CN113388323A - Molybdenum disulfide/organic silicon composite modified ultraviolet curing water-based polyurethane acrylate coating, and preparation method and application thereof - Google Patents
Molybdenum disulfide/organic silicon composite modified ultraviolet curing water-based polyurethane acrylate coating, and preparation method and application thereof Download PDFInfo
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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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- 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
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/20—Diluents or solvents
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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
- 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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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K2003/3009—Sulfides
Abstract
The invention belongs to the field of coatings, and particularly relates to a molybdenum disulfide/organic silicon composite modified ultraviolet curing water-based polyurethane acrylate coating, and a preparation method and application thereof, wherein the molybdenum disulfide/organic silicon composite modified ultraviolet curing water-based polyurethane acrylate coating comprises the following components in percentage by mass: (1-5), wherein the component A comprises organosilicon modified polyurethane acrylate water-soluble resin, water, a photoinitiator, a film forming additive, a defoaming agent, a wetting agent, an anti-flash rust agent and a leveling agent, and the component B is dopamine modified molybdenum disulfide. The invention integrates the advantages of the water-based paint and the ultraviolet curing paint, selects water as the reactive diluent, is green and environment-friendly, and simultaneously ensures that the paint has better comprehensive performance. The dopamine modified molybdenum disulfide is selected and combined into the polyurethane acrylate chain segment through a chemical bond, so that the dopamine modified molybdenum disulfide is more uniformly distributed in the coating, and the wear resistance and the corrosion resistance of the coating are improved. The preparation method of the invention has simple process and low cost.
Description
Technical Field
The invention belongs to the field of coatings, and particularly relates to a molybdenum disulfide/organic silicon composite modified ultraviolet curing water-based polyurethane acrylate coating, and a preparation method and application thereof.
Background
As one of the main pillars of the modern industrial society, the metal material is directly related to the life and property safety of people and the industrial and agricultural production and national defense construction. The economic loss caused by the corrosion of metal materials in the mechanical processing of China reaches nearly two trillion yuan each year, and the economic loss caused by the corrosion of metal materials accounts for about 4 percent of the total value of national production. Metal corrosion is a very slow chemical reaction, which means that a chemical or electrochemical multiphase reaction occurs at the interface of the metal, causing the metal to change into an oxidized (ionic) state. This can significantly reduce the mechanical properties of metal materials such as strength, plasticity, toughness, etc., destroy the geometric shape of metal components, increase the abrasion between parts, deteriorate the physical properties of electricity, optics, etc., shorten the service life of equipment, even cause disastrous accidents such as fire, explosion, etc., cause huge economic loss and significant social impact, and it is a very important task to solve the problem of metal corrosion.
The traditional polyurethane anticorrosive paint mainly adopts a solvent type, has high VOC content, and has great harm to the environment and human bodies. The ultraviolet curing water-based polyurethane acrylate coating combines the advantages of water-based coatings and ultraviolet curing coatings, has the advantages of high curing speed, high efficiency, short construction period and low coating equipment cost while being environment-friendly and safe, has better development prospect, makes modification research aiming at improving the mechanical property and the wear-resistant and corrosion-resistant properties of the coating, and further improves the applicability of the ultraviolet curing water-based polyurethane acrylate coating in medium and light metal corrosion protection.
Disclosure of Invention
One of the purposes of the invention is to provide the molybdenum disulfide/organic silicon composite modified ultraviolet curing water-based polyurethane acrylate coating which is excellent in comprehensive performance, low in surface energy and good in wear resistance and is environment-friendly.
The invention also aims to provide a preparation method of the molybdenum disulfide/organic silicon composite modified ultraviolet curing water-based polyurethane acrylate coating, which has simple and convenient preparation process and is easy to adjust.
The invention also aims to provide an application of the molybdenum disulfide/organic silicon composite modified ultraviolet curing water-based polyurethane acrylate coating.
The scheme adopted by the invention for realizing one of the purposes is as follows: the molybdenum disulfide/organic silicon composite modified ultraviolet curing water-based polyurethane acrylate coating comprises the following components in percentage by mass of 100: (1-5), wherein the component A comprises organic silicon modified polyurethane acrylate water-soluble resin, water, a photoinitiator, a film forming aid, a defoaming agent, a wetting agent, an anti-flash rust agent and a leveling agent, the dosage of the photoinitiator is 1-3% of the mass of the organic silicon modified polyurethane acrylate water-soluble resin, the total amount of the film forming aid, the defoaming agent, the wetting agent, the anti-flash rust agent and the leveling agent is 0.5-3% of the mass of the organic silicon modified polyurethane acrylate water-soluble resin, the mass ratio of the film forming aid, the defoaming agent, the wetting agent, the anti-flash rust agent and the leveling agent is 1:0.5:0.5: 0.5: 0.2-0.5, and the mass ratio of the organic silicon modified polyurethane acrylate water-soluble resin to the water is 1: (0.54-2.3), and the component B is dopamine modified molybdenum disulfide.
Preferably, the photoinitiator is any one of 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-acetone and 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide, and the film-forming assistant is at least one of dipropylene glycol methyl ether, dipropylene glycol butyl ether and alcohol ester twelve; the antiscalding agent is Haimass NALZIN FA 179 and/or Haimass NALZIN FA 379; the antifoaming agent is DAPRO-AP-7010 and/or NXZ; the wetting agent is Shanghai Hui Zhongspe 6 and/or Germany Wenkell WT 500; the leveling agent is a German BYK-R-605 and/or BYK-333 organosilicon leveling agent.
The second scheme adopted by the invention for achieving the purpose is as follows: the preparation method of the molybdenum disulfide/organic silicon composite modified ultraviolet light-cured water-based polyurethane acrylate coating comprises the following steps:
a1, preparation of component A: adding the organosilicon modified polyurethane acrylate water-soluble resin into water for high-speed shearing, respectively adding a photoinitiator, a film-forming assistant, a defoaming agent, a wetting agent, an anti-flash rust agent and a flatting agent, and uniformly stirring to obtain a component A;
a2, preparation of component B: adding micron-sized molybdenum disulfide into an organic solvent, uniformly dispersing to obtain a dispersion liquid, centrifuging the dispersion liquid, taking a supernatant, and drying a product obtained after the supernatant is washed to obtain nano-sized molybdenum disulfide; adding nano molybdenum disulfide into a Tris hydrochloric acid buffer solution, adding dopamine hydrochloride, stirring at normal temperature for reaction, washing and centrifuging after the reaction is finished, and drying the product to obtain the dopamine modified molybdenum disulfide.
Preferably, in the step a1, the preparation of the silicone-modified polyurethane acrylate water-soluble resin comprises the following steps:
b1, adding an isocyanate monomer and a catalyst into a solvent, uniformly mixing, heating to 40-50 ℃ under an inert atmosphere, adding polyether polyol, and reacting completely to obtain a prepolymer I;
b2, heating the prepolymer I to 75-85 ℃, sequentially adding organic silicone oil and dimethylolpropionic acid, and reacting completely to obtain a prepolymer II;
b3, cooling the prepolymer II to 55-65 ℃, adding a catalyst, uniformly mixing, adding an acrylate monomer, and reacting completely to obtain a prepolymer III;
and B4, cooling the prepolymer III to 20-40 ℃, adding an alkaline agent for neutralization and salt formation, and finally removing the solvent from the reactant to obtain the organosilicon modified urethane acrylate water-soluble resin.
Preferably, the mass ratio of the isocyanate monomer to the acrylate monomer to the polyether polyol to the solvent is 6:3 (4-6) to (3-6), the amount of the organic silicon oil is 0.5-5% of the mass of the organosilicon modified polyurethane acrylate water-soluble resin, and the amount of the dimethylolpropionic acid is 2-5% of the mass of the organosilicon modified polyurethane acrylate water-soluble resin.
Preferably, in the step B1, the isocyanate monomer is isophorone diisocyanate and/or toluene diisocyanate, and the catalyst is dibutyltin dilaurate and/or triethanolamine; the solvent is dimethyl carbonate and/or tetrahydrofuran; the polyether polyol is at least one of polyethylene glycol, polypropylene oxide glycol and 1, 4-butanediol.
Preferably, in the step B2, the organic silicone oil is hydroxyl silicone oil or amino silicone oil.
Preferably, in the step B3, the acrylate monomer is at least one of n-butyl acrylate, hydroxypropyl methacrylate, hydroxyethyl methacrylate and hydroxyethyl acrylate; the catalyst is dibutyltin dilaurate and/or triethanolamine.
Preferably, in the step A2, the mass ratio of the micron molybdenum disulfide to the organic solvent is (1-8):500, the organic solvent is at least one of N-vinyl pyrrolidone, N-methyl pyrrolidone and N, N-dimethylformamide, the supernatant is sequentially centrifuged by ethanol and distilled water, the pH of a Tris hydrochloric acid buffer solution is 8.5, the concentration is 10mmol/L, the mass fraction ratio of the Tris hydrochloric acid buffer solution, the nanometer molybdenum disulfide and dopamine hydrochloride is 1000 (1-3): 0.5-1, and after the reaction is finished, the product is sequentially centrifuged and washed by ethanol and distilled water.
The scheme adopted by the invention for realizing the third purpose is as follows: the application of the molybdenum disulfide/organic silicon composite modified ultraviolet light-cured waterborne polyurethane acrylate coating in light and medium metal corrosion prevention is disclosed.
The principle of the invention is as follows:
the organic silicon compound is a polymer with Si-O bond as a main chain, has large bond energy and no double bonds, and therefore has better thermal stability and radiation resistance and weather resistance. The main chain of the organic silicon is very flexible, and the intermolecular action force of the organic silicon is much weaker than that of a hydrocarbon compound, so that the coating has the characteristics of hydrophobicity and low surface energy, and Si-O-Si bonds formed in the film forming process improve the compactness and the elastic modulus of a coating film and enhance the water resistance of the coating film. The structure of the molybdenum disulfide is similar to that of graphite and is a hexagonal structure, a molybdenum disulfide single layer has a sandwich structure, a layer of Mo atoms is arranged between two layers of S atoms, and the arrangement of the Mo or S atoms is a graphene-like hexagonal structure, so that the two-dimensional molybdenum disulfide has the characteristics of large specific surface area, good hydrophobic property, high chemical stability, excellent mechanical property, good heat conductivity, good barrier property and the like; the polydopamine is used for carrying out surface modification on the molybdenum disulfide to reduce the agglomeration of the molybdenum disulfide and improve the dispersibility of the molybdenum disulfide in the water-based paint. Therefore, the molybdenum disulfide powder and the organic silicon compound are introduced into the water-based polyurethane acrylate coating system to form a whole with a coating film, so that the internal defects of the coating are reduced, and the wear resistance and the corrosion resistance of the coating are improved; the flaky structure of the molybdenum disulfide can effectively prevent water vapor and air from entering, so that the corrosion resistance of the molybdenum disulfide can be improved, and the applicability of the ultraviolet curing water-based polyurethane acrylate coating in corrosion prevention of light and medium metals is further improved.
The invention has the following advantages and beneficial effects:
1. the invention integrates the advantages of the water-based paint and the ultraviolet curing paint, selects water as the reactive diluent, and has the advantages of green and environment-friendly product and better comprehensive performance.
2. The dopamine modified molybdenum disulfide is selected and combined into the polyurethane acrylate chain segment through a chemical bond, so that the dopamine modified molybdenum disulfide is more uniformly distributed in the coating, and the wear resistance and the corrosion resistance of the coating are improved.
3. The preparation method of the invention has simple process and low cost.
Detailed Description
The following examples are provided to further illustrate the present invention for better understanding, but the present invention is not limited to the following examples.
[ example 1 ]
The molybdenum disulfide/organic silicon composite modified ultraviolet curing WPUA coating in the embodiment comprises the following steps by mass:
1. preparing organosilicon modified urethane acrylate water-soluble resin:
removing water at 110 deg.C for 1 hr for isophorone diisocyanate, butyl acrylate, methyl methacrylate, polyethylene glycol 1000, and dimethyl carbonate, weighing 22.22g isophorone diisocyanate (national group chemical reagent, Inc., AR), and 20g dimethyl carbonate (national group chemical reagent, Inc., A)R), 0.11g of dibutyltin dilaurate are added into a four-mouth flask, and the mixture is stirred and mixed uniformly; the flask was charged with nitrogen while heating to 40 ℃ and 11.2g of polyethylene glycol 400 and 4.85g of polypropylene glycol 400 (AR, national chemical Co., Ltd.) were added to the flask at a constant rate for 1 hour to react for 2 hours to obtain a prepolymer I. Heating the prepolymer I to 75 ℃, dropwise adding 0.25g of hydroxy silicone oil and 1.01g of dimethylolpropionic acid into the flask respectively within 0.5h and 1h in sequence by using a constant-pressure funnel, and reacting for 2.5h to obtain a prepolymer II. And (3) cooling the prepolymer II to 55 ℃, adding 0.1g of dibutyltin dilaurate, stirring and mixing uniformly, and adding 7.6g of hydroxyethyl acrylate into the flask at a constant speed within 1h for reaction for 2h to obtain a prepolymer III. And cooling the prepolymer III to 20 ℃, adding 0.77g of triethylamine to neutralize and salify, and reacting for 30 min. The reaction was rotary evaporated in vacuo at 40 ℃ to remove the solvent and finally 28g H was added2And O, stirring at a high speed to obtain the organic silicon modified polyurethane acrylate water-soluble resin.
2. Preparation of component A:
adding 0.54g of photoinitiator 1-hydroxycyclohexyl phenyl ketone, 0.11g of Haimaichi DAPRO-AP-7010 defoaming agent, 0.11g of Shanghai Hui Zhongzhou SPE 06 wetting agent, 0.11g of Haimaichi NALZIN FA 179 anti-flash rust agent and 0.05g of Germany BYK-R-605 flatting agent into the obtained water-soluble resin, and stirring for 40min at 800rpm in a high-speed stirrer to obtain a component A;
3. preparation of component B:
adding 0.2g of micron-sized molybdenum disulfide into 100 mLN-vinyl pyrrolidone, ultrasonically dispersing for 8h to obtain dispersion liquid, centrifuging the dispersion liquid at 800rpm for 30min, standing and taking supernatant. And centrifuging the supernatant with ethanol and distilled water in sequence, washing for 3 times, and drying the product in a vacuum drying oven at 60 ℃ for 12 hours to obtain the nano molybdenum disulfide. 10mmol/L Tris hydrochloric acid (ARA, Biotechnology, Ltd.) buffer solution with pH of 8.5 is prepared, 0.2g of nano molybdenum disulfide is added into 200mL Tris hydrochloric acid buffer solution, 0.1g of dopamine hydrochloride is added, and the mixture is stirred and reacts for 12 hours at normal temperature. And after the reaction is finished, sequentially centrifuging by using ethanol and distilled water, washing for 3 times, and drying the product in a vacuum drying oven at 60 ℃ for 12 hours to obtain the dopamine modified molybdenum disulfide.
4. Preparing the ultraviolet curing water-based polyurethane acrylate coating containing molybdenum disulfide and organic silicon:
when coating construction is carried out, the component A and the component B are taken according to the mass ratio of 100:1, are stirred and dispersed in a high-speed stirrer at 800rpm, are uniformly stirred and then are coated on a tinplate with the surface roughness of more than Sa2.5 grade by a wire bar coater, and the thickness of a wet film is controlled to be 30um, 60um and 80 um.
The above coating films were tested and the results were as follows:
TABLE 1
[ example 2 ]
The molybdenum disulfide/organic silicon composite modified ultraviolet curing WPUA coating in the embodiment comprises the following steps by mass:
1. preparing organosilicon modified urethane acrylate water-soluble resin:
toluene diisocyanate, 2-hydroxyethyl acrylate, polyethylene glycol 400 and dimethyl carbonate are dehydrated for 1 hour at the temperature of 110 ℃, 17.46g of toluene diisocyanate, 12.5g of dimethyl carbonate, 5g of butyl acetate and 0.12g of dibutyltin dilaurate are weighed and added into a four-neck flask, and the materials are stirred and mixed uniformly; the flask is filled with nitrogen, the temperature is raised to 50 ℃, 17.6g of polyethylene glycol 400 is added into the flask at a constant speed within 1 hour to react for 2 hours, and prepolymer I is obtained. Heating the prepolymer I to 85 ℃, dropwise adding 2.5g of hydroxy silicone oil and 1.54g of dimethylolpropionic acid into the flask respectively within 0.5h and 1h in sequence by using a constant-pressure funnel, and reacting for 2.5h to obtain a prepolymer II. And cooling the prepolymer II to 65 ℃, adding 0.09g of dibutyltin dilaurate, stirring and mixing uniformly, and adding 5.18g of hydroxyethyl acrylate into the flask at a constant speed within 1h for reaction for 2h to obtain a prepolymer III. And reducing the temperature of the prepolymer III to 40 ℃, adding 1.28g of triethylamine to neutralize and form salt, and reacting for 30 min. The reaction mass was rotary evaporated in vacuo at 40 ℃ to remove the solvent and finally 50g H was added2O is stirred at high speed to obtain the organosilicon modified urethane acrylate water-solubleAnd (3) a sex resin.
2. Preparation of component A:
to the obtained water-soluble resin were added 1.52g of 2-hydroxy-2-methyl-1-phenyl-1-propanone as a photoinitiator, 0.6g of a Haimax DAPRO-AP-7010 antifoaming agent, 0.6g of a German Unikeal WT 500 wetting agent, 1.2g of a Haimax NALZIN FA 379 antiscratch agent, and 0.6g of a German BYK-R-605 leveling agent, and the mixture was stirred in a high-speed stirrer at 1000rpm for 30 minutes to obtain a component A.
3. Preparation of component B:
adding 0.2g micron-sized molybdenum disulfide into 12.5mL of N-N dimethylformamide, performing ultrasonic dispersion for 10h to obtain a dispersion liquid, centrifuging the dispersion liquid at 600rpm for 30min, standing and taking a supernatant. And centrifuging the supernatant with ethanol and distilled water in sequence, washing for 3 times, and drying the product in a vacuum drying oven at 60 ℃ for 12 hours to obtain the nano molybdenum disulfide. Preparing 10mmol/L Tris hydrochloric acid buffer solution with the pH value of 8.5, adding 0.2g of nano molybdenum disulfide into 67mL Tris hydrochloric acid buffer solution, adding 0.13g of dopamine hydrochloride, and stirring and reacting for 12 hours at normal temperature. And after the reaction is finished, sequentially centrifuging by using ethanol and distilled water, washing for 3 times, and drying the product in a vacuum drying oven at 60 ℃ for 12 hours to obtain the dopamine modified molybdenum disulfide.
4. Preparing the ultraviolet curing water-based polyurethane acrylate coating containing molybdenum disulfide and organic silicon:
when coating construction is carried out, the component A and the component B are taken according to the mass ratio of 20:1, are stirred and dispersed in a high-speed stirrer at 800rpm, are uniformly stirred and then are coated on a tinplate with the surface roughness of more than Sa2.5 grade by a wire bar coater, and the wet film thickness is controlled to be 30um, 60um and 80 um.
The above coating films were tested and the results were as follows:
TABLE 2
[ example 3 ]
The molybdenum disulfide/organic silicon composite modified ultraviolet curing WPUA coating in the embodiment comprises the following steps by mass:
1. preparing organosilicon modified urethane acrylate water-soluble resin:
toluene diisocyanate, pentaerythritol-triacrylate, polyoxyethylene glycol and 1, 4-butanediol are dehydrated for 1h at the temperature of 110 ℃, 17.54g of toluene diisocyanate (AR), 20g of tetrahydrofuran (AR) and 0.15g of triethanolamine are weighed and added into a four-neck flask, and the mixture is stirred and mixed uniformly; a flask was charged with nitrogen gas while heating to 45 ℃ and 8.25g of polyoxyethylene glycol and 4.85g of 1, 4-butanediol (national chemical group, chemical Co., Ltd., AR) were added to the flask at a constant rate over 1 hour to react for 2 hours to obtain prepolymer I. Heating the prepolymer I to 80 ℃, dropwise adding 2.0g of hydroxy silicone oil and 1.65g of dimethylolpropionic acid into the flask respectively within 0.5h and 1h in sequence by using a constant-pressure funnel, and reacting for 2.5h to obtain a prepolymer II. And cooling the prepolymer II to 60 ℃, adding 0.15 of triethanolamine, stirring and mixing uniformly, and adding 10.36g of pentaerythritol-triacrylate into the flask at a constant speed within 1h for reaction for 2h to obtain a prepolymer III. And reducing the temperature of the prepolymer III to 40 ℃, adding 1.57g of triethylamine to neutralize and form salt, and reacting for 30 min. The reaction mass was vacuum rotary evaporated at 30 ℃ to remove the solvent and finally 50g H was added2And O, stirring at a high speed to obtain the organic silicon modified polyurethane acrylate water-soluble resin.
2. Preparation of component A:
adding 2.04g of photoinitiator 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, 2.0g of dipropylene glycol methyl ether film-forming aid, 1.0g of a medium NXZ defoaming agent, 1.0g of Shanghai Huizhong SPE 06 wetting agent, 1.0g of Haimazi NALZIN FA 179 anti-flash rust agent and 0.4g of Germany BYK-333 organic silicon leveling agent into the obtained water-soluble resin, and stirring for 40min at 1000rpm in a high-speed stirrer to obtain a component A;
3. preparation of component B:
adding 0.2g of micron-sized molybdenum disulfide into 30mL of N-methyl pyrrolidone, performing ultrasonic dispersion for 8h to obtain a dispersion liquid, centrifuging the dispersion liquid at 800rpm for 30min, standing and taking a supernatant. And centrifuging the supernatant with ethanol and distilled water in sequence, washing for 3 times, and drying the product in a vacuum drying oven at 60 ℃ for 12 hours to obtain the nano molybdenum disulfide. 10mmol/L Tris hydrochloric acid (ARA, Biotechnology, Ltd.) buffer solution with pH of 8.5 is prepared, 0.2g of nano molybdenum disulfide is added into 200mL Tris hydrochloric acid buffer solution, 0.1g of dopamine hydrochloride is added, and the mixture is stirred and reacts for 12 hours at normal temperature. And after the reaction is finished, sequentially centrifuging by using ethanol and distilled water, washing for 3 times, and drying the product in a vacuum drying oven at 60 ℃ for 12 hours to obtain the dopamine modified molybdenum disulfide.
4. Preparing the ultraviolet curing water-based polyurethane acrylate coating containing molybdenum disulfide and organic silicon:
when coating construction is carried out, the component A and the component B are taken according to the mass ratio of 100:3, are stirred and dispersed in a high-speed stirrer at 800rpm, are uniformly stirred and then are coated on a tinplate with the surface roughness of more than Sa2.5 grade by a wire bar coater, and the thickness of a wet film is controlled to be 30um, 60um and 80 um.
The above coating films were tested and the results were as follows:
TABLE 3
[ example 4 ]
The molybdenum disulfide/organic silicon composite modified ultraviolet curing WPUA coating in the embodiment comprises the following steps by mass:
1. preparing organosilicon modified urethane acrylate water-soluble resin:
adding 22.22g of isophorone diisocyanate (national medicine group chemical reagent company, Inc., AR), 20g of dimethyl carbonate (national medicine group chemical reagent company, Inc., AR) and 0.11g of dibutyltin dilaurate into a four-mouth flask, and uniformly stirring and mixing; charging nitrogen gas into flask, heating to 45 deg.C, adding 11.2g polyethylene glycol 400 and 4.85g polypropylene glycol 400 (AR) into flask at constant speed within 1h, and reacting for 2hTo obtain a prepolymer I. Heating the prepolymer I to 80 ℃, dropwise adding 1.0g of hydroxy silicone oil and 2.65g of dimethylolpropionic acid into the flask respectively within 0.5h and 1h in sequence by using a constant-pressure funnel, and reacting for 2.5h to obtain a prepolymer II. And cooling the prepolymer II to 60 ℃, adding 0.1g of dibutyltin dilaurate, stirring and mixing uniformly, mixing 6.96g of hydroxyethyl acrylate and 4.16g of hydroxyethyl methacrylate within 1 hour, adding into a flask at a constant speed, and reacting for 2 hours to obtain a prepolymer III. And reducing the temperature of the prepolymer III to 40 ℃, adding 2.14g of triethylamine to neutralize and form salt, and reacting for 30 min. The reaction mass was rotary evaporated in vacuo at 40 ℃ to remove the solvent and finally 45g H was added2And O, stirring at a high speed to obtain the organic silicon modified polyurethane acrylate water-soluble resin.
2. Preparation of component A:
adding 1.54g of photoinitiator 1-hydroxycyclohexyl phenyl ketone, 0.8g of Haimaisi DAPRO-AP-7010 antifoaming agent and 0.8g of Shanghai Huizhong SPE 06 wetting agent into the obtained water-soluble resin, and stirring at 800rpm for 40min to obtain a component A;
3. preparation of component B:
adding 0.2g of micron-sized molybdenum disulfide into 25ml of LN-vinyl pyrrolidone, ultrasonically dispersing for 8 hours to obtain dispersion liquid, centrifuging the dispersion liquid at 800rpm for 30min, standing and taking supernatant. And centrifuging the supernatant with ethanol and distilled water in sequence, washing for 3 times, and drying the product in a vacuum drying oven at 60 ℃ for 12 hours to obtain the nano molybdenum disulfide. 10mmol/L Tris hydrochloric acid (ARA, Biotechnology, Ltd.) buffer solution with pH of 8.5 is prepared, 0.2g of nano molybdenum disulfide is added into 200mL Tris hydrochloric acid buffer solution, 0.1g of dopamine hydrochloride is added, and the mixture is stirred and reacts for 12 hours at normal temperature. And after the reaction is finished, sequentially centrifuging by using ethanol and distilled water, washing for 3 times, and drying the product in a vacuum drying oven at 60 ℃ for 12 hours to obtain the dopamine modified molybdenum disulfide.
4. Preparing the ultraviolet curing water-based polyurethane acrylate coating containing molybdenum disulfide and organic silicon:
when coating construction is carried out, the component A and the component B are taken according to the mass ratio of 100:3, are stirred and dispersed in a high-speed stirrer at 800rpm, are uniformly stirred and then are coated on a tinplate with the surface roughness of more than Sa2.5 grade by a wire bar coater, and the thickness of a wet film is controlled to be 30um, 60um and 80 um.
The above coating films were tested and the results were as follows:
TABLE 1
From the above examples, it can be seen that the molybdenum disulfide/organosilicon composite modified ultraviolet-curable waterborne polyurethane acrylate coating prepared by the invention has excellent mechanical properties, meets the basic requirements of light and medium metal corrosion resistance on the coating, can be applied to the aspects of plastics, motors, building coatings, pipelines and the like, and has lower surface energy, so that pollution particles are difficult to attach to the surface of a coating film, and are easy to remove after adsorption, and the shielding effect of the coating layer is kept for longer time effectiveness.
While the foregoing is directed to the preferred embodiment of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.
Claims (10)
1. The molybdenum disulfide/organic silicon composite modified ultraviolet curing water-based polyurethane acrylate coating is characterized in that: comprises the following components in percentage by mass of 100: (1-5), wherein the component A comprises organosilicon modified polyurethane acrylate water-soluble resin, water, a photoinitiator, a film forming aid, a defoaming agent, a wetting agent, an anti-flash rust agent and a leveling agent, the dosage of the photoinitiator is 1-3% of the mass of the organosilicon modified polyurethane acrylate water-soluble resin, the total amount of the film forming aid, the defoaming agent, the wetting agent, the anti-flash rust agent and the leveling agent is 0.5-3% of the mass of the organosilicon modified polyurethane acrylate water-soluble resin, the mass ratio of the film forming aid, the defoaming agent, the wetting agent, the anti-flash rust agent and the leveling agent is 1:0.5:0.5: 0.5: 0.2-0.5, and the mass ratio of the organosilicon modified polyurethane acrylate water-soluble resin to the water is 1: (0.54-2.3), and the component B is dopamine modified molybdenum disulfide.
2. The molybdenum disulfide/organosilicon composite modified ultraviolet-curable aqueous polyurethane acrylate coating according to claim 1, wherein: the photoinitiator is any one of 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-acetone and 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide, and the film-forming auxiliary agent is at least one of dipropylene glycol methyl ether, dipropylene glycol butyl ether and alcohol ester twelve; the antiscalding agent is Haimass NALZIN FA 179 and/or Haimass NALZIN FA 379; the antifoaming agent is DAPRO-AP-7010 and/or NXZ; the wetting agent is Shanghai Hui Zhongspe 6 and/or Germany Wenkell WT 500; the leveling agent is a German BYK-R-605 and/or BYK-333 organosilicon leveling agent.
3. The preparation method of the molybdenum disulfide/organosilicon composite modified ultraviolet-curing water-based polyurethane acrylate coating as claimed in claim 1 or 2, characterized by comprising the following steps:
a1, preparation of component A: adding the organosilicon modified polyurethane acrylate water-soluble resin into water for high-speed shearing, then respectively adding a photoinitiator, a film-forming assistant, a defoaming agent, a wetting agent, an anti-flash rust agent and a flatting agent, and uniformly stirring to obtain a component A;
a2, preparation of component B: adding micron-sized molybdenum disulfide into an organic solvent, uniformly dispersing to obtain a dispersion liquid, centrifuging the dispersion liquid, taking a supernatant, and drying a product obtained after the supernatant is washed to obtain nano-sized molybdenum disulfide; adding nano molybdenum disulfide into a Tris hydrochloric acid buffer solution, adding dopamine hydrochloride, stirring at normal temperature for reaction, washing and centrifuging after the reaction is finished, and drying the product to obtain the dopamine modified molybdenum disulfide.
4. The preparation method of the molybdenum disulfide/organosilicon composite modified ultraviolet-curing water-based polyurethane acrylate coating according to claim 3, wherein the preparation method comprises the following steps: in the step A1, the preparation of the organosilicon modified urethane acrylate water-soluble resin comprises the following steps:
b1, adding an isocyanate monomer and a catalyst into a solvent, uniformly mixing, heating to 40-50 ℃ under an inert atmosphere, adding polyether polyol, and reacting completely to obtain a prepolymer I;
b2, heating the prepolymer I to 75-85 ℃, sequentially adding organic silicone oil and dimethylolpropionic acid, and reacting completely to obtain a prepolymer II;
b3, cooling the prepolymer II to 55-65 ℃, adding a catalyst, uniformly mixing, adding an acrylate monomer, and reacting completely to obtain a prepolymer III;
and B4, cooling the prepolymer III to 20-40 ℃, adding an alkaline agent for neutralization and salt formation, and finally removing the solvent from the reactant to obtain the organosilicon modified urethane acrylate water-soluble resin.
5. The preparation method of the molybdenum disulfide/organosilicon composite modified ultraviolet-curing water-based polyurethane acrylate coating according to claim 4, wherein the preparation method comprises the following steps: the mass ratio of the isocyanate monomer to the acrylate monomer to the polyether polyol to the solvent is 6:3 (4-6) to (3-6), the dosage of the organic silicon oil is 0.5-5% of the mass of the organic silicon modified polyurethane acrylate water-soluble resin, and the dosage of the dimethylolpropionic acid is 2-5% of the mass of the organic silicon modified polyurethane acrylate water-soluble resin.
6. The preparation method of the molybdenum disulfide/organosilicon composite modified ultraviolet-curing water-based polyurethane acrylate coating according to claim 4, wherein the preparation method comprises the following steps: in the step B1, the isocyanate monomer is isophorone diisocyanate and/or toluene diisocyanate, and the catalyst is dibutyltin dilaurate and/or triethanolamine; the solvent is dimethyl carbonate and/or tetrahydrofuran; the polyether polyol is at least one of polyethylene glycol, polypropylene oxide glycol and 1, 4-butanediol.
7. The preparation method of the molybdenum disulfide/organosilicon composite modified ultraviolet-curing water-based polyurethane acrylate coating according to claim 4, wherein the preparation method comprises the following steps: in the step B2, the organic silicone oil is hydroxyl silicone oil or amino silicone oil.
8. The preparation method of the molybdenum disulfide/organosilicon composite modified ultraviolet-curing water-based polyurethane acrylate coating according to claim 4, wherein the preparation method comprises the following steps: in the step B3, the acrylate monomer is at least one of n-butyl acrylate, hydroxypropyl methacrylate, hydroxyethyl methacrylate and hydroxyethyl acrylate; the catalyst is dibutyltin dilaurate and/or triethanolamine.
9. The preparation method of the molybdenum disulfide/organosilicon composite modified ultraviolet-curing water-based polyurethane acrylate coating according to claim 3, wherein the preparation method comprises the following steps: in the step A2, the mass ratio of the micron molybdenum disulfide to the organic solvent is (1-8):500, the organic solvent is at least one of N-vinyl pyrrolidone, N-methyl pyrrolidone and N, N-dimethylformamide, the supernatant is sequentially centrifuged by ethanol and distilled water, the pH of a Tris hydrochloric acid buffer solution is 8.5, the concentration of the Tris hydrochloric acid buffer solution is 10mmol/L, the mass fraction ratio of the Tris hydrochloric acid buffer solution, the nanometer molybdenum disulfide and dopamine hydrochloride is 1000 (1-3): 0.5-1, and after the reaction is finished, the product is sequentially centrifuged and washed by ethanol and distilled water.
10. The application of the molybdenum disulfide/organosilicon composite modified ultraviolet curing aqueous polyurethane acrylate coating as claimed in claim 1 or 2 or the molybdenum disulfide/organosilicon composite modified ultraviolet curing aqueous polyurethane acrylate coating prepared by the preparation method as claimed in any one of claims 3 to 9 in light and medium metal corrosion prevention.
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