CN115386255A - Two-dimensional material modified raw lacquer marine anticorrosive paint and preparation method thereof - Google Patents
Two-dimensional material modified raw lacquer marine anticorrosive paint and preparation method thereof Download PDFInfo
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- CN115386255A CN115386255A CN202211185832.6A CN202211185832A CN115386255A CN 115386255 A CN115386255 A CN 115386255A CN 202211185832 A CN202211185832 A CN 202211185832A CN 115386255 A CN115386255 A CN 115386255A
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- 239000004922 lacquer Substances 0.000 title claims abstract description 55
- 239000000463 material Substances 0.000 title claims abstract description 38
- 239000003973 paint Substances 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000000576 coating method Methods 0.000 claims abstract description 54
- 239000011248 coating agent Substances 0.000 claims abstract description 47
- 238000005260 corrosion Methods 0.000 claims abstract description 36
- 230000007797 corrosion Effects 0.000 claims abstract description 35
- 239000006185 dispersion Substances 0.000 claims abstract description 15
- 239000003112 inhibitor Substances 0.000 claims abstract description 15
- 125000005376 alkyl siloxane group Chemical group 0.000 claims abstract description 5
- 238000005530 etching Methods 0.000 claims abstract description 5
- 238000006136 alcoholysis reaction Methods 0.000 claims abstract description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000002135 nanosheet Substances 0.000 claims description 13
- 239000002383 tung oil Substances 0.000 claims description 12
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 5
- -1 dodecyl siloxane Chemical class 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 3
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 2
- 230000001476 alcoholic effect Effects 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 10
- 230000004888 barrier function Effects 0.000 abstract description 6
- 230000002195 synergetic effect Effects 0.000 abstract description 4
- 239000002657 fibrous material Substances 0.000 abstract 1
- 239000002966 varnish Substances 0.000 abstract 1
- 239000010936 titanium Substances 0.000 description 30
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 239000003921 oil Substances 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 7
- 238000005119 centrifugation Methods 0.000 description 6
- 230000007547 defect Effects 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000000047 product Substances 0.000 description 6
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- 238000012360 testing method Methods 0.000 description 6
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- 230000008901 benefit Effects 0.000 description 5
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- 239000010410 layer Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 238000005536 corrosion prevention Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- FZMJEGJVKFTGMU-UHFFFAOYSA-N triethoxy(octadecyl)silane Chemical compound CCCCCCCCCCCCCCCCCC[Si](OCC)(OCC)OCC FZMJEGJVKFTGMU-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
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- 239000003513 alkali Substances 0.000 description 2
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- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- RMTXUPIIESNLPW-UHFFFAOYSA-N 1,2-dihydroxy-3-(pentadeca-8,11-dienyl)benzene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1O RMTXUPIIESNLPW-UHFFFAOYSA-N 0.000 description 1
- QARRXYBJLBIVAK-UEMSJJPVSA-N 3-[(8e,11e)-pentadeca-8,11-dienyl]benzene-1,2-diol;3-[(8e,11e)-pentadeca-8,11,14-trienyl]benzene-1,2-diol;3-[(8e,11e,13e)-pentadeca-8,11,13-trienyl]benzene-1,2-diol;3-[(e)-pentadec-8-enyl]benzene-1,2-diol;3-pentadecylbenzene-1,2-diol Chemical compound CCCCCCCCCCCCCCCC1=CC=CC(O)=C1O.CCCCCC\C=C\CCCCCCCC1=CC=CC(O)=C1O.CCC\C=C\C\C=C\CCCCCCCC1=CC=CC(O)=C1O.C\C=C\C=C\C\C=C\CCCCCCCC1=CC=CC(O)=C1O.OC1=CC=CC(CCCCCCC\C=C\C\C=C\CC=C)=C1O QARRXYBJLBIVAK-UEMSJJPVSA-N 0.000 description 1
- IYROWZYPEIMDDN-UHFFFAOYSA-N 3-n-pentadec-8,11,13-trienyl catechol Natural products CC=CC=CCC=CCCCCCCCC1=CC=CC(O)=C1O IYROWZYPEIMDDN-UHFFFAOYSA-N 0.000 description 1
- 244000268590 Euryale ferox Species 0.000 description 1
- 235000006487 Euryale ferox Nutrition 0.000 description 1
- 108010029541 Laccase Proteins 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 244000153888 Tung Species 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
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- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
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- 239000011159 matrix material Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052572 stoneware Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- DQTMTQZSOJMZSF-UHFFFAOYSA-N urushiol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1O DQTMTQZSOJMZSF-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
- C09D5/08—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
- C09D193/00—Coating compositions based on natural resins; Coating compositions based on derivatives thereof
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
-
- 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
- C08K2201/011—Nanostructured additives
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
Abstract
The invention discloses a two-dimensional material modified raw lacquer marine anticorrosive paint and a preparation method thereof, and Ti is used 3 AlC 2 Etching to obtain Ti with a lamellar structure 3 C 2 And ultrasonically stripped into a dispersion. Subsequent alcoholysis reaction by alkylsiloxanes in ethanol solution, and Ti 3 C 2 Rich hydroxyl active sites on the surface, and grafting fatty chains on the surface of a two-dimensional material to ensure that Ti 3 C 2 From hydrophilic to lipophilic. And finally, dispersing the synthesized two-dimensional material in the varnish to prepare a corrosion inhibitor, and adding the corrosion inhibitor into the raw lacquer to prepare the raw lacquer-based marine anticorrosive paint. The coating prepared by the invention not only makes a labyrinth effect and prolongs a corrosion path due to the barrier effect of the two-dimensional material, but also improves the corrosion resistance and corrosion resistance of the coating through the synergistic effect of the coating and the wide oilThe dispersibility and compatibility of the fiber material in the organic coating improve the glossiness of the coating, play a role in synergistic corrosion resistance, and improve the corrosion resistance by 1-2 orders of magnitude compared with the original raw lacquer coating.
Description
Technical Field
The invention belongs to the field of organic coating marine corrosion prevention, and particularly relates to a two-dimensional material modified raw lacquer marine corrosion prevention coating and a preparation method thereof.
Background
Offshore oil and gas pipelines, port facilities, offshore wind power facilities, large ships and the like can not be separated from steel structures, and the corrosion and failure of steel can be accelerated in the severe high-salinity and high-humidity natural environment of ocean and offshore environments, so that the service life and safety of ocean engineering equipment and offshore structures are seriously threatened. Electrochemical corrosion is one of the important factors causing metal deterioration, and the application of organic polymer coatings to metal surfaces is the most convenient, most direct and most economical electrochemical corrosion prevention strategy. As it applies not only to newly constructed infrastructures but also to old equipment and vessels already existing and in service. The solvent-based and water-based anticorrosive coatings adopted at present inevitably have the defects of shrinkage, stress relaxation and internal defects caused by volatilization of solvents or water in the process of forming a coating film, and the resistance of the coating to corrosive media is seriously weakened, so that the service life of the coating is greatly reduced. Therefore, the development of novel light-weight, low-dosage and high-performance anticorrosive coatings becomes a key requirement for prolonging the service life and improving the use safety of ocean engineering equipment, and the research on novel metal anticorrosive coatings used by special and extreme environment facilities such as high-performance and multifunctional oceans and offshore facilities is urgently needed.
The raw lacquer has the reputation of 'three treasures' in China, has excellent performances of corrosion resistance, strong acid resistance, strong alkali resistance, moisture resistance, insulation, high temperature resistance and the like, and is cured to form a film under a mild condition through laccase catalytic oxidation. Since the age of the new stoneware, mainly used in the field of industrial art, the coating is very stable, durable and impermeable, and has excellent chemical resistance to corrosive media, and the coating can also be applied to metal anticorrosive coatings, such as urushiol titanium chelate high polymer anticorrosive coatings, which have excellent strong acid, strong alkali and high temperature resistance. Like other organic coatings, raw lacquer is used in the corrosion protection of metallic materials, and defects and inhomogeneities resulting from the curing process are important causes of corrosion failure thereof.
The two-dimensional nano material has high diameter/thickness ratio, outstanding water and oxygen barrier performance, ion impermeability and chemical stability, and the two-dimensional material with the nano barrier effect is introduced into the organic coating, so that a labyrinth effect is formed in the coating, and the permeation path of corrosive media is prolonged. Wherein, the two-dimensional transition metal carbide/nitride Ti 3 C 2 The nano material has a large transverse ratio, abundant surface chemical properties and excellent electric and heat conducting properties, and has wide application prospects in the fields of electromagnetic shielding materials, energy storage, catalysis, adsorption and the like. In particular Ti 3 C 2 The graphene has high elastic modulus in the reference plane direction, and the bending strength is higher than that of graphene with the same thickness. Single layer of Ti 3 C 2 Elastic modulus of about 300 GPa, greater than that of most of the layered two-dimensional material, ti 3 C 2 The large specific surface area of the protective layer is easy to form a large-area protective layer with micro-nano thickness. Thus, ti 3 C 2 Has great potential for improving the corrosion resistance and the wear resistance of the organic coating. The economic benefit and the social benefit of preparing and popularizing the raw lacquer-based anticorrosive coating with excellent anticorrosive performance are immeasurable.
Disclosure of Invention
The invention aims to provide a preparation method of a two-dimensional material modified raw lacquer marine anticorrosive coating, aiming at the defect of insufficient anticorrosive capability of a natural raw lacquer coating in a marine environment. The anticorrosive coating prepared by the invention not only has the barrier effect provided by a two-dimensional lamellar material and prolongs the path of corrosive ion permeation, but also has the synergistic anticorrosive effect with Guangdong oil, and compared with the original raw lacquer coating, the anticorrosive capability is improved by 1-2 orders of magnitude. In addition, ti grafted with aliphatic chain 3 C 2 The nano sheets can be well dissolved with the crude oil and uniformly dispersed in the raw lacquer coating, thereby avoiding the occurrence of agglomeration and effectively making up the defect generated after the raw lacquer is naturally dried. Of euryale feroxThe addition of the paint also obviously improves the glossiness of the raw lacquer, so that the coating is more bright and beautiful.
In order to realize the purpose, the invention adopts the following technical scheme:
the preparation method of the two-dimensional material modified raw lacquer marine anticorrosive paint comprises the following steps:
(1) Mixing Ti 3 AlC 2 Etching to obtain Ti with a lamellar structure 3 C 2 And ultrasonically exfoliating to Ti 3 C 2 A few-layer dispersion. Subsequent alcoholysis reaction by alkylsiloxanes in ethanol solution, and Ti 3 C 2 Rich hydroxyl active sites on the surface, and grafting fatty chains on the surface of a two-dimensional material to ensure that Ti 3 C 2 Changing hydrophilicity into lipophilicity to obtain oleophilic Ti 3 C 2 Nanosheets.
(2) Adding oleophilic Ti 3 C 2 The nano-sheets are dispersed in oleum sesami (boiled tung oil and polymerized tung oil), a corrosion inhibitor with a certain proportion is prepared, and the corrosion inhibitor is added into raw lacquer according to different mass ratios to prepare the two-dimensional material modified raw lacquer marine anticorrosive coating.
Further, ti 3 C 2 The few-layer dispersion is prepared by etching Ti with lithium fluoride and hydrochloric acid 3 AlC 2 And obtained by ultrasonic and centrifugal stripping; the Ti 3 C 2 A few-layer dispersion in deionized water, ti 3 C 2 The number of layers is less than 5, and the concentration is 10-15 mg/ml.
Further, the alkyl siloxane is one of dodecyl siloxane and octadecyl siloxane, and on one hand, modified Ti is 3 C 2 The compatibility with paint and wide oil is increased, and on the other hand, the contact angle of the coating is increased, the surface is hydrophobic, and the corrosion resistance is improved; the Guang oil is prepared by decocting raw tung oil at 230 ℃ for 6 hours, is used for improving the anti-corrosion performance, and cannot be naturally dried into a film when other oil substances are added into raw lacquer.
Further, ti in the corrosion inhibitor 3 C 2 The concentration of the raw lacquer is 2-5 mg/ml, and the adding proportion is 1-10 percent of the mass of the raw lacquer.
The raw lacquer-based marine anticorrosive coating prepared by the invention not only maintains the good physical and mechanical properties of natural raw lacquer, but also remarkably improves the corrosion resistance of the raw lacquer in marine environment, and can be used for protecting metal substrates. Meanwhile, the glossiness of the coating is greatly improved, and the coating is bright and beautiful.
Compared with the prior art, the two-dimensional material modified raw lacquer marine anticorrosive paint has the advantages that: the two-dimensional material modified raw lacquer marine anticorrosive paint takes natural raw lacquer as base resin, is an environment-friendly material, is non-toxic and pollution-free, and has low price; two-dimensional material Ti 3 C 2 The raw lacquer coating has the advantages of obvious layered structure, large specific surface area, good barrier effect, oleophylic and hydrophobic property after modification, and excellent corrosion resistance; and then the tung oil formed by squeezing tung tree fruits is decocted at high temperature to form wide oil with higher polymerization degree, which is used as a dispersant and a corrosion inhibitor and plays a role in improving the cross-linking density and the corrosion resistance of the raw lacquer together with the two-dimensional material.
Detailed Description
The technical solution of the present invention is further described with reference to the following examples, but is not limited to these examples, and the tung oil used in the present invention is purchased from Shanxi faucet national paint Mill, and can be called Guang oil and Ming oil.
Example 1
(1) Mixing 1g of Ti 3 AlC 2 2g lithium fluoride was added to 9M hydrochloric acid and reacted at 48h with the reaction temperature controlled at 40 ℃. After the reaction was complete, the product was centrifuged at 3500 rpm for 5 minutes and washed several times with 2M hydrochloric acid and deionized water until the supernatant pH reached 6.
(2) And (2) continuously adding deionized water into the product obtained in the step (1) for centrifugation, stopping centrifugation when no solid-liquid separation occurs in the solution, pouring the solution into a gas washing bottle, introducing inert gas, and performing ultrasonic treatment for 1 hour in an ice bath environment. Finally, the dispersion was centrifuged at 3500 rpm for 30 minutes, and the concentration of the dispersion was determined to be 10 mg/ml.
(3) Adding the dispersion prepared in the step (2) into a mixed solution of 200 ml ethanol and 10 ml ammonia water, stirring 24 h, adding octadecyltriethoxysilane, and continuously stirring 24 h. Finally centrifuging, washing and drying to obtain the parentOil type Ti 3 C 2 Nanosheets.
(4) Ultrasonically dispersing the nanosheets obtained in the step (3) in the oleum sesami to obtain the corrosion inhibitor with the concentration of 2 mg/ml.
(5) And adding 5wt% of corrosion inhibitor into the raw lacquer, and uniformly stirring to obtain the two-dimensional material modified raw lacquer marine anticorrosive coating.
The two-dimensional material modified raw lacquer marine anticorrosive coating prepared by the embodiment has the advantages of 1-grade adhesion, 55 cm impact resistance distance, 1 mm flexibility and 1008 h salt spray duration.
Example 2
(1) Mixing 1g of Ti 3 AlC 2 2g of lithium fluoride is added into 9M hydrochloric acid to react with 48h, and the reaction temperature is controlled at 40 ℃. After the reaction was complete, the product was centrifuged at 3500 rpm for 5 minutes and washed several times with 2M hydrochloric acid and deionized water until the supernatant pH reached 6.
(2) And (2) continuously adding deionized water into the product obtained in the step (1) for centrifugation, stopping centrifugation when no solid-liquid separation occurs in the solution, pouring the solution into a gas washing bottle, introducing inert gas, and performing ultrasonic treatment on the solution in an ice bath environment to obtain 1h. Finally, the mixture was centrifuged at 3500 rpm for 30 minutes, and the concentration of the dispersion was determined to be 10 mg/ml.
(3) Adding the dispersion prepared in the step (2) into a mixed solution of 200 ml ethanol and 10 ml ammonia water, stirring 24 h, adding octadecyltriethoxysilane, and continuously stirring 24 h. Finally centrifuging, washing and drying to obtain oleophilic Ti 3 C 2 Nanosheets.
(4) Ultrasonically dispersing the nanosheets obtained in the step (3) in the oleum sesami to obtain the corrosion inhibitor with the concentration of 5 mg/ml.
(5) And adding 3wt% of corrosion inhibitor into the raw lacquer, and uniformly stirring to obtain the two-dimensional material modified raw lacquer marine anticorrosive coating.
The two-dimensional material modified raw lacquer marine anticorrosive coating prepared in the embodiment has the adhesion force of grade 1, the impact resistance distance of 60 cm, the flexibility of 1 mm and the salt spray duration of 1080 h.
Example 3
(1) Mixing 1g of Ti 3 AlC 2 2g of lithium fluoride is added into 9M hydrochloric acid to react for 48 hours, and the reaction temperature is controlled at 40 ℃. After the reaction is finishedThe product was centrifuged at 3500 rpm for 5 minutes and washed several times with 2M hydrochloric acid and deionized water until the supernatant pH reached 6.
(2) And (2) continuously adding deionized water into the product obtained in the step (1) for centrifugation, stopping centrifugation when no solid-liquid separation occurs in the solution, pouring the solution into a gas washing bottle, introducing inert gas, and performing ultrasonic treatment for 1 hour in an ice bath environment. Finally, the dispersion was centrifuged at 3500 rpm for 30 minutes, and the concentration of the dispersion was determined to be 10 mg/ml.
(3) Adding the dispersion prepared in the step (2) into a mixed solution of 200 ml ethanol and 10 ml ammonia water, stirring 24 h, adding octadecyltriethoxysilane, and continuously stirring 24 h. Finally centrifuging, washing and drying to obtain oleophilic Ti 3 C 2 Nanosheets.
(4) Ultrasonically dispersing the nanosheets obtained in the step (3) in the oleum sesami to obtain the corrosion inhibitor with the concentration of 5 mg/ml.
(5) And adding 5wt% of corrosion inhibitor into the raw lacquer, and uniformly stirring to obtain the two-dimensional material modified raw lacquer marine anticorrosive coating.
The two-dimensional material modified raw lacquer marine anticorrosive coating prepared by the embodiment has the adhesion of grade 1, the impact resistance distance of 60 cm, the flexibility of 1 mm and the salt spray duration of 1320 h.
Testing the adhesion of the two-dimensional material modified raw lacquer marine anticorrosive coating prepared in the embodiment 1-3, referring to the national standard GB/T5210-2006; performing impact resistance test according to national standard GB/T1732-1993; flexibility test, referring to national standard GB/T6742-2007; salt spray test, refer to national standard GB/T1771-2007.
As is clear from the above, ti is added simultaneously in the present invention 3 C 2 And the salt spray test time of the examples of the boiled tung oil is more than 1000h (the natural raw lacquer is less than 600 h); but the test shows that the duration of the raw lacquer salt fog modified by adding only boiled tung oil (5% by weight) is 720h; addition of only Ti 3 C 2 The modified raw lacquer salt spray time is 960h, and the Ti of the invention can be seen 3 C 2 Has synergistic effect with boiled tung oil: first, modified Ti 3 C 2 The nano-sheets can be well dissolved with the boiled tung oil and uniformly dispersed in the raw lacquer coating, thereby effectively solving the problem that the traditional two-dimensional material exists in organic resinPoor dispersibility, easy agglomeration and the like, and the increase of the compactness of the two-dimensional material and the raw lacquer can reduce the generation of the internal defects of the coating, avoid the local micro-galvanic corrosion and further improve the long-acting corrosion resistance of the coating. Second, modified Ti 3 C 2 Can exert barrier effect with boiled tung oil, can prevent corrosive medium from entering into matrix resin, and simultaneously has lamellar Ti 3 C 2 And a complex labyrinth effect can be generated, and the permeation path of the corrosive medium is prolonged. Ti having excellent conductive properties when the coating is damaged 3 C 2 Can conduct electrons generated by the anode reaction to the surface of the coating, so that the cathode reaction is generated on the surface of the coating, and OH generated by the cathode reaction - Fe formed by reaction with anode 3+ Not capable of contact reaction with Fe 3+ The anodic reaction is inhibited, thereby achieving the effect of inhibiting the corrosion of the base material. Only the composite coating of the boiled tung oil is added, and only a corrosive medium can be isolated physically and simply, so that the anticorrosion effect is not improved obviously; by direct addition of Ti 3 C 2 Due to Ti 3 C 2 Can increase local micro-couple corrosion of the coating, leading to coating damage, and Ti is in the damaged position 3 C 2 It is possible to induce its own corrosion promoting activity and release electrons at the fastest speed, accelerating the corrosion of the metal substrate, thereby shortening the corrosion prevention time.
The foregoing is only a preferred embodiment of the present invention, and all equivalent changes and modifications made within the scope of the present invention should be covered by the present invention.
Claims (7)
1. A preparation method of a two-dimensional material modified raw lacquer marine anticorrosive paint is characterized by comprising the following steps:
(1) Mixing Ti 3 AlC 2 Etching to obtain Ti with a lamellar structure 3 C 2 And ultrasonically exfoliating to Ti 3 C 2 A few-layer dispersion, followed by alcoholysis of alkylsiloxanes in an alcoholic solution, and Ti 3 C 2 Rich hydroxyl active sites on the surface, and grafting fatty chains on Ti 3 C 2 Surface of Ti 3 C 2 Changing hydrophilicity into lipophilicity to obtain oleophilic Ti 3 C 2 Nanosheets;
(2) Subjecting the oleophilic Ti of step (1) to 3 C 2 The nano sheets are dispersed in the lard, the corrosion inhibitor is prepared, and then the corrosion inhibitor is added into the raw lacquer, so that the two-dimensional material modified raw lacquer marine anticorrosive coating is obtained.
2. The preparation method of the two-dimensional material modified raw lacquer marine anticorrosive paint according to claim 1, characterized by comprising the following steps: ti 3 C 2 The few-layer dispersion is prepared by etching Ti with lithium fluoride and hydrochloric acid 3 AlC 2 And obtaining the product by ultrasonic and centrifugal stripping.
3. The preparation method of the two-dimensional material modified raw lacquer marine anticorrosive paint according to claim 1, characterized by comprising the following steps: the Ti 3 C 2 The solvent in the less-layer dispersion liquid is deionized water and Ti 3 C 2 The number of layers is less than 5, and the concentration is 10-15 mg/ml.
4. The preparation method of the two-dimensional material modified raw lacquer marine anticorrosive paint according to claim 1, characterized by comprising the following steps: the alkyl siloxane is dodecyl siloxane or octadecyl siloxane.
5. The preparation method of the two-dimensional material modified raw lacquer marine anticorrosive paint according to claim 1, characterized by comprising the following steps: the oleum sesami is prepared by decocting raw tung oil at 230 deg.C.
6. The preparation method of the two-dimensional material modified raw lacquer marine anti-corrosive paint as claimed in claim 1, characterized in that: oleophilic Ti in the corrosion inhibitor 3 C 2 The concentration of the nano-sheets is 2-5 mg/ml, and the addition proportion is 1% -10% of the mass of the raw lacquer.
7. The two-dimensional material modified raw lacquer marine anti-corrosive coating prepared by the preparation method of claims 1-6.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115894185A (en) * | 2022-11-30 | 2023-04-04 | 闽江学院 | Artificial urushiol monomer containing long fluorocarbon chain and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110312766A (en) * | 2018-01-25 | 2019-10-08 | 株式会社Lg化学 | Coating composition, film and electromagnetic interference shield composite material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110312766A (en) * | 2018-01-25 | 2019-10-08 | 株式会社Lg化学 | Coating composition, film and electromagnetic interference shield composite material |
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| Title |
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| 万长鑫等: ""石墨烯/生漆复合抗静电涂层的制备与性能"" * |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115894185A (en) * | 2022-11-30 | 2023-04-04 | 闽江学院 | Artificial urushiol monomer containing long fluorocarbon chain and preparation method thereof |
| CN115894185B (en) * | 2022-11-30 | 2024-02-27 | 闽江学院 | Artificial urushiol monomer containing long fluorocarbon chain and preparation method thereof |
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