the magnetic particles have a particle size of less than 0.7 μm.
In a preferred scheme, the flame retardant consists of 50-80 mass percent of liquid phosphorus compound and 20-50 mass percent of modified ammonium phosphate powder.
Further preferably, the liquid phosphorus compound is selected from at least one of dimethyl methylphosphonate, diethyl methylphosphonate, dimethyl hydroxymethylphosphonate and diethyl hydroxymethylphosphonate.
Further preferably, the modified ammonium phosphate powder is obtained by the following steps: melamine, formaldehyde solution, acrylonitrile and acrylic acid are adopted to prepare pre-polymerized liquid, and ammonium polyphosphate is coated by utilizing a microcapsule technology.
Further preferably, the ammonium phosphate-based powder: melamine: formaldehyde: acrylonitrile: the weight ratio of acrylic acid is 100-500: 18-35: 10-30: 0.5-1: 0.05 to 1.
Further preferably, the modified ammonium phosphate powder is obtained by the following steps: firstly, uniformly mixing melamine and formaldehyde solution, reacting at 60-90 ℃ for 30-90 min to prepare a pre-polymerization solution, then adding ammonium polyphosphate powder into the pre-polymerization solution for primary coating, drying and crushing after coating, finally adding a solvent and an initiator into the ammonium polyphosphate powder after primary coating, uniformly mixing, then adding an acrylonitrile and acrylic acid mixed solution, reacting for 1-3 h at 50-70 ℃, drying and crushing to obtain two layers of in-situ coated ammonium polyphosphate powder, and thus obtaining the modified ammonium phosphate powder.
Further preferably, the initiator is a peroxide initiator.
Further preferably, the modified ammonium phosphate powder contains not less than 11% of N and P 2 O 3 The content is not less than 60%.
The inventor surprisingly found that the flame retardant effect can be greatly improved by modifying ammonium phosphate powder with melamine. The flame retardant provided by the invention has the flame retardant effect which is 1.0-1.3 times of the flame retardant capability of the liquid flame retardant in the same mass part, and the introduction of the modified ammonium phosphate powder can effectively improve the flame retardant capability of the wave-absorbing material.
Preferably, the thickener is at least one selected from the group consisting of polymethyl methacrylate and polybutyl methacrylate.
Further preferably, the particle size of the thickening agent is 0.05-1 mm, and the molecular weight is more than 300 ten thousand.
The inventor finds that the thickening agent is added after being crushed into irregular particles with the particle size of 0.05-1 mm, so that the dissolving efficiency can be improved.
The polymethyl methacrylate and the polybutyl methacrylate are prepared by adopting a free radical polymerization method, and the polymers are obtained by low-temperature polymerization of methyl methacrylate or butyl methacrylate for 72 hours by adopting 3-6 initiators.
The inventors have found that by this process it is possible to produce large quantities of polymer with a molecular weight greater than 300 million and that by adding only 4% wt to the resin, a viscosity of greater than 8000cps can be achieved in the resin system.
In a preferred embodiment, the initiator is selected from the group consisting of tert-butyl peroxybenzoate, tert-butyl peroxypivalate, and neodecanoyl peroxide
30-50% of acid cumyl ester by mass: 30-50%: 20-30%: 20-30% of the composition.
In a preferred scheme, the foaming agent is prepared from 10-50% of isopropanol and formamide by mass percent: 50-90% of the composition;
in a preferred embodiment, the crosslinking agent is at least one of allyl methacrylate, allyl acrylate, magnesium oxide, and calcium oxide.
In a preferred embodiment, the third monomer is at least one of acrylamide, methacrylamide, acrylamide, styrene, and itaconic acid.
In a preferred scheme, the polymerization inhibitor is hydroquinone or p-benzoquinone;
according to the technical scheme, the types and relative contents of the components in the formula such as the absorbent, the flame retardant and the like are comprehensively adjusted, so that the foam density and the electromagnetic absorption performance can be regulated and controlled, and the flame retardant performance and the heat resistance of the foam are improved.
The invention also provides a preparation method of the polymethacrylimide foam with the multilayer wave-absorbing structure, which comprises the steps of mixing the matrix mixed resin and the thickening agent to obtain viscous mixed resin, adding the initiator, the foaming agent, the polymerization inhibitor and the flame retardant into the viscous mixed resin to obtain mixed liquid, dividing the mixed liquid into n parts, adding the broadband wave-absorbing agent with different mass percentage contents according to the design components of each layer of the polymethacrylimide foam to obtain n parts of mixed base materials, paving the n parts of mixed base materials in a mould according to the design components in sequence, and performing prepolymerization, heat treatment I, radiation crosslinking, foaming and heat treatment II in sequence to obtain the polymethacrylimide foam.
Preferably, the matrix mixed resin and the thickening agent are mixed for 24-36 hours at 25-40 ℃ under stirring to obtain viscous mixed resin.
In the actual operation process, the matrix resin monomer and the thickening agent are poured into a closed reaction container in sequence, and are placed into a closed stirring container for stirring, wherein the stirring mode adopts electric stirring.
In the invention, the viscosity of the viscous mixed resin is controlled by the thickening agent, the obtained viscous mixed resin has high viscosity, uniformity and transparency, and the resin has high viscosity but is still in a liquid phase, so that certain permeation exists at the interface of two adjacent layers in the resin layering process, the combination of the two layers can be ensured, and the clarity of the two layers can be ensured.
Preferably, the viscosity of the mixed resin is 8000cps to 50000 cps.
According to the preferable scheme, after the n parts of mixed base materials are discharged, the mixed base materials are sequentially paved in a mould according to the designed components, and the mode of discharging the bubbles is ultrasonic waves and/or vacuum bubble discharge.
In the invention, the content of the absorbent of each layer of wave-absorbing PMI foam in the whole piece of wave-absorbing PMI foam with a multi-layer wave-absorbing structure and the thickness of the layer spread of the wave-absorbing PMI foam can be designed and adjusted.
In a preferred embodiment, the prepolymerization conditions are as follows: placing the die in a constant temperature environment, polymerizing for 1-5 h at 35-50 ℃, and then polymerizing for 36-120 h at 30-50 ℃;
preferably, the conditions of the heat treatment I are as follows: treating for 3-12 h in a hot air furnace at 60-100 ℃;
according to the preferable scheme, radiation crosslinking is carried out under the protection of nitrogen, and in the radiation crosslinking process, the radiation crosslinking absorption dose is 7-60 kGy.
In the invention, the radiation crosslinking energy reduces the residual monomer content, improves the crosslinking degree between interfaces, improves the uniformity of the whole foam plate, and further improves the physical and mechanical properties of the plate.
Preferably, the foaming conditions are as follows: foaming at 120-150 ℃ for 6-10 h; foaming for 0.5-3 h at 150-200 ℃;
preferably, the conditions of the heat treatment II are as follows: the treatment is carried out for 1-5 h at 100-140 ℃, and then for 1-5 h at 80-100 ℃.
The polymethacrylimide foam with a multilayer wave-absorbing structure is prepared by preparing high-viscosity mixed liquid by using basic mixed resin and a thickening agent, introducing components such as a flame retardant and a mixed foaming agent, adding a fibrous wave-absorbing agent and a composite broadband wave-absorbing agent consisting of granular absorption to prepare wave-absorbing PMI foam pre-polymerization liquid, then sequentially laying mixed base materials with different absorbent contents in a mold after discharging bubbles, polymerizing at two temperatures to prepare PMI foam copolymer with the absorbent distributed in a multilayer structure, and finally producing the broadband wave-absorbing PMI foam through the working procedures of radiation crosslinking, heat treatment, high-temperature foaming and the like. The specific production comprises the following steps:
(1) preparing a mixed solution: sequentially pouring the matrix mixed resin and the thickening agent into a closed reaction container, placing the closed reaction container into a closed stirring container, and stirring and mixing for 24-48 hours to obtain a high-viscosity mixed solution; the mixing mode is electric stirring and mixing; the temperature in the closed stirring container is controlled to be 25-40 ℃.
(2) Sequentially adding a foaming agent, a flame retardant, an initiator and a polymerization inhibitor into the mixed solution obtained in the step (1), mixing for 1-2 h, finally adding broadband wave absorbers with different mass ratios, stirring and mixing for 0.5-2 h until uniform dispersion is achieved, and obtaining PMI foam prepolymer liquid with different absorbent contents; the stirring and mixing mode is preferably electric stirring; the temperature in the closed stirring container is controlled to be 20-40 ℃.
(3) After defoaming the prepolymerization liquid prepared in the step (2), discharging bubbles, sequentially paving the bubbles in a mold, completely sealing, putting the mold into a circulating water bath system, polymerizing for 1-5 h at 35-50 ℃, and polymerizing for 36-120 h at 25-50 ℃ to obtain a PMI foam copolymer; the defoaming mode is ultrasonic or/and vacuum defoaming; the ply thickness and absorbent content of each ply may be determined by simulation design.
(4) Placing the crosslinked copolymer obtained in the step (3) in a hot air furnace, and treating for 3-12 hours at the temperature of 60-100 ℃ in the hot air furnace;
(5) and (4) carrying out radiation crosslinking on the crosslinked copolymer in the step (4). Radiation crosslinking conditions: carrying out radiation crosslinking under the protection of nitrogen, wherein the radiation crosslinking absorption dose is 7-60 kGy;
(6) foaming: the crosslinked interpolymer in step (5): foaming for 3-10 h at 120-170 ℃; foaming for 0.5-5 h at 170-200 ℃; the absorbing PMI foam can be obtained
(7) And (3) heat treatment: treating for 1-5 h at 100-140 ℃, and then treating for 1-5 h at 80-100 ℃ to obtain the flame-retardant wave-absorbing polymethacrylimide foam with a multilayer structure.
Compared with the prior art, the technical scheme of the invention has the following beneficial technical effects:
1) the flame-retardant wave-absorbing PMI foam layer of the multilayer structure has no interface, and the content and the thickness of each absorbent layer can be designed.
2) Compared with the existing wave-absorbing foam, the flame-retardant and wave-absorbing PMI foam with the multilayer structure greatly improves the absorption of electromagnetic waves in the wave-absorbing frequency band of 1-40 GHz, and has a remarkable effect;
2) compared with the flame-retardant property of the traditional PMI wave-absorbing foam, the flame-retardant and wave-absorbing PMI foam with the multilayer structure has more excellent flame-retardant property, and obviously reduces smoke and toxicity.
3) The flame-retardant and wave-absorbing PMI foam adopts a radiation crosslinking technology, and the prepared wave-absorbing foam has the characteristics of high strength, light weight, high uniformity and the like, and has the density of 40-300 kg/m 3 (ii) a Has excellent mechanical strength and good heat resistance, and the heat distortion temperature is about 180 ℃.
4) The preparation process of the flame-retardant and wave-absorbing PMI wave-absorbing foam is simple and convenient, is easy to operate and can be used for mass production.
5) The wave-absorbing PMI foam has the advantages of light weight, high strength, flame retardance, wave absorption and high temperature resistance, can be used as a wave-absorbing sandwich structure, and can be widely applied to the national defense industry fields of aerospace, ships and the like.
6) The wave-absorbing PMI foam layer has no interface, is free from adhesion, reduces the adhesive layer, further reduces the weight of the component, and avoids other risks caused by the adhesive layer.
Drawings
FIG. 1 is a schematic representation of a blended pre-polymerized liquid overlay of example 1.
FIG. 2 is a schematic representation of a blended pre-polymerized liquid overlay of example 2.
FIG. 3 is a schematic representation of a blended pre-polymerized liquid overlay of comparative example 1.
FIG. 4 is a schematic representation of a blended pre-polymerized liquid overlay of comparative example 2.
Detailed Description
The present invention is further illustrated by the following examples, but it should be noted that the scope of the present invention is not limited to the following examples.
The preparation process route of the modified ammonium phosphate comprises the steps of firstly, uniformly mixing 25 parts of melamine and 17 parts of formaldehyde solution, reacting at 70 ℃ for 90min to prepare a pre-polymerization solution, secondly, putting 200 parts of ammonium polyphosphate powder into the pre-polymerization solution for primary coating, drying and crushing after coating, finally, adding an alcohol solvent and a peroxide initiator into the 200 parts of ammonium polyphosphate powder after primary coating, uniformly mixing, then adding 0.5 part of acrylonitrile and 0.5 part of acrylic acid mixed solution, reacting at 60 ℃ for 3h, and drying and crushing to obtain two layers of in-situ coated ammonium polyphosphate powder.
Example 1
1kg of polymethyl methacrylate was added to 10kg of methacrylic acid and 10kg of methacrylonitrile, and stirred at 33 ℃ for 26 hours. 0.7kg of isopropyl alcohol, 0.8kg of formamide, 2kg of dimethyl phosphonate, 1.4kg of modified ammonium phosphate, 0.0008kg of hydroquinone, 0.014kg of peroxydicarbonate, 0.012kg of tert-butyl peroxybenzoate, 0.006kg of tert-butyl peroxypivalate and 0.006kg of cumyl peroxyneodecanoate were mixed for 2 hours to obtain a mixed solution A.
(1) Adding 10g of magnetized carbon fiber and 10g of carbon particles into 1kg of mixed liquid A, stirring for 1h, and removing bubbles to obtain mixed liquid B 1 (ii) a (2) Adding 12g of magnetized carbon fiber and 11g of carbon particles into 1kg of mixed liquid A, stirring for 1h, and discharging bubbles to obtain mixed liquid B 2 (ii) a (3) Adding 15g of magnetized fiber and 12g of high-conductivity carbon particles into 1kg of mixed liquid A, stirring for 1h, and removing bubbles to obtain mixed liquid B 3 . (4) Adding 18g of magnetized fiber and 12g of high-conductivity carbon particles into 1kg of mixed liquid A, stirring for 1h, and removing bubbles to obtain mixed liquid B 4 . (5) Adding 20g of magnetic fiber and 36g of high-conductivity carbon particles into 1kg of mixed liquid A, stirring for 1h, and removing bubbles to obtain mixed liquid B 5 。
Mixing the pre-polymerized liquid B 1 、B 2 、B 3 Spreading into a mold, sealing, placing into a circulating water bath system, polymerizing at 37 deg.C for 8 hr, and polymerizing at 30 deg.C for 180 hr to obtain PMI foam copolymer as shown in FIG. 2; then placing the crosslinked copolymer in a hot air furnace, and treating for 5 hours at 60 ℃ and 100 ℃; then radiation crosslinking is carried out on the crosslinked copolymer under the conditions of nitrogen protection and radiation crosslinking absorption dose of 20 kGy; then placing the crosslinked copolymer at 170 ℃ for foaming for 4 h; foaming for 2h at 200 ℃; obtaining the wave-absorbing PMI foam; and finally, treating the foam at 130 ℃ for 2.5h, and then at 100 ℃ for 4h to obtain the finished product of the wave-absorbing PMI foam with a multilayer structure.
The density of the wave-absorbing PMI foam prepared by the embodiment is 80-110 kg/m 3 And a heat distortion temperature of 170 ℃. The foam self-extinguishes within 10s after leaving fire, and the foam has excellent wave absorbing performance due to the adoption of the efficient broadband wave absorbing agent, and the average reflectivity values of the foam in wave bands of 1-2 GHz, 2-18 GHz and 26.5-40 GHz are-23.88 db, -23.63db and-27.14 db respectively; the compression strength is 1.65MPa to 2.68 MPa.
Example 2
1kg of polymethyl methacrylate was added to 10kg of methacrylic acid and 10kg of methacrylonitrile, and stirred at 33 ℃ for 26 hours. 0.7kg of isopropyl alcohol, 0.8kg of formamide, 2kg of dimethyl phosphonate, 1.4kg of modified ammonium phosphate, 0.0008kg of hydroquinone, 0.014kg of peroxydicarbonate, 0.012kg of tert-butyl peroxybenzoate, 0.006kg of tert-butyl peroxypivalate and 0.006kg of cumyl peroxyneodecanoate were mixed for 2 hours to obtain a mixed solution A.
(1) 10g of magnetized carbon fiber and 10g of carbon particles were mixedAdding 1kg of mixed liquid A, stirring for 1h, and removing bubbles to obtain mixed liquid B 1 (ii) a (2) Adding 12g of magnetized carbon fiber and 11g of carbon particles into 1kg of mixed liquid A, stirring for 1h, and removing bubbles to obtain mixed liquid B 2 (ii) a (3) Adding 15g of magnetized fiber and 12g of high-conductivity carbon particles into 1kg of mixed liquid A, stirring for 1h, and removing bubbles to obtain mixed liquid B 3 . (4) Adding 15g of magnetized fiber and 20g of high-conductivity carbon particles into 1kg of mixed liquid A, stirring for 1h, and removing bubbles to obtain mixed liquid B 4 . (5) Adding 16g of magnetized fiber and 30g of high-conductivity carbon particles into 1kg of mixed liquid A, stirring for 1h, and removing bubbles to obtain mixed liquid B 5 . (6) Adding 18g of magnetized fiber and 30g of high-conductivity carbon particles into 1kg of mixed liquid A, stirring for 1h, and removing bubbles to obtain mixed liquid B 6 . (7) Adding 20g of magnetic fiber and 36g of high-conductivity carbon particles into 1kg of mixed liquid A, stirring for 1h, and removing bubbles to obtain mixed liquid B 7 。
Mixing the pre-polymerized liquid B 1 、B 2 、B 3 Spreading into a mold, sealing, placing into a circulating water bath system, polymerizing at 37 deg.C for 8 hr, and polymerizing at 30 deg.C for 180 hr to obtain PMI foam copolymer as shown in FIG. 2; then placing the crosslinked copolymer in a hot air furnace, and treating for 5 hours at 60 ℃ and 100 ℃; then radiation crosslinking is carried out on the crosslinked copolymer under the conditions of nitrogen protection and radiation crosslinking absorption dose of 20 kGy; then placing the crosslinked copolymer at 170 ℃ for foaming for 4 h; foaming for 2h at 200 ℃; obtaining the wave-absorbing PMI foam; and finally, treating the foam at 130 ℃ for 2.5 hours, and then at 100 ℃ for 4 hours to obtain a finished product of the wave-absorbing PMI foam with a multilayer structure.
The density of the wave-absorbing PMI foam prepared by the embodiment is 77-110 kg/m 3 And a heat distortion temperature of 170 ℃. The foam self-extinguishes within 10s after leaving fire, and the foam has excellent wave absorbing performance due to the adoption of the efficient broadband wave absorbing agent, wherein the average reflectivity values of the foam in wave bands of 1-2 GHz, 2-18 GHz and 26.5-40 GHz are-25.38 db, -24.13db and-30.55 db respectively; the compressive strength is 1.57MPa to 2.81 MPa.
Comparative example 1
1kg of polymethyl methacrylate was added to 10kg of methacrylic acid and 10kg of methacrylonitrile, and stirred at 33 ℃ for 26 hours. 0.7kg of isopropyl alcohol, 0.8kg of formamide, 2kg of dimethyl phosphonate, 1.4kg of modified ammonium phosphate, 0.0008kg of hydroquinone, 0.014kg of peroxydicarbonate, 0.012kg of tert-butyl peroxybenzoate, 0.006kg of tert-butyl peroxypivalate and 0.006kg of cumyl peroxyneodecanoate were mixed for 2 hours to obtain a mixed solution A. And adding 100g of magnetic fibers and 180g of high-conductivity carbon particles into 5kg of the mixed liquid A, stirring for 1h, and removing bubbles to prepare a mixed liquid B.
Mixing the pre-polymerized liquid B 5 Spreading the mixture into a mold, sealing the mold as shown in FIG. 3, putting the mold into a circulating water bath system, and polymerizing for 8 hours at 37 ℃ and then for 180 hours at 30 ℃ to obtain a PMI foam copolymer; then placing the crosslinked copolymer in a hot air furnace, and treating for 5 hours at 60 ℃ and 100 ℃; then radiation crosslinking is carried out on the crosslinked copolymer under the conditions of nitrogen protection and radiation crosslinking absorption dose of 20 kGy; then placing the crosslinked copolymer at 170 ℃ for foaming for 4 h; foaming for 2h at 200 ℃; obtaining the wave-absorbing PMI foam; and finally, treating the foam at 130 ℃ for 2.5h, and then at 100 ℃ for 4h to obtain the finished product of the wave-absorbing PMI foam with a multilayer structure.
The density of the wave-absorbing PMI foam prepared by the comparative example is 84-120 kg/m 3 And a heat distortion temperature of 170 ℃. Self-extinguishing within 10s after leaving fire, and because only a single-layer wave-absorbing structure is adopted, the mean values of the reflectivities of wave bands of 1-2 GHz, 2-18 GHz and 26.5-40 GHz are only-17.01 db, -19.53db and-23.64 db respectively; the compressive strength is 1.71MPa to 3.2 MPa.
Comparative example 2
1kg of polymethyl methacrylate was added to 10kg of methacrylic acid and 10kg of methacrylonitrile and stirred at 33 ℃ for 26 hours. 0.7kg of isopropyl alcohol, 0.8kg of formamide, 2kg of dimethyl phosphonate, 1.4kg of modified ammonium phosphate, 0.0008kg of hydroquinone, 0.014kg of peroxydicarbonate, 0.012kg of tert-butyl peroxybenzoate, 0.006kg of tert-butyl peroxypivalate and 0.006kg of cumyl peroxyneodecanoate were mixed for 2 hours to obtain a mixed solution A.
(1) Adding 10g of magnetized carbon fiber and 10g of carbon particles into 1kg of mixed liquid A, stirring for 1h, and removing bubbles to obtain mixed liquid B 1 (ii) a (2) Adding 12g of magnetized carbon fiber and 11g of carbon particles into 1kg of mixed liquid A, stirring for 1h, and discharging bubbles to obtain mixed liquid B 2 (ii) a (3) Adding 15g of magnetized fiber and 12g of high-conductivity carbon particles into 1kg of mixed liquid A, stirring for 1h, and removing bubbles to obtain mixed liquid B 3 . (4) Adding 18g of magnetized fiber and 12g of high-conductivity carbon particles into 1kg of mixed liquid A, stirring for 1h, and removing bubbles to obtain mixed liquid B 4 . (5) Adding 20g of magnetic fiber and 36g of high-conductivity carbon particles into 1kg of mixed liquid A, stirring for 1h, and removing bubbles to obtain mixed liquid B 5 。
Mixing the pre-polymerized liquid B 1 、B 2 、B 3 、B 4 、B 5 Spreading into a mold, sealing, placing into a circulating water bath system, polymerizing at 38 deg.C for 8h, and then at 30 deg.C for 180h to obtain PMI foam copolymer as shown in FIG. 4; then placing the crosslinked copolymer in a hot air furnace, and treating for 5 hours at 60 ℃ and 120 ℃; directly placing at 170 deg.C, foaming for 4 h; foaming for 2h at 200 ℃; obtaining the wave-absorbing PMI foam; and finally, treating the foam at 130 ℃ for 2.5h, and then at 100 ℃ for 4h to obtain the finished product of the wave-absorbing PMI foam with a multilayer structure.
The density of the wave-absorbing PMI foam prepared by the embodiment is 70-107 kg/m 3 The average reflectivity values of the wave bands of 1-2 GHz, 2-18 GHz and 26.5-40 GHz are-22.37 db, -23.00db and-25.94 db respectively; the compressive strength is 1.4MPa to 2.38 MPa.
Claims (10)
1. The utility model provides a polymethacrylimide foam with multilayer absorbing structure which characterized in that: the polymethacrylimide foam is divided into n layers, wherein n is not less than 2, and the polymethacrylimide foam is prepared from the following raw materials in parts by mass through layering, radiation crosslinking, low-temperature polymerization and high-temperature foaming:
100 parts of matrix mixed resin; 0.1-3 parts of a third monomer; 0.2-30 parts of a broadband wave absorbing agent; 3-20 parts of a thickening agent; 20-100 parts of a flame retardant; 0.01-0.5 part of an initiator; 0.1-5 parts of a crosslinking agent; 3-12 parts of a foaming agent; 0.01-0.05 part of polymerization inhibitor;
the matrix mixed resin is a mixture consisting of a acrylonitrile resin monomer and an acrylic resin monomer;
the broadband wave absorbing agent is a mixture consisting of a magnetized fiber broadband wave absorbing agent and a granular absorbent;
the flame retardant is a mixture consisting of a liquid phosphorus compound and modified ammonium phosphate powder.
2. The polymethacrylimide foam with a multilayer wave-absorbing structure as claimed in claim 1, wherein: the polymethacrylimide foam is divided into 3-20 layers;
the thickness of any layer of the polymethacrylimide foam is 1-20 mm;
in the polymethacrylimide foam, in two layers which are contacted randomly, the adding amount of the broadband wave absorbing agent in the upper layer is 0.9-3 times of the mass of the broadband wave absorbing agent in the lower layer.
3. The polymethacrylimide foam with a multilayer wave-absorbing structure as claimed in claim 1, wherein: in the matrix mixed resin, the mass ratio of the acrylonitrile resin monomer to the acrylic resin monomer is 0.8-1.2: 1;
the broadband wave absorbing agent comprises the following components in percentage by mass: 5-60% of magnetized fiber broadband wave absorbing agent and 40-95% of granular absorbent.
The fibrous broadband wave absorber is selected from at least one of fibers and magnetized fibers;
the granular absorbent is at least one of carbon particles and magnetic particles;
the grain diameter of the carbon particles is less than 15 mu m, and the specific resistance is less than 0.15 omega-cm 2 ；
The particle size of the magnetic particles is less than 0.7 μm.
4. The polymethacrylimide foam with a multilayer wave-absorbing structure as claimed in claim 1, wherein: the flame retardant consists of 50-80 mass percent of liquid phosphorus compound and 20-50 mass percent of modified ammonium phosphate powder;
the modified ammonium phosphate powder contains N not less than 11% and P 2 O 3 The content is not less than 60%.
5. The polymethacrylimide foam with a multilayer wave-absorbing structure as claimed in claim 1, wherein: the thickening agent is at least one selected from polymethyl methacrylate and polybutyl methacrylate;
the particle size of the thickening agent is 0.05-1 mm, and the molecular weight is more than 300 ten thousand;
the initiator is prepared from tert-butyl peroxybenzoate, tert-butyl peroxypivalate and cumyl peroxyneodecanoate in a mass percentage of 30-50%: 30-50%: 20-30%: 20-30% of the composition;
the foaming agent is prepared from 10-50% of isopropanol and formamide by mass percent: 50-90% of the composition.
6. The polymethacrylimide foam with a multilayer wave-absorbing structure as claimed in claim 1, wherein: the cross-linking agent is at least one of allyl methacrylate, allyl acrylate, magnesium oxide and calcium oxide.
The third monomer is at least one of acrylamide, methacrylamide, acrylamide, styrene and itaconic acid.
The polymerization inhibitor is hydroquinone or p-benzoquinone.
7. The preparation method of polymethacrylimide foam with a multilayer wave-absorbing structure as claimed in any one of claims 1 to 6, characterized in that: mixing matrix mixed resin and a thickening agent to obtain viscous mixed resin, adding an initiator, a foaming agent, a polymerization inhibitor and a flame retardant into the viscous mixed resin to obtain mixed liquid, dividing the mixed liquid into n parts, adding broadband wave absorbers with different mass percentage contents according to the design components of each layer of the polymethacrylimide foam to obtain n parts of mixed base materials, sequentially paving the n parts of mixed base materials in a mould according to the design components, and sequentially carrying out prepolymerization, heat treatment I, radiation crosslinking, foaming and heat treatment II to obtain the polymethacrylimide foam.
8. The preparation method of the polymethacrylimide foam with the multilayer wave-absorbing structure according to claim 7, wherein the preparation method comprises the following steps: mixing the matrix mixed resin and the thickening agent at 25-40 ℃ for 24-36 h under stirring to obtain viscous mixed resin; the viscosity of the mixed resin is 8000cps to 50000 cps.
9. The preparation method of the polymethacrylimide foam with the multilayer wave-absorbing structure according to claim 7, wherein the preparation method comprises the following steps: and (3) after discharging bubbles from the n parts of mixed base materials, sequentially paving the mixed base materials in a mould according to the designed components, wherein the mode of discharging the bubbles is ultrasonic waves and/or vacuum bubble discharge.
10. The preparation method of the polymethacrylimide foam with the multilayer wave-absorbing structure according to claim 7, wherein the preparation method comprises the following steps:
the prepolymerization conditions are as follows: placing the die in a constant temperature environment, polymerizing for 1-5 h at 35-50 ℃, and then polymerizing for 36-120 h at 30-50 ℃;
conditions of the heat treatment I: treating for 3-12 h in a hot air furnace at 60-100 ℃;
carrying out radiation crosslinking under the protection of nitrogen, wherein in the radiation crosslinking process, the radiation crosslinking absorption dose is 7-60 kGy;
the foaming conditions are as follows: foaming at 120-150 ℃ for 6-10 h; foaming for 0.5-3 h at 150-200 ℃;
conditions of the heat treatment II: the treatment is carried out for 1-5 h at 100-140 ℃, and then for 1-5 h at 80-100 ℃.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115124646A (en) * | 2022-08-10 | 2022-09-30 | 湖南兆恒材料科技有限公司 | Super-thick high-temperature-resistant light broadband wave-absorbing PMI foam and preparation method thereof |
| CN115366506A (en) * | 2022-08-26 | 2022-11-22 | 苏州高泰电子技术股份有限公司 | Broadband wave-absorbing composite material and broadband wave-absorbing patch |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101700706A (en) * | 2009-11-18 | 2010-05-05 | 中南大学 | Lightweight and broadband wave absorbing material with foam sandwich structure and method for producing same |
| US20130041056A1 (en) * | 2010-05-06 | 2013-02-14 | Evonik Roehm Gmbh | Polymethacrylimide foam materials having reduced flammability and method for producing same |
| CN103588992A (en) * | 2013-11-06 | 2014-02-19 | 四川大学 | In-situ polymerized double-layer-wrapped modified ammonium polyphosphate, and preparation method and application thereof |
| CN106939110A (en) * | 2017-04-18 | 2017-07-11 | 湖南博翔新材料有限公司 | A kind of lightweight broad-band inhales ripple PMI foams and preparation method thereof |
| CN110804121A (en) * | 2019-11-19 | 2020-02-18 | 湖南博翔新材料有限公司 | Low-smoke low-toxicity high-flame-retardancy polymethacrylimide foam |
| CN112126089A (en) * | 2020-09-01 | 2020-12-25 | 中国电子科技集团公司第三十三研究所 | Carbon nano composite broadband wave-absorbing gradient structure material and preparation method thereof |
-
2022
- 2022-06-24 CN CN202210721310.7A patent/CN114874481A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101700706A (en) * | 2009-11-18 | 2010-05-05 | 中南大学 | Lightweight and broadband wave absorbing material with foam sandwich structure and method for producing same |
| US20130041056A1 (en) * | 2010-05-06 | 2013-02-14 | Evonik Roehm Gmbh | Polymethacrylimide foam materials having reduced flammability and method for producing same |
| CN103588992A (en) * | 2013-11-06 | 2014-02-19 | 四川大学 | In-situ polymerized double-layer-wrapped modified ammonium polyphosphate, and preparation method and application thereof |
| CN106939110A (en) * | 2017-04-18 | 2017-07-11 | 湖南博翔新材料有限公司 | A kind of lightweight broad-band inhales ripple PMI foams and preparation method thereof |
| CN110804121A (en) * | 2019-11-19 | 2020-02-18 | 湖南博翔新材料有限公司 | Low-smoke low-toxicity high-flame-retardancy polymethacrylimide foam |
| CN112126089A (en) * | 2020-09-01 | 2020-12-25 | 中国电子科技集团公司第三十三研究所 | Carbon nano composite broadband wave-absorbing gradient structure material and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115124646A (en) * | 2022-08-10 | 2022-09-30 | 湖南兆恒材料科技有限公司 | Super-thick high-temperature-resistant light broadband wave-absorbing PMI foam and preparation method thereof |
| CN115366506A (en) * | 2022-08-26 | 2022-11-22 | 苏州高泰电子技术股份有限公司 | Broadband wave-absorbing composite material and broadband wave-absorbing patch |
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