CN114410222A - Modified hexagonal boron nitride and epoxy organic silicon resin coating material and preparation method thereof - Google Patents
Modified hexagonal boron nitride and epoxy organic silicon resin coating material and preparation method thereof Download PDFInfo
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- CN114410222A CN114410222A CN202210204038.5A CN202210204038A CN114410222A CN 114410222 A CN114410222 A CN 114410222A CN 202210204038 A CN202210204038 A CN 202210204038A CN 114410222 A CN114410222 A CN 114410222A
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- boron nitride
- hexagonal boron
- polydopamine
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- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 229910052582 BN Inorganic materials 0.000 title claims abstract description 80
- 238000000576 coating method Methods 0.000 title claims abstract description 39
- 239000011248 coating agent Substances 0.000 title claims abstract description 38
- 229920005989 resin Polymers 0.000 title claims abstract description 33
- 239000011347 resin Substances 0.000 title claims abstract description 33
- 239000004593 Epoxy Substances 0.000 title claims abstract description 26
- 239000000463 material Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 16
- 239000010703 silicon Substances 0.000 title claims abstract description 16
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 47
- 229920001690 polydopamine Polymers 0.000 claims abstract description 39
- 239000011787 zinc oxide Substances 0.000 claims abstract description 21
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 20
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 17
- 239000006185 dispersion Substances 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 229920002050 silicone resin Polymers 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 9
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 9
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 8
- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 150000003751 zinc Chemical class 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 6
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical group [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- 239000007853 buffer solution Substances 0.000 claims description 3
- 239000003085 diluting agent Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000002861 polymer material Substances 0.000 abstract description 3
- 238000006557 surface reaction Methods 0.000 abstract 1
- 230000007797 corrosion Effects 0.000 description 9
- 238000005260 corrosion Methods 0.000 description 9
- 239000000945 filler Substances 0.000 description 8
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 7
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical group CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 7
- 239000000047 product Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000000635 electron micrograph Methods 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000002912 waste gas Substances 0.000 description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical group CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 229960003638 dopamine Drugs 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 229910001425 magnesium ion Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000011343 solid material Substances 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 2
- 229910001250 2024 aluminium alloy Inorganic materials 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000000227 bioadhesive Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000004299 exfoliation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
-
- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
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- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/382—Boron-containing compounds and nitrogen
- C08K2003/385—Binary compounds of nitrogen with boron
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
The invention discloses a modified hexagonal boron nitride and epoxy organic silicon resin coating material and a preparation method thereof, and relates to the technical field of anticorrosive materials. The modified hexagonal boron nitride has the structure that polydopamine is coated outside the hexagonal boron nitride, and nano zinc oxide is grafted on the surface of the polydopamine. According to the invention, the hexagonal boron nitride is subjected to surface functionalization treatment, and is coated by polydopamine, so that the distribution of the hexagonal boron nitride in resin is improved, and meanwhile, the interface compatibility of the hexagonal boron nitride and the resin is further improved by grafting nano zinc oxide by using active groups on the surface of the polydopamine. The modified hexagonal boron nitride has good dispersibility in polymer materials, and the application field of the hexagonal boron nitride is further expanded.
Description
Technical Field
The invention relates to the technical field of anticorrosive materials, in particular to a modified hexagonal boron nitride and epoxy organic silicon resin coating material and a preparation method thereof.
Background
The corrosion and protection of equipment in the marine environment are technical problems faced by naval of various countries in the world and are also main problems of equipment guarantee. The shipboard aircraft is in service in a marine environment, not only is corroded by marine atmosphere, seawater and continuous dry/wet alternate circulation, but also is corroded by ship combustion waste gas, shipboard aircraft engine waste gas and the like, and a high-acidity wet liquid film with the pH value of 2.4-4.0 is formed by the waste gas and marine salt fog, so that the service life of the shipboard aircraft is greatly shortened. The corrosion phenomenon in the marine environment seriously affects the equipment performance and equipment management work, directly or indirectly reduces the safety and reliability of equipment, the coating protection is generally adopted due to simple construction, convenient maintenance, low cost and wide adaptability, and is the most main technical means for corrosion prevention of carrier-based aircrafts, and more than 70 percent of the corrosion protection work of carrier-based flight equipment is finished by coating anticorrosive paint.
The two-dimensional material has unique structure and peculiar mechanical, thermal, electrical, optical and other properties, overcomes the defects of the traditional inorganic filler to a certain extent, and provides a new idea for researching and developing novel anticorrosive paint. The impermeability and chemical stability of the two-dimensional material are beneficial to converting the nano barrier effect into the labyrinth effect on the organic coating structure, thereby prolonging the permeation path of corrosive media and having great application potential. Hexagonal boron nitride (h-BN), also known as "white graphene", has received wide attention from researchers due to its high thermal conductivity, high insulating properties and chemical inertness, and compared to graphene, hexagonal boron nitride is non-conductive and does not undergo galvanic corrosion in a 3.5% sodium chloride solution in cooperation with a metal matrix, thus exhibiting great application potential in the field of corrosion protection. However, due to the high specific surface area of hexagonal boron nitride and the strong van der waals force between layers, h-BN is easily agglomerated in the polymer material, and the compatibility at the filler-resin interface is poor, so that covalent bond method or non-covalent bond method modification is often required on the surface of nano hexagonal boron nitride to improve the dispersibility and agglomeration phenomenon in the resin.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a modified hexagonal boron nitride and epoxy organic silicon resin coating material with good dispersibility and interface compatibility in a polymer material and a preparation method thereof.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the modified hexagonal boron nitride is characterized in that polydopamine is coated outside the hexagonal boron nitride (h-BN), and nano zinc oxide is grafted on the surface of the polydopamine.
The polydopamine can generate self-polymerization reaction under certain conditions, and can be coated on the surfaces of various solid materials to improve the compatibility of the functional solid materials and resin. In addition, the nano zinc oxide is grafted outside the hexagonal boron nitride coated by the polydopamine, and can be connected with epoxy organic silicon resin through an dioxane bond, so that the chemical bonding between the resin and the filler is realized, and the interface compatibility between the filler and the resin is enhanced.
In addition, the invention also discloses a preparation method of the modified hexagonal boron nitride, which comprises the following steps:
(1) dispersing hexagonal boron nitride in a Tirs buffer solution with the pH value of 8.0-8.5 to obtain a dispersion liquid;
(2) adding dopamine hydrochloride into the dispersion liquid for full reaction;
(3) filtering, washing and drying the reacted solution to obtain polydopamine-coated hexagonal boron nitride (PDA-BN);
(4) and (3) adding the product prepared in the step (3) into a mixed solution of zinc salt and hexamethylenetetramine, performing ultrasonic dispersion, performing hydrothermal reaction, filtering, washing and drying to obtain the modified hexagonal boron nitride (PDA-BN @ ZnO).
According to the invention, the polydopamine-coated hexagonal boron nitride is prepared through the self-polymerization reaction of polydopamine, and then the hydrothermal reaction is carried out to graft the nano zinc oxide. The hexagonal boron nitride has a remarkable shielding effect, can prolong the propagation path of a corrosive medium in a resin material, and greatly improves the corrosion resistance of the epoxy organic silicon resin. The following formula is the principle of improving the interface compatibility of nano zinc oxide:
preferably, after the step (3) is finished, putting the polydopamine-coated hexagonal boron nitride into a magnesium chloride solution, stirring, filtering and drying.
The significance of stirring the hexagonal boron nitride coated by the polydopamine in the magnesium chloride solution is that magnesium ions and zinc ions have similar ionic radii, the polydopamine can react with the magnesium ions to form a metal ion chelate, so that nucleation sites on the polydopamine are fully opened, and the nano zinc oxide generated by the hydrothermal reaction can fully cover the surface of the polydopamine.
Further preferably, the concentration of magnesium chloride in the magnesium chloride solution is 0.05-0.2 mol/L, and the stirring time is 10-15 h.
Preferably, in the process of preparing polydopamine-coated hexagonal boron nitride, the mass ratio of the hexagonal boron nitride to dopamine hydrochloride is 1 (0.4-0.6), the concentration of the dopamine hydrochloride in a buffer solution is 0.6-1.2 mg/mL, and the reaction temperature is 50-70 ℃. When the proportion and the concentration of the raw materials meet the above limits, the polymerization of dopamine is more favorable.
Preferably, in the process of grafting the nano zinc oxide, the zinc salt is zinc nitrate and/or zinc nitrate hexahydrate, and when the zinc salt is zinc nitrate hexahydrate, the mass ratio of the zinc salt to the polydopamine-coated hexagonal boron nitride is 1: (2.5-3.0). In the mixed liquid of zinc nitrate hexahydrate and hexamethylenetetramine, the mass ratio of zinc nitrate hexahydrate, hexamethylenetetramine and water is (0.6-0.8): (0.3-0.4): (80-90), wherein the reaction temperature in the step (4) is 80-100 ℃. When the proportion of the raw materials meets the above limit, nano zinc oxide can be uniformly grafted on the surface of the polydopamine-coated hexagonal boron nitride.
Meanwhile, the invention also discloses an epoxy organic silicon resin coating material which contains the modified hexagonal boron nitride. The preparation method of the epoxy organic silicon resin coating material comprises the following steps:
(1) dissolving modified hexagonal boron nitride in a diluent, and performing ultrasonic dispersion to obtain a dispersion liquid;
(2) adding epoxy organic silicon resin into the dispersion liquid, and uniformly mixing to obtain a mixed liquid;
(3) adding a silane coupling agent into the mixed solution, uniformly stirring and curing;
(4) and coating the cured product, and drying to obtain the epoxy organic silicon resin coating material.
Preferably, the epoxy silicone resin is
An EF resin; the diluent is butyl acetate; the silane coupling agent is 3-aminopropyl triethoxysilane. The silane coupling agent and the filler have interaction, the resin also needs to be matched with the curing agent, and when the types of the components meet the above limits, the prepared epoxy organic silicon resin coating can be ensured to have higher crosslinking density.
Preferably, the coating manner is spin coating or spray coating.
Compared with the prior art, the invention has the beneficial effects that: according to the invention, the polydopamine is used for coating the hexagonal boron nitride, and the nano zinc oxide is grafted, so that the dispersibility of the hexagonal boron nitride in a resin material is improved, the interface compatibility between the hexagonal boron nitride filler and the resin is improved, and the corrosion resistance of the epoxy organic silicon resin coating is greatly improved. In addition, the introduction of the nano zinc oxide also endows the coating with certain antibacterial and uvioresistant performances; in addition, dopamine and the like are green and environment-friendly products, and the products cannot pollute the natural environment in the preparation and use processes.
Drawings
FIG. 1 is a schematic diagram of the preparation process of the epoxy silicone resin coating material of the present invention;
FIG. 2 is an electron micrograph of dispersed hexagonal boron nitride, intermediate polydopamine coated hexagonal boron nitride, and final product modified hexagonal boron nitride during preparation of example 1;
fig. 3 is a graph showing the effect of dispersing hexagonal boron nitride dispersed during the preparation of example 1, intermediate polydopamine coated hexagonal boron nitride, and final product modified hexagonal boron nitride in butyl acetate.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to the accompanying drawings and specific embodiments.
Example 1
In an embodiment of the modified hexagonal boron nitride of the present invention, a preparation method of the modified hexagonal boron nitride of the present embodiment is as follows:
(1) preparing a Tris buffer solution with the pH value of 8.5;
(2) adding 2 parts of hexagonal boron nitride into 97.2 parts of Tris buffer solution for ultrasonic dispersion to obtain a dispersion solution;
(3) adding 0.8 part of dopamine hydrochloride into the dispersion, and placing the dispersion in a water bath kettle at 60 ℃ for full reaction for 24 hours;
(4) carrying out suction filtration, washing and drying on the reacted solution to obtain polydopamine-coated hexagonal boron nitride;
(5) adding 2 parts of polydopamine-coated hexagonal boron nitride into a mixed solution of zinc nitrate hexahydrate and hexamethylenetetramine, ultrasonically dispersing for 10min, then placing the mixture in a water bath, reacting for 2.5h at 90 ℃, and performing suction filtration, washing and drying to obtain modified hexagonal boron nitride; the mixed solution of zinc nitrate hexahydrate and hexamethylenetetramine comprises the following components: 0.8 part of zinc nitrate hexahydrate, 0.38 part of hexamethylenetetramine and 90 parts of deionized water.
Example 2
In an embodiment of the modified hexagonal boron nitride according to the present invention, the only difference between this embodiment and embodiment 1 is that after step (4) is completed, the polydopamine-coated hexagonal boron nitride is put into an aqueous magnesium chloride solution with a magnesium chloride concentration of 0.1mol/L, stirred for 12 hours, filtered and dried.
Example 3
An example of modified hexagonal boron nitride according to the present invention differs from example 1 in that: in the step (3), the weight part of dopamine hydrochloride is 1.2 parts; in the step (5), 0.72 part by weight of zinc nitrate hexahydrate, 0.34 part by weight of hexamethylenetetramine, and 80 parts by weight of deionized water.
Example 4
An embodiment of the modified hexagonal boron nitride of the present invention is different from embodiment 1 in that, in step (3), the part by weight of dopamine hydrochloride is 1 part; in the step (5), 0.67 part by weight of zinc nitrate hexahydrate, 0.32 part by weight of hexamethylenetetramine, and 85 parts by weight of deionized water.
Examples 5 to 8
In the embodiments of the epoxy organic silicon resin coating material of the invention, the embodiments 5 to 8 respectively contain the modified hexagonal boron nitride described in the embodiments 1 to 4; the preparation method of the embodiment 5-8 is shown in figure 1, and concretely comprises the following steps:
(1) ultrasonically cleaning a 2024 aluminum alloy sheet with the thickness of 5 x 3.5 x 0.2cm by using ethanol, cleaning for 10min to remove impurities such as grease, dust and the like on the surface of the sheet, and drying at 80 ℃;
(2) taking 3 parts of modified hexagonal boron nitride and 68 parts of modified hexagonal boron nitride
EF epoxy silicone resin and 17 parts of aminopropyltriethoxysilane (Texaco AMEO) are added into 12 parts of butyl acetate, uniformly dispersed epoxy silicone resin coating is obtained through ultrasonic and mechanical stirring, then the coating is coated on the surface of pretreated metal through a spin coating method, and the epoxy silicone resin coating is obtained after the coating is rotated at a high speed of 100rpm for 8s and then cured for 12 hours at room temperature.
Comparative example 1
An epoxy silicone resin coating that differs from example 5 in that it does not contain modified hexagonal boron nitride and in that the butyl acetate is 15 parts by weight.
Comparative example 2
An epoxy silicone resin coating that differs from example 5 in that modified hexagonal boron nitride is replaced with hexagonal boron nitride.
Comparative example 3
An epoxy silicone resin coating that differs from example 5 in that modified hexagonal boron nitride is replaced with polydopamine-coated hexagonal boron nitride.
The coatings prepared above were immersed in 3.5 wt% NaCl solution for 30 days and tested for low frequency impedance modulus, with the results shown in Table 1:
TABLE 1
As can be seen from Table 1, the addition of hexagonal boron nitride to the resin can increase the corrosion resistance of the coating to a certain extent, and the low-frequency impedance modulus is increased by two orders of magnitude due to better compatibility of the filler and the resin after modification by polydopamine. Compared with the modified hexagonal boron nitride grafted with the nano zinc oxide, the corrosion resistance of the coating is further improved; in addition, the test results show that the performance of the modified hexagonal boron nitride prepared by stirring the polydopamine-coated hexagonal boron nitride in magnesium chloride is obviously superior to that of the untreated modified hexagonal boron nitride.
The glass transition temperature of the above coating was tested and the test results are shown in table 2:
TABLE 2
The higher the glass transition temperature, the higher the crosslinking density of the composite material, and correspondingly, the higher the compactness of the composite material, the tighter the combination of the filler and the resin. The test results show that the modified boron nitride prepared by the method of the invention is used as the filler, the coating prepared by mixing the modified boron nitride with the resin has the highest crosslinking density, and the compatibility between the filler and the resin is better.
FIG. 2 is an electron micrograph of h-BN dispersed during the preparation of example 1, intermediate PDA-BN formed, and final PDA-BN @ ZnO; in FIGS. (a, b), the unmodified h-BN exhibits a platelet morphology, indicating successful exfoliation of the h-BN; in graphs (c, d), the modified PDA-BN showed a rough, uneven surface, indicating that the polydopamine coating has been successfully modified on the h-BN surface, and that the polydopamine also easily binds h-BN with similar particle size during the formation of the surface coating due to the properties of the polydopamine bioadhesive, which explains why the observed phenomenon of increased particle size of h-BN compared to that before modification after modification of the polydopamine coating; the graphs (e, f) are electron micrographs of PDA-BN @ ZnO, compared with the graphs (c, d), particulate matters are obviously generated on the surface of the material, which is attributed to the successful grafting of the nano zinc oxide on the surface of the material, and the nano zinc oxide also has different forms, the nano zinc oxide particles in the graph (e) are mainly spherical, and the rod-shaped nano zinc oxide product is found in the graph (f), which is attributed to the reaction temperature, wherein the zinc oxide product is mainly spherical when the reaction temperature is less than 90 ℃, the dendritic zinc oxide when the reaction temperature is more than 110 ℃, and the reaction temperature is between the two when the material is synthesized, so the generated zinc oxide has two different forms.
FIG. 3 is a graph showing the effect of dispersing hexagonal boron nitride dispersed during the preparation of example 1, intermediate polydopamine coated hexagonal boron nitride, and final product modified boron nitride (from left to right) in butyl acetate; as can be seen from the figure, even if stirring and ultrasonic dispersion are carried out, h-BN is difficult to be uniformly dispersed in butyl acetate, and remarkable sedimentation phenomenon occurs, while PDA-BN and PDA-BN @ ZnO can be well dispersed. After standing for 4h, the PDA-BN also has obvious sedimentation phenomenon, and the PDA-BN @ ZnO still shows a better dispersion state. Therefore, the dispersibility of h-BN can be obviously improved by the PDA coating in the butyl acetate solvent, and the dispersibility of the raw material is further improved after the ZnO is grafted on the surface.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (8)
1. The modified hexagonal boron nitride is characterized in that the modified hexagonal boron nitride is structurally characterized in that polydopamine is coated outside the hexagonal boron nitride, and nano zinc oxide is grafted on the surface of the polydopamine.
2. A method of preparing modified hexagonal boron nitride according to claim 1, comprising the steps of:
(1) dispersing hexagonal boron nitride in a buffer solution with the pH value of 8.0-8.5 to obtain a dispersion liquid;
(2) adding dopamine hydrochloride into the dispersion liquid for full reaction;
(3) filtering, washing and drying the reacted solution to obtain polydopamine-coated hexagonal boron nitride;
(4) and (4) adding the product prepared in the step (3) into a mixed solution of zinc salt and hexamethylenetetramine, performing ultrasonic dispersion, fully reacting, filtering, washing and drying to obtain the modified hexagonal boron nitride.
3. The method for preparing modified hexagonal boron nitride according to claim 2, wherein after the step (3) is finished, the polydopamine-coated hexagonal boron nitride is put into a magnesium chloride solution to be stirred, filtered and dried.
4. The preparation method according to claim 3, wherein the concentration of magnesium chloride in the magnesium chloride solution is 0.05 to 0.2mol/L, and the stirring time is 10 to 15 hours.
5. The preparation method according to claim 2, wherein the mass ratio of the hexagonal boron nitride to the dopamine hydrochloride is 1 (0.4-0.6).
6. The preparation method according to claim 2, wherein the zinc salt is zinc nitrate and/or zinc nitrate hexahydrate, and when the zinc salt is zinc nitrate hexahydrate, the mass ratio of the zinc salt to the polydopamine-coated hexagonal boron nitride is 1: (2.5-3.0).
7. An epoxy silicone resin coating material characterized by containing the modified hexagonal boron nitride according to claim 1.
8. A method for preparing the epoxy silicone resin coating material according to claim 7, comprising the steps of:
(1) dissolving modified hexagonal boron nitride in a diluent, and performing ultrasonic dispersion to obtain a dispersion liquid;
(2) adding epoxy organic silicon resin into the dispersion liquid, and uniformly mixing to obtain a mixed liquid;
(3) adding a silane coupling agent into the mixed solution, uniformly stirring and curing;
(4) and coating the cured product, and drying to obtain the epoxy organic silicon resin coating material.
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| CN115946417A (en) * | 2022-11-07 | 2023-04-11 | 镇江市宜扬密封制品有限公司 | Composite multilayer structure's anticorrosive type polytetrafluoroethylene gasket |
| WO2024094032A1 (en) * | 2023-05-29 | 2024-05-10 | 合肥杰事杰新材料股份有限公司 | Antibacterial agent, antibacterial high-performance pom composite material and preparation method therefor |
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| CN111134133A (en) * | 2019-12-30 | 2020-05-12 | 西南大学 | Bio-based antibacterial and antiviral nano material and preparation method and application thereof |
| CN112552727A (en) * | 2020-11-12 | 2021-03-26 | 厦门大学 | Preparation method and application of boron nitride-based composite material anti-corrosion auxiliary agent |
| CN113388312A (en) * | 2021-06-18 | 2021-09-14 | 中国船舶重工集团公司第七二五研究所 | High-performance ceramic-based epoxy modified organic silicon coating and preparation and application methods thereof |
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| CN111134133A (en) * | 2019-12-30 | 2020-05-12 | 西南大学 | Bio-based antibacterial and antiviral nano material and preparation method and application thereof |
| CN112552727A (en) * | 2020-11-12 | 2021-03-26 | 厦门大学 | Preparation method and application of boron nitride-based composite material anti-corrosion auxiliary agent |
| CN113388312A (en) * | 2021-06-18 | 2021-09-14 | 中国船舶重工集团公司第七二五研究所 | High-performance ceramic-based epoxy modified organic silicon coating and preparation and application methods thereof |
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| CN115946417A (en) * | 2022-11-07 | 2023-04-11 | 镇江市宜扬密封制品有限公司 | Composite multilayer structure's anticorrosive type polytetrafluoroethylene gasket |
| WO2024094032A1 (en) * | 2023-05-29 | 2024-05-10 | 合肥杰事杰新材料股份有限公司 | Antibacterial agent, antibacterial high-performance pom composite material and preparation method therefor |
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