CN116333532A - Electromagnetic shielding rubber wave-absorbing coating - Google Patents
Electromagnetic shielding rubber wave-absorbing coating Download PDFInfo
- Publication number
- CN116333532A CN116333532A CN202310262883.2A CN202310262883A CN116333532A CN 116333532 A CN116333532 A CN 116333532A CN 202310262883 A CN202310262883 A CN 202310262883A CN 116333532 A CN116333532 A CN 116333532A
- Authority
- CN
- China
- Prior art keywords
- wave
- parts
- stirring
- absorbing
- electromagnetic shielding
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000011248 coating agent Substances 0.000 title claims abstract description 43
- 238000000576 coating method Methods 0.000 title claims abstract description 43
- 229920001971 elastomer Polymers 0.000 title claims abstract description 29
- 239000000899 Gutta-Percha Substances 0.000 claims abstract description 31
- 240000000342 Palaquium gutta Species 0.000 claims abstract description 31
- 229920000588 gutta-percha Polymers 0.000 claims abstract description 31
- 239000004020 conductor Substances 0.000 claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 24
- 239000013078 crystal Substances 0.000 claims abstract description 22
- 239000004593 Epoxy Substances 0.000 claims abstract description 21
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 18
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 13
- 239000003822 epoxy resin Substances 0.000 claims abstract description 12
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims description 52
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 42
- 238000006243 chemical reaction Methods 0.000 claims description 39
- 238000010438 heat treatment Methods 0.000 claims description 34
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- 229910021389 graphene Inorganic materials 0.000 claims description 32
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 24
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 20
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 20
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 19
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 16
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 15
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 14
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 12
- 239000002270 dispersing agent Substances 0.000 claims description 12
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 12
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 10
- 235000019253 formic acid Nutrition 0.000 claims description 10
- 239000000178 monomer Substances 0.000 claims description 10
- 239000003208 petroleum Substances 0.000 claims description 10
- 239000002518 antifoaming agent Substances 0.000 claims description 9
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 8
- 235000019441 ethanol Nutrition 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 150000001263 acyl chlorides Chemical class 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000013067 intermediate product Substances 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 238000010790 dilution Methods 0.000 claims description 5
- 239000012895 dilution Substances 0.000 claims description 5
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000002390 rotary evaporation Methods 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 239000011358 absorbing material Substances 0.000 abstract description 13
- 230000032683 aging Effects 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 7
- 238000000034 method Methods 0.000 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 229920000587 hyperbranched polymer Polymers 0.000 abstract description 5
- 238000002360 preparation method Methods 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 5
- 230000003064 anti-oxidating effect Effects 0.000 abstract description 3
- 239000006087 Silane Coupling Agent Substances 0.000 abstract description 2
- 238000010073 coating (rubber) Methods 0.000 abstract description 2
- 239000011241 protective layer Substances 0.000 abstract description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 20
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 238000005260 corrosion Methods 0.000 description 7
- 230000007797 corrosion Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 5
- 239000004202 carbamide Substances 0.000 description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 239000004952 Polyamide Substances 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 239000011231 conductive filler Substances 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 229920002647 polyamide Polymers 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 239000013530 defoamer Substances 0.000 description 3
- 229920000767 polyaniline Polymers 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000005670 electromagnetic radiation Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 229920003212 trans-1,4-polyisoprene Polymers 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D109/00—Coating compositions based on homopolymers or copolymers of conjugated diene hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/24—Electrically-conducting paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/32—Radiation-absorbing paints
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/04—Antistatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)
Abstract
The invention discloses an electromagnetic shielding rubber wave-absorbing coating, which belongs to the technical field of rubber coatings and comprises the following raw materials in parts by weight: 70 parts of epoxy resin, 30 parts of epoxy modified gutta-percha, 5-6 parts of wave-absorbing main material, 5-6 parts of organic conductive material, 2.4-3 parts of auxiliary agent and 50-52 parts of curing agent; and aiming at the problem of poor dispersibility of raw materials in the wave-absorbing material, in the preparation process of the wave-absorbing main material, the silane coupling agent is used for treating Fe 3 O 4 The needle-shaped surface of the crystal forms a protective layer on the surface of the crystal, improves the stability of the crystal in the use process, introduces amino, and then sends out the amino and the grafting monomerThe introduction of hyperbranched polymer has better antioxidation effect and can inhibit the aging of the coating after film formation compared with the wave-absorbing material without hyperbranched polymer grafting.
Description
Technical Field
The invention belongs to the technical field of rubber coatings, and particularly relates to an electromagnetic shielding rubber wave-absorbing coating.
Background
A wave-absorbing material is a material that can be used to absorb or substantially attenuate electromagnetic wave energy received by its surface, thereby reducing electromagnetic radiation or interference. The rubber-based wave-absorbing coating is more and more paid attention to by scientists in recent years, and rubber is used as a film forming substance of a wave-absorbing material to play a role of binding an adsorbent and other fillers, so that the physical property, environmental resistance and other properties of the adsorption material are determined.
Since conductivity is an essential property of electromagnetic shielding wave-absorbing coating, the conductivity of electromagnetic shielding wave-absorbing coating prepared from non-conductive organic polymer material mainly comes from conductive filler. The common conductive filler has the advantages that an oxide film is easy to form on the surface in the use process, the compatibility between the common conductive filler and the wave-absorbing material is poor, and a better electromagnetic shielding effect cannot be formed; in addition, corrosion problems are required to be considered for the ship wave-absorbing coating, the dispersibility of the wave-absorbing material is poor, the thickness of the coating is uneven after film formation, and when charges accumulate to a certain degree, discharge phenomenon can occur, the coating can be broken down, even the device is damaged, and the corrosion resistance is not improved.
Disclosure of Invention
The invention aims to provide an electromagnetic shielding rubber wave-absorbing coating, which is used for solving the problem of poor dispersibility of wave-absorbing materials in the coating.
The aim of the invention can be achieved by the following technical scheme:
an electromagnetic shielding rubber wave-absorbing coating comprises the following raw materials in parts by weight: 70 parts of epoxy resin, 30 parts of epoxy modified gutta-percha, 5-6 parts of wave-absorbing main material, 5-6 parts of organic conductive material, 2.4-3 parts of auxiliary agent and 50-52 parts of curing agent; the wave-absorbing main material is prepared by the following steps:
step S11, fe 3 O 4 Adding needle-like crystals into gamma-aminopropyl triethoxysilane and ethanol water solution with the volume fraction of 90%, stirring and dispersing, heating to 80 ℃ for heating and refluxing reaction for 12 hours, washing with absolute ethanol and water after the reaction is finished, and vacuum drying at 40 ℃ to obtain an intermediate product;
step S12, adding triethylene diamine and methyl acrylate into methanol under the protection of nitrogen at the temperature of 0 ℃, stirring and mixing, heating to 20 ℃, and stirring and reacting for 5 hours to obtain a grafted monomer;
and S13, adding the intermediate product and the grafting monomer into methanol, removing the solvent by rotary evaporation, then heating to 60 ℃ for reaction for 1h, heating to 80 ℃ for reaction for 1h, heating to 100 ℃ for reaction for 2h, heating to 120 ℃ for reaction for 2h, heating to 140 ℃ for reaction for 3h, washing with methanol after the reaction is finished, and drying in vacuum at 35 ℃ to obtain the wave-absorbing main material.
Further, fe in step S11 3 O 4 The dosage ratio of the needle-shaped crystal, the gamma-aminopropyl triethoxysilane and the ethanol aqueous solution is 1g:2g:10mL; in the step S12, the dosage ratio of triethylene diamine, methyl acrylate and methanol is 30mL:26mL:60mL; the ratio of the intermediate, grafting monomer and methanol used in step S13 was 3g:10g:30mL.
Further, the organic conductive material is prepared by the steps of:
step S21, mixing graphene oxide and N, N-dimethylformamide, stirring and dispersing, adding thionyl chloride, heating and refluxing for 4 hours, washing with tetrahydrofuran to obtain acyl chloride graphene oxide, stirring and reacting the acyl chloride graphene oxide and octadecylamine at 90 ℃ for 24 hours, and drying at 80 ℃ after the reaction is finished to obtain pretreated graphene oxide; the graphene oxide is introduced into an acyl chloride structure under the action of thionyl chloride, then reacts with octadecylamine, and introduces an alkyl long chain.
And S22, adding the pretreated graphene oxide into sulfuric acid solution, stirring and dispersing, adding aniline, continuously stirring for 20min, adding ammonium persulfate, stirring and reacting for 3h at the temperature of 20 ℃, and washing with deionized water and absolute ethyl alcohol in sequence after the reaction is finished to obtain the organic conductive material. The organic conductive material is composed of polyaniline and pretreated graphene oxide, is not easy to oxidize compared with common metal conductive fillers, and cannot reduce shielding performance due to oxidization; the graphene oxide is treated before being used to obtain pretreated graphene oxide, so that compared with untreated graphene oxide, the graphene oxide has better dispersibility, is favorable for the deposition of polyaniline, and is matched with the unique nano structure and stable capacitance performance of graphene, so that the conductive stability is improved, and more importantly, the hydrophobic performance of the paint can be better improved by introducing an alkyl long chain into the pretreated graphene oxide, and the problem of corrosion resistance can be well met. In the step S21, the dosage ratio of graphene oxide, thionyl chloride and N, N-dimethylformamide is 10mg:0.5mL:10mL; the concentration of the sulfuric acid solution in the step S22 is 1mol/L, and the dosage ratio of the pretreated graphene oxide, aniline, ammonium persulfate and sulfuric acid solution is 2.5g:100mL:2g:4g.
Wherein Fe is 3 O 4 Needle-like crystals are prepared by the steps of:
adding ferric chloride and urea into ethylene glycol, adding polyvinylpyrrolidone, mixing, adding the reaction solution into a stainless steel reaction kettle with a tetrafluoroethylene substrate, heating to 220 ℃ after sealing, cooling to room temperature after heat preservation for 6 hours, filtering, washing with absolute ethyl alcohol and deionized water, and drying to obtain Fe 3 O 4 Needle-like crystals. Wherein, the dosage ratio of ferric chloride, urea, ethylene glycol and polyvinylpyrrolidone is 0.3g:0.3g:25mL:0.05g. Preparation of needle-like Fe by hydrothermal method using ferric chloride and urea as raw materials 3 O 4 And (5) a crystal. By Fe 3 O 4 The needle-shaped crystal is a raw material of the wave absorbing material, and has better dispersing effect and conductivity compared with the flaky or granular raw material.
Further, the epoxy modified gutta-percha is prepared by the following steps:
mixing gutta-percha and petroleum ether, stirring and dissolving at 50 ℃, adding deionized water for dilution, adding formic acid and hydrogen peroxide, continuously stirring and reacting for 2 hours, washing with ethanol after the reaction is finished, and vacuum drying at 30 ℃ to obtain the epoxy modified gutta-percha. The main component of the gutta-percha is trans-1, 4-polyisoprene rubber, which has a trans-structure, huge molecular weight and higher hardness, is selected as a film forming substance, is favorable for improving the hardness of the coating after film forming, but is easy to crystallize at normal temperature, so that the polymer contains a large amount of crystals; the adhesion is poor, a large amount of crystals are contained in the polymer, and the polymer can be better mixed with epoxy resin after epoxy modification, so that the toughening effect is achieved, the brittleness of the epoxy resin is improved, the corrosion resistance of the coating is further enhanced, and the effects of the wave-absorbing main material and the organic conductive material are better exerted; the dosage ratio of gutta-percha, petroleum ether, deionized water, formic acid and hydrogen peroxide is 10g:150mL:80mL:5mL:30mL.
An electromagnetic shielding rubber wave-absorbing coating is prepared by the following steps:
weighing raw materials according to parts by weight; mixing the epoxy modified gutta-percha and the solvent, heating to 40 ℃, stirring, adding the epoxy resin, adding the auxiliary agent, the wave-absorbing main material and the organic conductive material, continuously stirring for 50-60min, adding the curing agent, and uniformly stirring to obtain the electromagnetic shielding rubber wave-absorbing coating.
Further, the auxiliary agent comprises a dispersing agent, a leveling agent and a defoaming agent; the mass ratio of the dispersing agent, the leveling agent and the defoaming agent is 1:1:1, a step of; the dispersing agent is dispersing agent F-428; the leveling agent is leveling agent F-385; the defoaming agent is a defoaming agent F-280.
Further, the epoxy resin is epoxy resin E-51; the curing agent is polyamide 651; the solvent is toluene, and the addition amount of the solvent is 4-5 times of the mass of the epoxy modified gutta-percha.
The invention has the beneficial effects that:
the invention prepares an electromagnetic shielding rubber wave-absorbing coating by using raw materials such as a wave-absorbing main material, an organic conductive material, a film-forming material and the like, and aims at the problem of poor dispersibility of the raw materials in the wave-absorbing material, and in the preparation process of the wave-absorbing main material, fe is treated by using a silane coupling agent 3 O 4 The needle-shaped polymer is grafted on the surface of the crystal, the hyperbranched polymer with high branching degree is grafted on the surface of the crystal due to higher branching degree, low viscosity and modified Fe, and a protective layer is formed on the surface of the crystal, so that the stability of the crystal in the use process is improved, amino groups are introduced, and then grafting reaction is carried out with a grafting monomer 3 O 4 The needle-shaped crystal can be better dispersed in the matrix material, and meanwhile, compared with a wave-absorbing material which is not grafted by the hyperbranched polymer, the wave-absorbing material has better antioxidation effect and can inhibit aging of the coating after film formation.
Fe in the wave-absorbing main material in the invention 3 O 4 The needle-shaped crystal can be converted into electric energy, and then the organic conductive material composed of polyaniline and graphene which are organic conductive materials can better guide and disperse the electric energy converted by radar waves; in addition, the introduction of long alkyl chains in the organic conductive material can better improve the hydrophobicity of the coatingPreventing penetration of corrosive media. The prepared coating not only has good conductivity, but also can well meet the requirement of salt spray corrosion resistance.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The embodiment provides a wave-absorbing main material, which is prepared by the following steps:
s11, adding ferric chloride and urea into ethylene glycol, adding polyvinylpyrrolidone, mixing, adding the reaction solution into a stainless steel reaction kettle with a tetrafluoroethylene substrate, heating to 220 ℃ after sealing, cooling to room temperature after heat preservation for 6 hours, filtering, washing with absolute ethyl alcohol and deionized water, and drying to obtain Fe 3 O 4 Needle-like crystals. Wherein, the dosage ratio of ferric chloride, urea, ethylene glycol and polyvinylpyrrolidone is 0.3g:0.3g:25mL:0.05g; fe is added to 3 O 4 Adding needle-like crystals into gamma-aminopropyl triethoxysilane and ethanol water solution with the volume fraction of 90%, stirring and dispersing, heating to 80 ℃ for heating and refluxing reaction for 12 hours, washing with absolute ethanol and water after the reaction is finished, and vacuum drying at 40 ℃ to obtain an intermediate product; fe (Fe) 3 O 4 The dosage ratio of the needle-shaped crystal, the gamma-aminopropyl triethoxysilane and the ethanol aqueous solution is 1g:2g:10mL;
step S12, adding triethylene diamine and methyl acrylate into methanol under the protection of nitrogen at the temperature of 0 ℃, stirring and mixing, heating to 20 ℃, and stirring and reacting for 5 hours to obtain a grafted monomer; the dosage ratio of triethylene diamine, methyl acrylate and methanol is 30mL:26mL:60mL;
and S13, adding the intermediate product and the grafting monomer into methanol, removing the solvent by rotary evaporation, then heating to 60 ℃ for reaction for 1h, heating to 80 ℃ for reaction for 1h, heating to 100 ℃ for reaction for 2h, heating to 120 ℃ for reaction for 2h, heating to 140 ℃ for reaction for 3h, washing with methanol after the reaction is finished, and drying in vacuum at 35 ℃ to obtain the wave-absorbing main material. The ratio of the amount of intermediate, grafting monomer and methanol was 3g:10g:30mL.
Example 2
The embodiment provides an organic conductive material, which is prepared by the following steps:
step S21, mixing graphene oxide and N, N-dimethylformamide, stirring and dispersing, adding thionyl chloride, heating and refluxing for 4 hours, washing with tetrahydrofuran to obtain acyl chloride graphene oxide, stirring and reacting the acyl chloride graphene oxide and octadecylamine at 90 ℃ for 24 hours, and drying at 80 ℃ after the reaction is finished to obtain pretreated graphene oxide; graphene oxide, thionyl chloride and N, N-dimethylformamide are used in an amount ratio of 10mg:0.5mL:10mL;
and S22, adding the pretreated graphene oxide into sulfuric acid solution, stirring and dispersing, adding aniline, continuously stirring for 20min, adding ammonium persulfate, stirring and reacting for 3h at the temperature of 20 ℃, and washing with deionized water and absolute ethyl alcohol in sequence after the reaction is finished to obtain the organic conductive material. The concentration of the sulfuric acid solution is 1mol/L, and the dosage ratio of the pretreated graphene oxide, aniline, ammonium persulfate and sulfuric acid solution is 2.5g:100mL:2g:4g.
Comparative example 1
This comparative example provides an organic conductive material prepared by the steps of:
adding graphene oxide into sulfuric acid solution, stirring and dispersing, adding aniline, continuously stirring for 20min, adding ammonium persulfate, stirring and reacting for 3h at 20 ℃, and washing with deionized water and absolute ethyl alcohol in sequence after the reaction is finished to obtain the organic conductive material. The concentration of the sulfuric acid solution is 1mol/L, and the dosage ratio of graphene oxide, aniline, ammonium persulfate and sulfuric acid solution is 2.5g:100mL:2g:4g.
Example 3
The embodiment provides an electromagnetic shielding rubber wave-absorbing coating, which is prepared by the following steps:
mixing gutta-percha and petroleum ether, stirring and dissolving at 50 ℃, adding deionized water for dilution, adding formic acid and hydrogen peroxide, continuously stirring and reacting for 2 hours, washing with ethanol after the reaction is finished, and vacuum drying at 30 ℃ to obtain the epoxy modified gutta-percha. The dosage ratio of gutta-percha, petroleum ether, deionized water, formic acid and hydrogen peroxide is 10g:150mL:80mL:5mL:30mL.
According to parts by weight, 70 parts of epoxy modified gutta-percha and toluene are mixed, the addition amount of toluene is 4 times of the mass of the epoxy modified gutta-percha, 30 parts of epoxy resin E-51 is added after heating to 40 ℃ and stirring, then 2.4 parts of auxiliary agent, 5 parts of the wave-absorbing main material prepared in example 1 and 5 parts of the organic conductive material prepared in example 2 are added, stirring is continued for 50 min, 50 parts of polyamide 651 is added, and after uniform stirring, the electromagnetic shielding rubber wave-absorbing coating is obtained. The auxiliary agent comprises a dispersing agent F-428, a leveling agent F-385 and a defoaming agent F-280; the mass ratio of the dispersant F-428 to the leveling agent F-385 to the defoamer F-280 is 1:1:1.
example 4
The embodiment provides an electromagnetic shielding rubber wave-absorbing coating, which is prepared by the following steps:
mixing gutta-percha and petroleum ether, stirring and dissolving at 50 ℃, adding deionized water for dilution, adding formic acid and hydrogen peroxide, continuously stirring and reacting for 2 hours, washing with ethanol after the reaction is finished, and vacuum drying at 30 ℃ to obtain the epoxy modified gutta-percha. The dosage ratio of gutta-percha, petroleum ether, deionized water, formic acid and hydrogen peroxide is 10g:150mL:80mL:5mL:30mL.
According to parts by weight, 70 parts of epoxy modified gutta-percha and toluene are mixed, the addition amount of toluene is 4.5 times of the mass of the epoxy modified gutta-percha, 30 parts of epoxy resin E-51 is added after heating to 40 ℃ and stirring, then 2.8 parts of auxiliary agent, 5.5 parts of wave-absorbing main material prepared in example 1 and 5.5 parts of organic conductive material prepared in example 2 are added, stirring is continued for 55 min, 51 parts of polyamide 651 is added, and after stirring is uniform, the electromagnetic shielding rubber wave-absorbing paint is obtained. The auxiliary agent comprises a dispersing agent F-428, a leveling agent F-385 and a defoaming agent F-280; the mass ratio of the dispersant F-428 to the leveling agent F-385 to the defoamer F-280 is 1:1:1.
example 5
The embodiment provides an electromagnetic shielding rubber wave-absorbing coating, which is prepared by the following steps:
mixing gutta-percha and petroleum ether, stirring and dissolving at 50 ℃, adding deionized water for dilution, adding formic acid and hydrogen peroxide, continuously stirring and reacting for 2 hours, washing with ethanol after the reaction is finished, and vacuum drying at 30 ℃ to obtain the epoxy modified gutta-percha. The dosage ratio of gutta-percha, petroleum ether, deionized water, formic acid and hydrogen peroxide is 10g:150mL:80mL:5mL:30mL.
According to parts by weight, 70 parts of epoxy modified gutta-percha and toluene are mixed, the addition amount of toluene is 5 times of the mass of the epoxy modified gutta-percha, 30 parts of epoxy resin E-51 is added after heating to 40 ℃ and stirring, then 3 parts of auxiliary agent, 6 parts of the wave-absorbing main material prepared in example 1 and 6 parts of the organic conductive material prepared in example 2 are added, stirring is continued for 60min, 52 parts of polyamide 651 is added, and after stirring is uniform, the electromagnetic shielding rubber wave-absorbing paint is obtained. The auxiliary agent comprises a dispersing agent F-428, a leveling agent F-385 and a defoaming agent F-280; the mass ratio of the dispersant F-428 to the leveling agent F-385 to the defoamer F-280 is 1:1:1.
comparative example 2
In this comparative example, compared with example 5, the wave-absorbing material was changed to the intermediate product prepared in example 1, and the remaining raw materials and the preparation process were kept the same as in example 5.
Comparative example 3
In this comparative example, compared with comparative example 2, the organic conductive material was changed to the sample prepared in comparative example 1, and the remaining raw materials and preparation process were kept the same as comparative example 2.
Performance tests were performed on examples 3-5 and comparative examples 2-3; the test contents comprise conductivity, salt spray resistance test and aging resistance test, wherein the salt spray resistance test comprises the following steps: the room temperature is 27.2 ℃, and the salt fog pressure is regulated to 0.5-1.7kg/cm 2 Spraying sodium chloride solution with the concentration of 5% for 600 hours, observing the change of the surface of the coating at regular time to observe whether obvious corrosion phenomenon exists or not, and testing the adhesive force;
aging resistance test: test according to GB/T1766-1995 colourRating criteria for paint and varnish coating aging; artificial aging conditions: intensity of illumination 0.71 (W.m) -2 ) The illumination time is 4 hours (60 ℃) and the condensation time is 4 hours (50 ℃) and the aging is 370 hours.
The results are shown in Table 1:
TABLE 1
| Project | Example 3 | Example 4 | Example 5 | Comparative example 2 | Comparative example 3 |
| Coating areal Density (kg/m) 2 ) | 1.614 | 1.621 | 1.633 | 1.635 | 1.628 |
| Conductivity (S/cm) | 9.27×10 -3 | 9.29×10 -3 | 9.32×10 -3 | 7.74×10 -3 | 6.37×10 -3 |
| Whether or not to corrode | Whether or not | Whether or not | Whether or not | Whether or not | Is that |
| Adhesion decrease Rate (%) | 28.1 | 28.5 | 28.7 | 36.7 | 42.5 |
| △E | 4.8 | 4.6 | 4.7 | 17.9 | 18.2 |
As can be seen from Table 1, the electromagnetic shielding rubber wave-absorbing coating prepared by the invention has good conductivity, and is characterized in that the wave-absorbing main material and the organic conductive material have better dispersibility, the conductivity is superior to that of powder, meanwhile, the introduction of hyperbranched structure in the wave-absorbing main material can play a role in coating free radicals, and the electromagnetic shielding rubber wave-absorbing coating has better antioxidation effect and inhibits aging of the coating after film formation compared with the wave-absorbing material without hyperbranched polymer grafting. Meanwhile, the introduction of the alkyl long chain in the organic conductive material can better improve the hydrophobic property of the coating, thereby improving the salt spray corrosion resistance of the coating after film formation.
It is noted that relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (7)
1. The electromagnetic shielding rubber wave-absorbing coating is characterized by comprising the following raw materials in parts by weight: 70 parts of epoxy resin, 30 parts of epoxy modified gutta-percha, 5-6 parts of wave-absorbing main material, 5-6 parts of organic conductive material, 2.4-3 parts of auxiliary agent and 50-52 parts of curing agent;
the wave-absorbing main material is prepared by the following steps:
step S11, fe 3 O 4 Adding needle-like crystals into gamma-aminopropyl triethoxysilane and ethanol water solution with the volume fraction of 90%, stirring and dispersing, heating to 80 ℃ and carrying out heating reflux reaction for 12 hours to obtain an intermediate product;
step S12, adding triethylene diamine and methyl acrylate into methanol under the protection of nitrogen at the temperature of 0 ℃, stirring and mixing, heating to 20 ℃, and stirring and reacting for 5 hours to obtain a grafted monomer;
and S13, adding the intermediate product and the grafting monomer into methanol, removing the solvent by rotary evaporation, then heating to 60 ℃ for reaction for 1h, heating to 80 ℃ for reaction for 1h, heating to 100 ℃ for reaction for 2h, heating to 120 ℃ for reaction for 2h, and heating to 140 ℃ for reaction for 3h to obtain the wave-absorbing main material.
2. The electromagnetic shielding rubber wave-absorbing coating according to claim 1, wherein the step SFe in 11 3 O 4 The dosage ratio of the needle-shaped crystal, the gamma-aminopropyl triethoxysilane and the ethanol aqueous solution is 1g:2g:10mL; in the step S12, the dosage ratio of triethylene diamine, methyl acrylate and methanol is 30mL:26mL:60mL; the ratio of the intermediate, grafting monomer and methanol used in step S13 was 3g:10g:30mL.
3. The electromagnetic shielding rubber wave absorbing coating according to claim 1, wherein the organic conductive material is prepared by the steps of:
step S21, mixing graphene oxide and N, N-dimethylformamide, stirring and dispersing, adding thionyl chloride, heating and refluxing for 4 hours, washing with tetrahydrofuran to obtain acyl chloride graphene oxide, stirring and reacting the acyl chloride graphene oxide and octadecylamine at 90 ℃ for 24 hours, and drying at 80 ℃ after the reaction is finished to obtain pretreated graphene oxide; graphene oxide, thionyl chloride and N, N-dimethylformamide are used in an amount ratio of 10mg:0.5mL:10mL;
s22, adding pretreated graphene oxide into sulfuric acid solution, stirring and dispersing, adding aniline, continuously stirring for 20min, adding ammonium persulfate, stirring and reacting for 3h at 20 ℃, and washing with deionized water and absolute ethyl alcohol in sequence after the reaction is finished to obtain an organic conductive material; the concentration of the sulfuric acid solution is 1mol/L, and the dosage ratio of the pretreated graphene oxide, aniline, ammonium persulfate and sulfuric acid solution is 2.5g:100mL:2g:4g.
4. The electromagnetic shielding rubber wave-absorbing coating according to claim 1, wherein the epoxy modified gutta percha is prepared by the steps of:
mixing gutta-percha and petroleum ether, stirring and dissolving at 50 ℃, adding deionized water for dilution, adding formic acid and hydrogen peroxide, continuously stirring and reacting for 2 hours, washing with ethanol after the reaction is finished, and vacuum drying at 30 ℃ to obtain epoxy modified gutta-percha; the dosage ratio of gutta-percha, petroleum ether, deionized water, formic acid and hydrogen peroxide is 10g:150mL:80mL:5mL:30mL.
5. The electromagnetic shielding rubber wave absorbing coating according to claim 1, wherein the electromagnetic shielding rubber wave absorbing coating is prepared by the following steps:
mixing the epoxy modified gutta-percha and the solvent, heating to 40 ℃, stirring, adding the epoxy resin, adding the auxiliary agent, the wave-absorbing main material and the organic conductive material, continuously stirring for 50-60min, adding the curing agent, and uniformly stirring to obtain the electromagnetic shielding rubber wave-absorbing coating.
6. The electromagnetic shielding rubber wave-absorbing coating according to claim 5, wherein the auxiliary agent comprises a dispersing agent, a leveling agent and a defoaming agent; the mass ratio of the dispersing agent, the leveling agent and the defoaming agent is 1:1:1.
7. the electromagnetic shielding rubber wave-absorbing coating according to claim 5, wherein the addition amount of the solvent is 4-5 times of the mass of the epoxy modified gutta percha.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310262883.2A CN116333532A (en) | 2023-03-17 | 2023-03-17 | Electromagnetic shielding rubber wave-absorbing coating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310262883.2A CN116333532A (en) | 2023-03-17 | 2023-03-17 | Electromagnetic shielding rubber wave-absorbing coating |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116333532A true CN116333532A (en) | 2023-06-27 |
Family
ID=86880050
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310262883.2A Pending CN116333532A (en) | 2023-03-17 | 2023-03-17 | Electromagnetic shielding rubber wave-absorbing coating |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116333532A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112175484A (en) * | 2020-09-29 | 2021-01-05 | 沈阳化工大学 | Preparation method of electromagnetic shielding coating containing crystalline gutta-percha |
| CN114656702A (en) * | 2022-05-10 | 2022-06-24 | 安徽永正密封件有限公司 | Flame-retardant rubber for building safety net and preparation method thereof |
-
2023
- 2023-03-17 CN CN202310262883.2A patent/CN116333532A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112175484A (en) * | 2020-09-29 | 2021-01-05 | 沈阳化工大学 | Preparation method of electromagnetic shielding coating containing crystalline gutta-percha |
| CN114656702A (en) * | 2022-05-10 | 2022-06-24 | 安徽永正密封件有限公司 | Flame-retardant rubber for building safety net and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 化学工业部科学技术情报研究所: "《化工产品手册 有机化工原料 上册》", vol. 1, 北京：化学工业出版社, pages: 513 - 514 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114316732B (en) | Functional hexagonal boron nitride epoxy composite anticorrosive coating material based on phytic acid | |
| US20200239708A1 (en) | Anticorrosive Grafted Graphene Filler for Organic Coating and Methods of Preparing the Same | |
| CN110054965B (en) | Modified graphene oxide co-cured waterborne epoxy resin coating and preparation method thereof | |
| CN111978771B (en) | Modified graphene oxide, preparation method thereof, anticorrosive paint containing modified graphene oxide and preparation method | |
| CN114561118B (en) | Polypyrrole-coated graphene corrosion inhibitor container and preparation method thereof, composite coating and application thereof | |
| CN112011251A (en) | Graphene-modified water-based phenolic epoxy anticorrosive paint and preparation method thereof | |
| CN109385181B (en) | Preparation method of epoxy eucommia rubber-containing paint | |
| CN108976977B (en) | Graphene in-situ polymerization modified conductive anticorrosion aqueous adhesive emulsion and preparation method thereof | |
| Ding et al. | A novel waterborne epoxy coating with anticorrosion properties on rusty steel | |
| CN113527964B (en) | Water-based acrylic acid protective coating | |
| CN116333532A (en) | Electromagnetic shielding rubber wave-absorbing coating | |
| CN116426193A (en) | Water-based environment-friendly anticorrosive paint | |
| CN113150640B (en) | Cerium ion-loaded two-dimensional nanomaterial-based self-healing barrier dual-function coating and preparation method and application thereof | |
| CN114561140A (en) | Electrostatic shielding graphene anticorrosive material and preparation method thereof | |
| CN111850532B (en) | Chromium-free surface treatment liquid for electro-galvanized steel plate and preparation method thereof | |
| CN115216203A (en) | Water-based chromium-free Dacromet green coating and preparation method thereof | |
| CN116463033B (en) | Phytic acid/poly (m-phenylenediamine) modified nano SiO 2 Modified waterborne epoxy resin anticorrosive paint and preparation method thereof | |
| CN115820091B (en) | Preparation of GO-PDA-CeO 2 Method for preparing PU wear-resistant super-hydrophobic long-acting anti-corrosion coating | |
| CN113248960B (en) | Nano container filler with multiple self-repairing and anti-corrosion functions and application thereof | |
| Meng et al. | A novel anticorrosive performance coating through introducing epoxidized hydroxyl terminated polybutadiene | |
| CN113088038B (en) | High-hardness corrosion-resistant synthetic resin and preparation method thereof | |
| Feng et al. | Novel Lignin‐Functionalized Waterborne Epoxy Composite Coatings with Excellent Anti‐Aging, UV Resistance, and Interfacial Anti‐Corrosion Performance | |
| CN117363148B (en) | Graphene anticorrosive paint | |
| CN111073458B (en) | Preparation method for improving drying speed of water-based epoxy primer | |
| CN114410185B (en) | Preparation method and application of electrostatic spinning film-silicate mineral-2D Co-MOFs epoxy resin coating |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |