CN113248873A - Low-density conductive wave-absorbing epoxy resin foam material and preparation method thereof - Google Patents
Low-density conductive wave-absorbing epoxy resin foam material and preparation method thereof Download PDFInfo
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- CN113248873A CN113248873A CN202110713816.9A CN202110713816A CN113248873A CN 113248873 A CN113248873 A CN 113248873A CN 202110713816 A CN202110713816 A CN 202110713816A CN 113248873 A CN113248873 A CN 113248873A
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- epoxy resin
- resin foam
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- chemical foaming
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- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 121
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 120
- 239000006261 foam material Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title abstract description 17
- 239000000126 substance Substances 0.000 claims abstract description 73
- 239000004088 foaming agent Substances 0.000 claims abstract description 72
- 238000005187 foaming Methods 0.000 claims abstract description 61
- 238000000034 method Methods 0.000 claims abstract description 31
- 239000006096 absorbing agent Substances 0.000 claims abstract description 23
- 239000006260 foam Substances 0.000 claims description 67
- 239000000463 material Substances 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 238000002156 mixing Methods 0.000 claims description 23
- 229920000103 Expandable microsphere Polymers 0.000 claims description 19
- 239000003795 chemical substances by application Substances 0.000 claims description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- 239000011256 inorganic filler Substances 0.000 claims description 17
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 17
- 239000004094 surface-active agent Substances 0.000 claims description 17
- 239000013008 thixotropic agent Substances 0.000 claims description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- 238000011417 postcuring Methods 0.000 claims description 15
- 239000012745 toughening agent Substances 0.000 claims description 15
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 14
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 13
- 229910052782 aluminium Inorganic materials 0.000 claims description 13
- 229920000459 Nitrile rubber Polymers 0.000 claims description 11
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 9
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 claims description 8
- 235000019399 azodicarbonamide Nutrition 0.000 claims description 8
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 claims description 8
- -1 organobentonite Chemical compound 0.000 claims description 8
- 239000004156 Azodicarbonamide Substances 0.000 claims description 7
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 7
- 239000002666 chemical blowing agent Substances 0.000 claims description 7
- 229910002804 graphite Inorganic materials 0.000 claims description 7
- 239000010439 graphite Substances 0.000 claims description 7
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 6
- 229910021485 fumed silica Inorganic materials 0.000 claims description 6
- 238000009775 high-speed stirring Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 6
- 239000004593 Epoxy Substances 0.000 claims description 5
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 4
- 239000005995 Aluminium silicate Substances 0.000 claims description 4
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 4
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 claims description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 4
- 239000004952 Polyamide Substances 0.000 claims description 4
- 235000012211 aluminium silicate Nutrition 0.000 claims description 4
- 239000004917 carbon fiber Substances 0.000 claims description 4
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- 235000019438 castor oil Nutrition 0.000 claims description 4
- 229920001971 elastomer Polymers 0.000 claims description 4
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 4
- 229910021389 graphene Inorganic materials 0.000 claims description 4
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 4
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 239000010445 mica Substances 0.000 claims description 4
- 229910052618 mica group Inorganic materials 0.000 claims description 4
- 229920001084 poly(chloroprene) Polymers 0.000 claims description 4
- 229920002647 polyamide Polymers 0.000 claims description 4
- 229920006122 polyamide resin Polymers 0.000 claims description 4
- 239000005077 polysulfide Substances 0.000 claims description 4
- 229920001021 polysulfide Polymers 0.000 claims description 4
- 150000008117 polysulfides Polymers 0.000 claims description 4
- 239000000454 talc Substances 0.000 claims description 4
- 229910052623 talc Inorganic materials 0.000 claims description 4
- 239000010456 wollastonite Substances 0.000 claims description 4
- 229910052882 wollastonite Inorganic materials 0.000 claims description 4
- 229920001213 Polysorbate 20 Polymers 0.000 claims description 3
- YDVJBLJCSLVMSY-UHFFFAOYSA-N carbamoyl cyanide Chemical compound NC(=O)C#N YDVJBLJCSLVMSY-UHFFFAOYSA-N 0.000 claims description 3
- 238000009826 distribution Methods 0.000 claims description 3
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 claims description 3
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 claims description 3
- ISNKSXRJJVWFIL-UHFFFAOYSA-N (sulfonylamino)amine Chemical compound NN=S(=O)=O ISNKSXRJJVWFIL-UHFFFAOYSA-N 0.000 claims description 2
- 239000004604 Blowing Agent Substances 0.000 claims description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims 2
- 230000008569 process Effects 0.000 abstract description 13
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- 229920005989 resin Polymers 0.000 description 10
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- 238000010521 absorption reaction Methods 0.000 description 7
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- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
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- 238000007906 compression Methods 0.000 description 4
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- 239000011148 porous material Substances 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
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- 238000011161 development Methods 0.000 description 3
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- 239000004743 Polypropylene Substances 0.000 description 2
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- 229920001155 polypropylene Polymers 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 229920001214 Polysorbate 60 Polymers 0.000 description 1
- LWZFANDGMFTDAV-BURFUSLBSA-N [(2r)-2-[(2r,3r,4s)-3,4-dihydroxyoxolan-2-yl]-2-hydroxyethyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O LWZFANDGMFTDAV-BURFUSLBSA-N 0.000 description 1
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- 150000001875 compounds Chemical class 0.000 description 1
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- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
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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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/32—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof from compositions containing microballoons, e.g. syntactic foams
-
- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0066—Use of inorganic compounding ingredients
-
- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/102—Azo-compounds
- C08J9/103—Azodicarbonamide
-
- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/104—Hydrazines; Hydrazides; Semicarbazides; Semicarbazones; Hydrazones; Derivatives thereof
- C08J9/105—Hydrazines; Hydrazides; Semicarbazides; Semicarbazones; Hydrazones; Derivatives thereof containing sulfur
-
- 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
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
-
- 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
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/18—Binary blends of expanding agents
- C08J2203/184—Binary blends of expanding agents of chemical foaming agent and physical blowing agent, e.g. azodicarbonamide and fluorocarbon
-
- 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
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
- C08J2363/02—Polyglycidyl ethers of bis-phenols
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention provides an epoxy resin foam material, which has the density of 70-200 kg/m3(ii) a The aperture of the epoxy resin foam material is 0.2-0.5 mm. The epoxy resin foam material has low density, high performance and high conductive and wave-absorbing performance, and the density of the epoxy resin foam material is still only 70-200 kg/m after the wave-absorbing agent filler is added3And the full foaming is realized, and the comprehensive performance is maintained at the basic level. The invention utilizes the combination of physical foaming and chemical foaming methods, utilizes the heat accumulation existing in the chemical foaming process, adopts a specific physical foaming agent and expandsThe chemical foaming agent can absorb heat accumulation brought by chemical foaming during expansion, and the problem of overlarge density is solved by the chemical foaming agent. In addition, the preparation method provided by the invention has simple process and easy control, and is beneficial to realizing industrial continuous production.
Description
Technical Field
The invention belongs to the technical field of conductive wave-absorbing epoxy resin foam materials, relates to an epoxy resin foam material and a preparation method thereof, and particularly relates to a low-density conductive wave-absorbing epoxy resin foam material and a preparation method thereof.
Background
With the continuous development of the electronic information society, the composite material with special conductive performance is receiving attention of people increasingly. Compared with phenolic resin, unsaturated resin, vinyl resin and the like, the epoxy resin has the advantages of good mechanical property, good heat resistance, good water resistance, excellent chemical corrosion resistance and the like, and the epoxy resin-based composite material is widely applied to the fields of wind power, rail transit, aerospace, automobiles and the like. The epoxy resin has a plurality of excellent properties,
the invention patent CN107868409A compounds and cures epoxy resin and conductive material to form conductive composite material, but the material density obtained by the method is high, and the development requirements of light weight, low carbon and economy in modern society are not satisfied. The epoxy resin is prepared into the epoxy resin foam through a physical and chemical foaming process, so that certain characteristics superior to those of the traditional foam can be obtained, and the epoxy resin foam can be better applied in some fields. Compared with the traditional polyurethane, styrene and polypropylene foams, the mechanical property, the heat resistance, the weather resistance and the moisture absorption of the epoxy resin foam are far better than those of the traditional polyurethane, styrene and polypropylene foams. Compared with novel PVC (polyvinyl chloride) hard foam and Polymethacrylimide (PMI) foam, the epoxy resin foam has better corrosion resistance, high compression modulus, chemical corrosion resistance and high resin-based compatibility. The excellent performances enable the conductive wave-absorbing epoxy resin foam to be widely applied to the fields of aerospace, deep sea exploration, military, communication and the like. However, as the requirements of various application industries on the performance of epoxy resin foams are further improved, the aspects of stable and multifunctional low-density comprehensive performance and the like become bottlenecks which hinder the continuous development of epoxy resin foams.
Epoxy resin foams can be broadly divided into three preparation methods: chemical foaming, physical foaming and hollow microsphere filling. The chemical foaming method mainly utilizes resin curing heat to decompose a chemical foaming agent in a formula to generate gas. The physical foaming method is to add a low boiling point liquid or expandable microspheres as a foaming agent to a resin and to foam by the curing heat of the resin. The hollow microsphere filling method is to directly fill hollow glass microspheres or hollow carbon microspheres and the like in epoxy resinAnd curing the resin to obtain the foam. Chemical blowing agents as described in patent publication No. CN101289570A were used to produce a density of 300g/cm3An epoxy resin foam having a compressive strength of about 1 MPa. The hollow glass microspheres with the publication number of CN85106037A are used as filling materials to prepare the epoxy resin foam with the density of 600kg/cm3The patent with publication number CN1827691A prepares epoxy resin foam by using expandable hollow microspheres, and the density can reach 300g/cm3. When the conductive wave-absorbing filler is added, the density of the epoxy resin foam is greatly improved, and the invention patent CN108929518A utilizes the epoxy resin to be added with the hollow glass microspheres and the conductive filler to prepare the epoxy resin foam with the density of 850g/cm3The conductive foam of (1).
However, the above foaming methods have problems, chemical foaming is difficult to control, resulting in a decrease in the overall performance of the foamed material, and physical foaming and hollow microsphere filling methods have the drawback of higher density, and the density is further increased by adding multifunctional additives.
Therefore, how to find a more suitable way to obtain epoxy resin foam with low density, good comprehensive performance and multiple functions has become one of the problems to be solved by many research and development enterprises and front-line researchers in the field.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide an epoxy resin foam material and a preparation method thereof, and particularly to a low-density conductive wave-absorbing epoxy resin foam material.
The invention provides an epoxy resin foam material, which has the density of 70-200 kg/m3；
The aperture of the epoxy resin foam material is 0.2-0.5 mm.
Preferably, the epoxy resin foam material is obtained by foaming a physical foaming material and a chemical foaming agent together;
the epoxy resin foam material has uniform cell distribution;
the epoxy resin foam material contains a wave absorbing agent;
the core of the epoxy foam material does not have a yellow appearance resulting from internal coring and/or implosion.
Preferably, the physically foamable material comprises expandable microspheres;
the chemical blowing agent comprises an organic blowing agent;
the organic foaming agent comprises an azo chemical foaming agent and/or a sulfonyl hydrazine chemical foaming agent;
the cells are closed cell structures.
Preferably, the chemical blowing agent comprises one or more of azoisobutyryl cyano formamide, azodicarbonamide, azodiisobutyronitrile and 2, 4-xylene disulfonyl hydrazide;
the mass ratio of the physical foaming material to the chemical foaming agent is (2-10): (0.1-2);
the epoxy resin foam material is low-density conductive wave-absorbing epoxy resin foam.
The invention provides an epoxy resin foam material, which comprises the following raw materials in parts by weight
Preferably, the epoxy resin comprises bisphenol a epoxy resin;
the curing agent comprises one or more of diaminodiphenylmethane, diaminodiphenyl sulfone, diethylenetriamine, m-phenylenediamine, polyamide and ethylenediamine;
the wave absorbing agent comprises one or more of conductive graphite, conductive carbon black, carbon nanotubes, graphene and conductive carbon fibers;
the physically foamable material comprises expandable microspheres;
the chemical foaming agent comprises an azo chemical foaming agent and/or a sulfonyl hydrazide chemical foaming agent;
the toughening agent comprises one or more of nitrile rubber, polyamide resin, polysulfide rubber, hydroxyl-terminated liquid nitrile rubber and chloroprene rubber.
Preferably, the bisphenol A epoxy resin comprises one or more of E-54, E-51, E-44, E-31 and E-20;
the expandable microspheres comprise one or more of 053DU40, EML101, EMH204, 120DU25, 130DU25, FN-100M and FN-105;
the chemical foaming agent comprises one or more of azoisobutyryl cyano formamide, azodicarbonamide, azodiisobutyronitrile and 2, 4-xylene disulfonyl hydrazide;
the thixotropic agent comprises one or more of fumed silica, precipitated silica, organobentonite, kaolin and hydrogenated castor oil;
the surfactant comprises Tween-20, AK-8805, AK-8882, B-4900, B-8870, L-64 or L-44.
The inorganic filler comprises one or more of calcium carbonate, talc, wollastonite and mica.
The invention provides a preparation method of the epoxy resin foam material in any one of the technical schemes, which comprises the following steps:
(1) mixing epoxy resin, a curing agent, a wave absorbing agent, a toughening agent, a thixotropic agent, a surfactant and an inorganic filler, and then carrying out prepolymerization reaction in a mold to obtain a reaction system;
(2) and mixing the physical foaming material and the chemical foaming agent again, adding the mixture into the reaction system obtained in the step, foaming and curing the mixture, and performing post-curing to obtain the epoxy resin foam material.
Preferably, the mixing means includes high speed stirring;
the mixing speed is 500-2000 r/min;
the mold comprises an aluminum mold;
the temperature of the prepolymerization reaction is 50-80 ℃;
the prepolymerization reaction time is 1-2 hours;
preferably, the remixing means includes high speed stirring;
the rotation speed of the remixing is 500-2000 r/min;
the foaming and curing temperature is 100-120 ℃;
the foaming and curing time is 1-2 hours;
the post-curing temperature is 150-160 ℃;
the post-curing time is 2-4 hours.
The invention provides an epoxy resin foam material, which has the density of 70-200 kg/m3(ii) a The aperture of the epoxy resin foam material is 0.2-0.5 mm. Compared with the prior art, the preparation process of the epoxy resin foam is researched, the foaming process is particularly selected in a targeted manner, and the chemical foaming agent is considered to be decomposed and foamed at a certain temperature, and heat is released and accumulated along with the progress of a crosslinking reaction, so that the internal core burning, implosion and comprehensive performance are reduced; the physical foaming agent or the method for filling the hollow microspheres has higher density of the obtained foam body due to the inherent defects of the foaming material, and is difficult to solve.
The epoxy resin foam material has low density, high performance, high level maintaining and conductive and wave absorbing functions, and the density of the epoxy resin foam material is still only 70-200 kg/m after the wave absorbing agent filler is added3And the full foaming is realized, the pore diameter of the pores reaches 0.2-0.5 mm, and meanwhile, the comprehensive performance is maintained at the basic level without obvious reduction. The invention creatively utilizes a mode of combining physical foaming and chemical foaming methods, utilizes heat accumulation existing in chemical foaming, adopts a specific physical foaming agent, needs to absorb heat in expansion, can absorb heat accumulation brought by chemical foaming, and solves the problem of overlarge density of the chemical foaming agent.
The invention further realizes the cooperative control of the foaming reaction of the epoxy resin base and the resin curing molding by controlling the content proportion of the curing agent, the selection of the physical foaming agent and the type of the chemical foaming agent. By controlling the formula proportion of the physical foaming agent and the chemical foaming agent, the foaming capacity is maximized, the phenomena of high density of the physical foaming agent, core burning, implosion and the like of the chemical foaming agent are avoided, the epoxy resin foam with lower density and the conductive and wave-absorbing function can be obtained after a large amount of wave-absorbing conductive materials are added, and the performance can also keep a higher level. In addition, the preparation method provided by the invention has simple process and easy control, and is beneficial to realizing industrial continuous production.
Experimental results show that the density of the low-density conductive wave-absorbing epoxy resin foam provided by the invention can reach 100kg/m3The glass transition temperature reaches 160 ℃, the foam has certain temperature resistance, the compression strength can reach about 5Mpa, and the mechanical property is greatly improved compared with common low-density rigid foam. Meanwhile, in the sweep frequency range of 8-18 GHz, the maximum absorption peak value R is about-15.0 dB, and the reflectivity of the material in the frequency range of 8-18 GHz is uniform<10 dB. It has better wave-absorbing performance.
Drawings
FIG. 1 is a photograph of a core of an epoxy resin foam prepared by a conventional chemical foaming process;
FIG. 2 is a photograph of a core of an epoxy resin foam prepared according to the present invention.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
All of the starting materials of the present invention, without particular limitation as to their source, may be purchased commercially or prepared according to conventional methods well known to those skilled in the art.
All of the starting materials of the present invention are not particularly limited in their purity, and the present invention preferably employs purity requirements that are conventional in the art of analytically pure or polyepoxide resin foam preparation.
All the raw materials, the marks and the acronyms thereof belong to the conventional marks and acronyms in the field, each mark and acronym is clear and definite in the field of related application, and the raw materials can be purchased from the market or prepared by a conventional method by the technical staff in the field according to the marks, the acronyms and the corresponding application.
The invention provides an epoxy resin foam material, which has the density of 70-200 kg/m3；
The aperture of the epoxy resin foam material is 0.2-0.5 mm.
In the present invention, the epoxy resin foam is preferably obtained by co-foaming a physical foaming material and a chemical foaming agent.
In the present invention, the physically foaming material preferably comprises expandable microspheres.
In the present invention, the chemical foaming agent preferably includes an organic foaming agent, and more specifically, the organic foaming agent preferably includes an azo-based chemical foaming agent and/or a sulfonyl hydrazide-based chemical foaming agent, and more preferably, an azo-based chemical foaming agent or a sulfonyl hydrazide-based chemical foaming agent.
In the present invention, the chemical blowing agent preferably includes one or more of azoisobutyrylcyanamide, azodicarbonamide, azobisisobutyronitrile, and 2, 4-xylene disulfonylhydrazide, and more preferably, azoisobutyrylcyanamide, azodicarbonamide, azobisisobutyronitrile, or 2, 4-xylene disulfonylhydrazide.
In the invention, the mass ratio of the physical foaming material to the chemical foaming agent is preferably (2-10): (0.1-2), more preferably (3-9): (0.1-2), more preferably (4-8): (0.1-2), more preferably (5-7): (0.1-2), more preferably (2-10): (0.5 to 1.6), more preferably (2 to 10): (0.9-1.2).
In the present invention, the epoxy resin foam preferably has a uniform cell distribution, and more particularly, the cells are preferably of a closed cell structure.
In the invention, the epoxy resin foam material is preferably low-density conductive wave-absorbing epoxy resin foam. Specifically, the epoxy resin foam material preferably contains a wave absorber.
In the present invention, the core of the epoxy resin foam preferably has no internal core and/or yellow appearance due to implosion, and more preferably has no internal core and yellow appearance due to implosion.
The invention provides an epoxy resin foam material, which comprises the following raw materials in parts by weight
The addition amount of the epoxy resin is 50-70 parts by weight, preferably 54-66 parts by weight, and more preferably 58-62 parts by weight. The epoxy resin preferably comprises bisphenol A epoxy resin, in particular, the bisphenol A epoxy resin preferably comprises one or more of E-54, E-51, E-44, E-31 and E-20, and more preferably E-54, E-51, E-44, E-31 or E-20.
The addition amount of the curing agent is 3-15 parts by weight, preferably 5-13 parts by weight, and more preferably 7-11 parts by weight. The curing agent preferably comprises one or more of diaminodiphenylmethane, diaminodiphenylsulfone, diethylenetriamine, m-phenylenediamine, polyamide and ethylenediamine, more preferably diaminodiphenylmethane, diaminodiphenylsulfone, diethylenetriamine, m-phenylenediamine, polyamide or ethylenediamine.
The wave absorber is added in an amount of 5-15 parts by weight, preferably 7-13 parts by weight, and more preferably 9-11 parts by weight. The wave absorbing agent preferably comprises one or more of conductive graphite, conductive carbon black, carbon nanotubes, graphene and conductive carbon fibers, and more preferably conductive graphite, conductive carbon black, carbon nanotubes, graphene or conductive carbon fibers.
The addition amount of the physical foaming material is 2-10 parts by weight, preferably 3-9 parts by weight, more preferably 4-8 parts by weight, and more preferably 5-7 parts by weight. The physically foamable material preferably comprises expandable microspheres, in particular, the expandable microspheres preferably comprise one or more of 053DU40, EML101, EMH204, 120DU25, 130DU25, FN-100M and FN-105, more preferably 053DU40, EML101, EMH204, 120DU25, 130DU25, FN-100M or FN-105.
The addition amount of the chemical foaming agent is 0.1-2 parts by weight, preferably 0.5-1.6 parts by weight, and more preferably 0.9-1.2 parts by weight. The chemical foaming agent preferably includes an azo-based chemical foaming agent and/or a sulfonyl hydrazide-based chemical foaming agent, and more preferably an azo-based chemical foaming agent or a sulfonyl hydrazide-based chemical foaming agent. Specifically, the chemical blowing agent preferably includes one or more of azoisobutyrylcyanamide, azodicarbonamide, azobisisobutyronitrile, and 2, 4-xylene disulfonylhydrazide, and more preferably, azoisobutyrylcyanamide, azodicarbonamide, azobisisobutyronitrile, or 2, 4-xylene disulfonylhydrazide.
The toughening agent is added in an amount of 5-20 parts by weight, preferably 8-17 parts by weight, and more preferably 11-14 parts by weight. The toughening agent preferably comprises one or more of nitrile rubber, polyamide resin, polysulfide rubber, hydroxyl-terminated liquid nitrile rubber and chloroprene rubber, and more preferably nitrile rubber, polyamide resin, polysulfide rubber, hydroxyl-terminated liquid nitrile rubber or chloroprene rubber.
The addition amount of the thixotropic agent is 1-10 parts by weight, preferably 3-8 parts by weight, and more preferably 5-6 parts by weight. The thixotropic agent preferably comprises one or more of fumed silica, precipitated silica, organobentonite, kaolin and hydrogenated castor oil, more preferably silica, precipitated silica, organobentonite, kaolin or hydrogenated castor oil.
The addition amount of the surfactant is 1 to 5 parts by weight, preferably 1.5 to 4.5 parts by weight, more preferably 2 to 4 parts by weight, and still more preferably 2.5 to 3.5 parts by weight. The surfactant preferably comprises Tween-20 (polyoxyethylene sorbitan laurate), AK-8805, AK-8882, B-4900, B-8870, L-64 or L-44.
The inorganic filler is added in an amount of 2 to 10 parts by weight, preferably 3 to 9 parts by weight, more preferably 4 to 8 parts by weight, and still more preferably 5 to 7 parts by weight. The inorganic filler preferably comprises one or more of calcium carbonate, talc, wollastonite and mica, more preferably calcium carbonate, talc, wollastonite or mica.
The invention adopts a method of combining a chemical foaming agent and a physical foaming agent to prepare the epoxy resin foam. The material comprises the following components in percentage by weight: 50-70% of epoxy resin, 3-15% of curing agent, 5-15% of wave absorbing agent and 2-10% of expandable microspheres. 0.1-2% of chemical foaming agent, 5-20% of toughening agent, 1-10% of thixotropic agent, 1-5% of surfactant and 2-10% of inorganic filler.
The invention also provides a preparation method of the epoxy resin foam material, which comprises the following steps:
(1) mixing epoxy resin, a curing agent, a wave absorbing agent, a toughening agent, a thixotropic agent, a surfactant and an inorganic filler, and then carrying out prepolymerization reaction in a mold to obtain a reaction system;
(2) and mixing the physical foaming material and the chemical foaming agent again, adding the mixture into the reaction system obtained in the step, foaming and curing the mixture, and performing post-curing to obtain the epoxy resin foam material.
The preparation method comprises the steps of mixing epoxy resin, a curing agent, a wave absorbing agent, a toughening agent, a thixotropic agent, a surfactant and an inorganic filler, and then carrying out prepolymerization reaction in a mold to obtain a reaction system.
In the present invention, the mixing means preferably includes high-speed stirring.
In the invention, the rotation speed of the mixing is preferably 500-2000 r/min, more preferably 800-1700 r/min, and more preferably 1100-1400 r/min.
In the present invention, the mold preferably comprises an aluminum mold.
In the invention, the temperature of the prepolymerization reaction is preferably 50-80 ℃, more preferably 55-75 ℃, and more preferably 60-70 ℃.
In the present invention, the time of the prepolymerization reaction is preferably 1 to 2 hours, more preferably 1.2 to 1.8 hours, and still more preferably 1.4 to 1.6 hours.
According to the invention, the physical foaming material and the chemical foaming agent are mixed again, added into the reaction system obtained in the step, foamed and cured, and post-cured to obtain the epoxy resin foam material.
In the present invention, the remixing means preferably includes high-speed stirring.
In the invention, the rotation speed of the remixing is preferably 500-2000 r/min, more preferably 800-1700 r/min, and more preferably 1100-1400 r/min.
In the invention, the foaming and curing temperature is preferably 100-120 ℃, more preferably 104-116 ℃, and more preferably 108-112 ℃.
In the invention, the time for foaming and curing is preferably 1 to 2 hours, more preferably 1.2 to 1.8 hours, and still more preferably 1.4 to 1.6 hours.
In the invention, the post-curing temperature is preferably 150-160 ℃, more preferably 152-158 ℃, and more preferably 154-156 ℃.
In the present invention, the post-curing time is preferably 2 to 4 hours, more preferably 2.4 to 3.6 hours, and still more preferably 2.8 to 3.2 hours.
The invention is a complete and detailed integral technical scheme, better ensures the appearance and structure of the epoxy resin foam material, and better improves the comprehensive performance of the epoxy resin foam material, and the preparation method of the epoxy resin foam material can specifically comprise the following steps:
respectively weighing epoxy resin, a curing agent, a wave absorbing agent, a toughening agent, a thixotropic agent, a surfactant and an inorganic filler according to a mass ratio, stirring at a high speed, uniformly mixing, placing in an aluminum mold, heating at 50-80 ℃ for 1-2 hours, taking out, adding expandable microspheres and a chemical foaming agent, adding into the aluminum mold after uniform mixing, heating at 100-120 ℃ for 1-2 hours, foaming and curing in the process, and heating to 150-160 ℃ for post-curing for 2-4 hours. Taking out and cooling to room temperature to obtain the foam.
More specifically:
(1) respectively weighing the epoxy resin, the curing agent, the wave absorbing agent, the toughening agent, the thixotropic agent, the surfactant and the inorganic filler according to the mass ratio, stirring at a high speed, mixing uniformly, and placing in an aluminum die.
(2) Carrying out prepolymerization reaction, heating at 50-80 ℃ for 1-2 hours, taking out,
(3) adding expandable microspheres and a chemical foaming agent, stirring at a high speed, uniformly mixing, adding into an aluminum die, heating at 100-120 ℃ for 1-2 hours, foaming and curing in the process,
(4) post-curing, and then heating to 150-160 ℃ for post-curing for 2 hours. Taking out and cooling to room temperature to obtain the foam.
The invention provides a low-density conductive wave-absorbing epoxy resin foam material and a preparation method thereof. The invention provides the epoxy resin foam which has low density, high performance and high level and has a conductive and wave-absorbing function, and the density of the epoxy resin foam material is still only 70-200 kg/m after the wave-absorbing agent filler is added3And the full foaming is realized, the pore diameter of the pores reaches 0.2-0.5 mm, and meanwhile, the comprehensive performance is maintained at the basic level without obvious reduction. The invention creatively utilizes a mode of combining physical foaming and chemical foaming methods, utilizes heat accumulation existing in chemical foaming, adopts a specific physical foaming agent, needs to absorb heat when expanding, can absorb heat accumulation brought by chemical foaming, solves the problem of overlarge density by using the chemical foaming agent and the physical foaming agent, and also solves the problem that low-density epoxy foam is difficult to obtain after adding wave-absorbing filler, so that the invention can obtain conductive wave-absorbing epoxy foam with lower density, and the performance can keep higher level.
The invention further realizes the cooperative control of the foaming reaction of the epoxy resin base and the resin curing molding by controlling the content proportion of the curing agent, the selection of the physical foaming agent and the type of the chemical foaming agent. By controlling the formula proportion of the physical foaming agent and the chemical foaming agent, the foaming capacity is maximized, the phenomena of high density of the physical foaming agent, core burning, implosion and the like of the chemical foaming agent are avoided, the epoxy resin foam with lower density and the conductive and wave-absorbing function can be obtained after a large amount of wave-absorbing conductive materials are added, and the performance can also keep a higher level. In addition, the preparation method provided by the invention has simple process and easy control, and is beneficial to realizing industrial continuous production.
Experimental results show that the density of the low-density conductive wave-absorbing epoxy resin foam provided by the invention can reach 100kg/m3The glass transition temperature reaches 160 ℃, the foam has certain temperature resistance, the compression strength can reach about 5Mpa, and the mechanical property is greatly improved compared with common low-density rigid foam. Meanwhile, in the sweep frequency range of 8-18 GHz, the maximum absorption peak value R is about-15.0 dB, and the reflectivity of the material in the frequency range of 8-18 GHz is uniform<10 dB. It has better wave-absorbing performance.
For further illustration of the present invention, the following will describe in detail an epoxy resin foam material and a preparation method thereof with reference to the following examples, but it should be understood that these examples are carried out on the premise of the technical solution of the present invention, and the detailed embodiments and specific procedures are given only for further illustration of the features and advantages of the present invention, not for limitation of the claims of the present invention, and the scope of protection of the present invention is not limited to the following examples.
Example 1
60 parts of bisphenol A epoxy resin E-54, 5 parts of curing agent diaminodiphenylmethane, 10 parts of wave absorber conductive graphite, 3 parts of expandable microspheres 130DU25, 2 parts of chemical foaming agent azodiisobutyronitrile, 10 parts of toughening agent hydroxyl-terminated liquid nitrile rubber, 3 parts of thixotropic agent fumed silica, 2 parts of surfactant B-8870 and 5 parts of inorganic filler calcium carbonate. Respectively weighing the epoxy resin, the curing agent, the wave absorbing agent, the toughening agent, the thixotropic agent, the surfactant and the inorganic filler according to the mass ratio, stirring at a high speed, mixing uniformly, and placing in an aluminum die. Carrying out prepolymerization reaction, heating at 75 ℃ for 1 hour, taking out, adding expandable microspheres and a chemical foaming agent, stirring at a high speed, mixing uniformly, adding into an aluminum die, heating at 110 ℃ for 2 hours, foaming and curing in the process, and heating to 160 ℃ for post-curing for 2 hours. Taking out and cooling to room temperature to obtain the foam.
The low-density conductive wave-absorbing epoxy resin foam material prepared in the embodiment 1 of the invention is subjected to wave-absorbing performance detection.
The result shows that the foam has a maximum peak value at 14.5GHz within a frequency sweep range of 8-18 GHz, the maximum absorption peak value R is-16.5 dB, and the reflectivity of the material within a frequency range of 8-18 GHz is less than 10 dB.
The physical property detection is carried out on the low-density conductive wave-absorbing epoxy resin foam material prepared in the embodiment 1 of the invention.
Referring to Table 1, Table 1 shows the physical properties of the epoxy resin foams prepared in the examples of the present invention.
TABLE 1
| Performance of | Example 1 | Example 2 | Example 3 |
| Density of | 95kg/m3 | 120kg/m3 | 75kg/m3 |
| Glass transition temperature | 180℃ | 165℃ | 162℃ |
| 5% thermal weight loss temperature | 320℃ | 315℃ | 312℃ |
| Compressive strength | 5.26Mpa | 6.12Mpa | 4.89Mpa |
| Compressive strength at 120 DEG C | 4.08Mpa | 4.81Mpa | 3.89Mpa |
As can be seen from Table 1, the density of the low-density conductive wave-absorbing epoxy resin foam provided by the invention can reach 100kg/m3The glass transition temperature reaches 160 ℃, the foam has certain temperature resistance, the compression strength can reach about 5Mpa, and the mechanical property is greatly improved compared with common low-density rigid foam. Meanwhile, in the sweep frequency range of 8-18 GHz, the maximum absorption peak value R is about-15.0 dB, and the reflectivity of the material in the frequency range of 8-18 GHz is uniform<10 dB. It has better wave-absorbing performance.
Example 2
According to the weight portions of 60 percent of bisphenol A epoxy resin E-51, 3 percent of curing agent diethylenetriamine, 10 percent of wave absorbing agent conductive graphite, 8 percent of expandable microsphere 130DU25, 1 percent of chemical foaming agent azo isobutyl cyano formamide, 10 percent of nitrile rubber, 2 percent of thixotropic agent fumed silica, 1 percent of surfactant L-64 and 5 percent of inorganic filler calcium carbonate. Respectively weighing the epoxy resin, the curing agent, the wave absorbing agent, the toughening agent, the thixotropic agent, the surfactant and the inorganic filler according to the mass ratio, stirring at a high speed, mixing uniformly, and placing in an aluminum die. Carrying out prepolymerization reaction, heating at 60 ℃ for 1 hour, taking out, adding expandable microspheres and a chemical foaming agent, stirring at a high speed, mixing uniformly, adding into an aluminum die, heating at 100 ℃ for 2 hours, foaming and curing in the process, and heating to 150 ℃ for post-curing for 2 hours. Taking out and cooling to room temperature to obtain the foam.
The low-density conductive wave-absorbing epoxy resin foam material prepared in the embodiment 2 of the invention is subjected to wave-absorbing performance detection.
The result shows that the foam has a maximum peak value at 13.5GHz within the frequency sweep range of 8-18 GHz, the maximum absorption peak value R is-15.0 dB, and the reflectivity of the material within the frequency range of 8-18 GHz is less than 10 dB.
The physical property detection is carried out on the low-density conductive wave-absorbing epoxy resin foam material prepared in the embodiment 2 of the invention.
Referring to Table 1, Table 1 shows the physical properties of the epoxy resin foams prepared in the examples of the present invention.
Example 3
55 percent of bisphenol A epoxy resin E-51, 3 percent of curing agent diethylenetriamine, 10 percent of wave absorber conductive graphite, 10 percent of expandable microsphere FN-105, 2 percent of chemical foaming agent azo isobutyl cyano formamide, 10 percent of nitrile rubber, 2 percent of thixotropic agent fumed silica, 2 percent of surfactant L-64 and 6 percent of inorganic filler calcium carbonate. Respectively weighing the epoxy resin, the curing agent, the wave absorbing agent, the toughening agent, the thixotropic agent, the surfactant and the inorganic filler according to the mass ratio, stirring at a high speed, mixing uniformly, and placing in an aluminum die. Carrying out prepolymerization reaction, heating at 65 ℃ for 1 hour, taking out, adding expandable microspheres and a chemical foaming agent, stirring at a high speed, mixing uniformly, adding into an aluminum die, heating at 100 ℃ for 2 hours, foaming and curing in the process, and heating to 150 ℃ for post-curing for 2 hours. Taking out and cooling to room temperature to obtain the foam.
The low-density conductive wave-absorbing epoxy resin foam material prepared in the embodiment 3 of the invention is subjected to wave-absorbing performance detection.
The result shows that the foam has a maximum peak value at 14.0GHz within a frequency sweep range of 8-18 GHz, the maximum absorption peak value R is-13.0 dB, and the reflectivity of the material within a frequency range of 8-18 GHz is less than 10 dB.
The physical property detection is carried out on the low-density conductive wave-absorbing epoxy resin foam material prepared in the embodiment 3 of the invention.
Referring to Table 1, Table 1 shows the physical properties of the epoxy resin foams prepared in the examples of the present invention.
The low-density conductive wave-absorbing epoxy resin foam material prepared by the embodiment of the invention is compared with the core part of the epoxy resin foam material prepared by the existing chemical foaming.
Referring to fig. 1, fig. 1 is a photograph of a core of an epoxy resin foam prepared by a conventional chemical foaming process.
Referring to fig. 2, fig. 2 is a photograph of a core of an epoxy resin foam prepared according to the present invention.
As is clear from FIGS. 1 and 2, the core of the epoxy resin foam prepared by the present invention has no internal core burning and implosion, etc., resulting in a yellowish appearance.
While the present invention has been described in detail with reference to a low density conductive wave absorbing epoxy resin foam and a method for making the same, the present invention is described in terms of its principles and embodiments with specific examples being included to facilitate the understanding of the methods and their core concepts, including the best mode, and to enable any person skilled in the art to practice the invention, including making and using any devices or systems and performing any incorporated methods. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention. The scope of the invention is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.
Claims (10)
1. The epoxy resin foam material is characterized in that the density of the epoxy resin foam material is 70-200 kg/m3；
The aperture of the epoxy resin foam material is 0.2-0.5 mm.
2. The epoxy resin foam material as claimed in claim 1, wherein the epoxy resin foam material is obtained by co-foaming a physical foaming material and a chemical foaming agent;
the epoxy resin foam material has uniform cell distribution;
the epoxy resin foam material contains a wave absorbing agent;
the core of the epoxy foam material does not have a yellow appearance resulting from internal coring and/or implosion.
3. The epoxy resin foam of claim 2, wherein the physically foamable material comprises expandable microspheres;
the chemical blowing agent comprises an organic blowing agent;
the organic foaming agent comprises an azo chemical foaming agent and/or a sulfonyl hydrazine chemical foaming agent;
the cells are closed cell structures.
4. The epoxy resin foam of claim 2, wherein the chemical blowing agent comprises one or more of azoisobutyronitrile formamide, azodicarboxamide, azodiisobutyronitrile, and 2, 4-xylene disulfonyl hydrazide;
the mass ratio of the physical foaming material to the chemical foaming agent is (2-10): (0.1-2);
the epoxy resin foam material is low-density conductive wave-absorbing epoxy resin foam.
5. An epoxy resin foam material is characterized by comprising the following raw materials in parts by weight
6. The epoxy resin foam of claim 5, wherein the epoxy resin comprises a bisphenol A epoxy resin;
the curing agent comprises one or more of diaminodiphenylmethane, diaminodiphenyl sulfone, diethylenetriamine, m-phenylenediamine, polyamide and ethylenediamine;
the wave absorbing agent comprises one or more of conductive graphite, conductive carbon black, carbon nanotubes, graphene and conductive carbon fibers;
the physically foamable material comprises expandable microspheres;
the chemical foaming agent comprises an azo chemical foaming agent and/or a sulfonyl hydrazide chemical foaming agent;
the toughening agent comprises one or more of nitrile rubber, polyamide resin, polysulfide rubber, hydroxyl-terminated liquid nitrile rubber and chloroprene rubber.
7. The epoxy resin foam of claim 5, wherein the bisphenol a epoxy resin comprises one or more of E-54, E-51, E-44, E-31, and E-20;
the expandable microspheres comprise one or more of 053DU40, EML101, EMH204, 120DU25, 130DU25, FN-100M and FN-105;
the chemical foaming agent comprises one or more of azoisobutyryl cyano formamide, azodicarbonamide, azodiisobutyronitrile and 2, 4-xylene disulfonyl hydrazide;
the thixotropic agent comprises one or more of fumed silica, precipitated silica, organobentonite, kaolin and hydrogenated castor oil;
the surfactant comprises Tween-20, AK-8805, AK-8882, B-4900, B-8870, L-64 or L-44.
The inorganic filler comprises one or more of calcium carbonate, talc, wollastonite and mica.
8. A method for preparing the epoxy resin foam material according to any one of claims 1 to 7, characterized by comprising the steps of:
(1) mixing epoxy resin, a curing agent, a wave absorbing agent, a toughening agent, a thixotropic agent, a surfactant and an inorganic filler, and then carrying out prepolymerization reaction in a mold to obtain a reaction system;
(2) and mixing the physical foaming material and the chemical foaming agent again, adding the mixture into the reaction system obtained in the step, foaming and curing the mixture, and performing post-curing to obtain the epoxy resin foam material.
9. The method of claim 8, wherein the mixing comprises high speed stirring;
the mixing speed is 500-2000 r/min;
the mold comprises an aluminum mold;
the temperature of the prepolymerization reaction is 50-80 ℃;
the prepolymerization time is 1-2 hours.
10. The method of claim 8, wherein the remixing means includes high speed stirring;
the rotation speed of the remixing is 500-2000 r/min;
the foaming and curing temperature is 100-120 ℃;
the foaming and curing time is 1-2 hours;
the post-curing temperature is 150-160 ℃;
the post-curing time is 2-4 hours.
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| CN112679141A (en) * | 2020-12-23 | 2021-04-20 | 江苏科化新材料科技有限公司 | Epoxy resin composition for improving appearance of semiconductor package and preparation method thereof |
| CN113698762A (en) * | 2021-08-31 | 2021-11-26 | 江苏中科聚合新材料产业技术研究院有限公司 | Low-density high-toughness bismaleimide foam material and preparation method thereof |
| CN113817210A (en) * | 2021-10-21 | 2021-12-21 | 中国电子科技集团公司第三十三研究所 | Carbon nano composite wave-absorbing heat-insulating epoxy foam material and preparation method thereof |
| CN114133700A (en) * | 2021-12-17 | 2022-03-04 | 江苏宝利金材科技有限公司 | Efficient light electromagnetic absorption material with closed pore structure and preparation method thereof |
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| CN112679141A (en) * | 2020-12-23 | 2021-04-20 | 江苏科化新材料科技有限公司 | Epoxy resin composition for improving appearance of semiconductor package and preparation method thereof |
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| CN113698762A (en) * | 2021-08-31 | 2021-11-26 | 江苏中科聚合新材料产业技术研究院有限公司 | Low-density high-toughness bismaleimide foam material and preparation method thereof |
| CN113817210A (en) * | 2021-10-21 | 2021-12-21 | 中国电子科技集团公司第三十三研究所 | Carbon nano composite wave-absorbing heat-insulating epoxy foam material and preparation method thereof |
| CN114133700A (en) * | 2021-12-17 | 2022-03-04 | 江苏宝利金材科技有限公司 | Efficient light electromagnetic absorption material with closed pore structure and preparation method thereof |
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