MXene-based self-migration reinforced hardening medium-corrosion absorbing UV coating and preparation method thereof

Abstract

The application provides a MXene-based self-migration reinforced strong curing medium corrosion-resistant wave-absorbing UV paint, which comprises 35-45 parts of an acrylate resin oligomer, 45-55 parts of an acrylate monomer, 0.5-10 parts of MXene, 10-15 parts of graphene, and 0.5-1.8 parts of an additive; the MXene is organosilicon-modified MXene; a preparation method comprises the following steps: mixing MXene and graphene with water to form a dispersion liquid; dividing the acrylate monomer into three equal parts, ultrasonically mixing and dissolving the nanodispersion liquid and the acrylate monomer I to obtain a mixture I; ultrasonically mixing and dissolving the additive and the acrylate monomer II to obtain a mixture II; ultrasonically mixing and dissolving the acrylate resin oligomer and the acrylate monomer III to obtain a mixture III; water-bath heating the three mixtures to complete dissolution, filtering out bubbles and impurities, and obtaining a composite resin paint; and the paint prepared by the application has excellent corrosion resistance, self-repairing ability, durability, stability and wave-absorbing performance, and the curing time is reduced and the curing efficiency is high.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of organic chemical industry, and particularly relates to a self-migration strong solidification moderate corrosion absorption UV coating based on MXene and a preparation method thereof. BACKGROUND

[0002] MXene is a two-dimensional material composed of several atomic layers of transition metal carbide, nitride or carbonitride. It has high specific surface area, high mechanical strength, excellent thermal and electrical conductivity, etc., which makes it show good application prospect in the field of metal protection.

[0003] UV-curable coating is mainly composed of photosensitive resin, active diluent, photoinitiator and various additives. The curing process is actually a polymerization and crosslinking process. When UV light irradiates on the UV-curable coating, the photoinitiator first absorbs energy and is excited to form active centers, which interact with the unsaturated carbon-carbon double bonds in the system, open the double bonds, and undergo chain polymerization reaction, thereby crosslinking into a film. And MXene, like other two-dimensional materials, due to the interaction between adjacent nanosheets and the existence of hydrogen bonds, MXene is prone to irreversible self-accumulation and aggregation, which reduces the exposed active surface area and slows down ion transport / diffusion, thus it may be more likely to promote the occurrence of curing reaction. Therefore, the UV coating prepared by using MXene has the disadvantages of low UV curing efficiency, inability to thick coating, and low corrosion resistance. Therefore, the present application proposes a self-migration strong solidification moderate corrosion absorption UV coating based on MXene and a preparation method thereof to solve the above problems. SUMMARY

[0004] The purpose of the present application is to overcome the shortcomings of the prior art, based on the research of UV-curable coating, to explore and optimize the formula of UV-curable coating, to provide a self-migration strong solidification moderate corrosion absorption UV coating based on MXene and a preparation method thereof, to solve the conflict between light curing and light aging caused by the mutual influence of each component of the coating, and to greatly improve the corrosion and wave absorption performance of the coating.

[0005] The application adopts the following technical scheme:

[0006] (I) The present application provides a self-migration strong solidification moderate corrosion absorption UV coating based on MXene, which comprises: 35-45 parts of acrylate resin oligomer, 45-55 parts of acrylate monomer, 0.5-10 parts of MXene, 10-15 parts of graphene, and 0.5-1.8 parts of additives.

[0007] Further, the acrylate resin oligomer is urethane acrylate; and the acrylate monomer is methyl methacrylate.

[0008] Further, the auxiliary agent includes a wetting dispersant, an antifoaming agent, and a thickening agent, and the mass ratio is 10:(2-5):(3-6).

[0009] Further, the wetting dispersant is polyvinyl alcohol, the antifoaming agent is silicone oil, and the thickening agent is polyurethane.

[0010] Further, the preparation method of the MXene includes the following steps: (1) weighing LiF and adding it into a polytetrafluoroethylene container, adding HCl solution while stirring until complete dissolution to obtain a mixed solution; (2) placing Ti3AlC2 in the mixed solution, sealing the container opening with a plastic wrap, using a syringe to pierce a plurality of small holes in the plastic wrap, and placing the container in a water bath, and obtaining a suspension after reaction; (3) filtering the suspension, adding the lower precipitate into HCl solution until complete dissolution, and magnetically stirring at room temperature to obtain a mixed solution; (4) mixing the mixed solution of step (3) with acrylate-modified polysiloxane, treating by ultrasonic wave to form a uniform dispersion, centrifuging the dispersion and washing the precipitate, and freeze-drying the precipitate to obtain a MXene material.

[0011] Further, the mass ratio of LiF, Ti3AlC2 and acrylate-modified polysiloxane is 1:1:0.5.

[0012] Further, the preparation method of the acrylate-modified polysiloxane is as follows: adding acrylate and low-hydrogen-containing silicone oil into a four-necked flask, slowly heating to 100°C, adding a solution of Karstedt catalyst in isopropanol, controlling the temperature at 100-110°C, and after the reaction is completed, removing the low-boiling substances under reduced pressure to obtain acrylate-modified polysiloxane.

[0013] Further, the acrylate monomer is selected from one or a mixture of several of n-butyl methacrylate, 2-hydroxyethyl acrylate, 3-hydroxyethyl acrylate, trifluoroethyl methacrylate, acrylamide, and acrylonitrile; and the low-hydrogen-containing silicone oil is a silicone oil with a hydrogen content of 0.1%-0.2%.

[0014] Further, the molar ratio of acrylate to low-hydrogen-containing silicone oil is 1.1:1; the mass fraction of Karstedt catalyst in the isopropanol solution of Karstedt catalyst is 1%; the mass of the added isopropanol solution of Karstedt catalyst accounts for 1.5% of the total mass of the reactants; and the reaction time is 6h.

[0015] Further, in step (1), the concentration of the HCl solution is 9mol·L -1; in the step (2), the temperature of the water bath is adjusted to 45 DEG C, the rotation speed of the rotor is adjusted to 400 rpm, the reaction time is 24 hours, and the suspension is obtained after standing for 2 hours after the reaction; in the step (3), the concentration of the HCl solution is 11 mol / L -1 ; the rotation speed of the magnetic stirring is 200 rpm, and the stirring time is 30 minutes; in the step (4), the centrifugation is performed twice, the rotation speed of the centrifuge is 8000 rpm, and the centrifugation time is 10 minutes each time; after the centrifugation, the filtration is performed, the precipitate is washed with deionized water, the centrifugation is performed, the above steps are repeated three times, and the MXene material is obtained after the freeze-drying.

[0016] (II) The application further provides a preparation method of the self-migration strong solidification moderate corrosion prevention wave-absorbing UV coating based on MXene.

[0017] S1, dispersing MXene and graphene in water, and performing ultrasonic treatment by using an ultrasonic instrument to obtain a uniform nanodispersion liquid;

[0018] S2, dividing acrylic ester monomers into three equal parts by weight, and numbering them as acrylic ester monomer I, acrylic ester monomer II and acrylic ester monomer III;

[0019] S3, ultrasonically mixing the nanodispersion liquid and the acrylic ester monomer I to make them completely dissolved, obtaining a mixture I; ultrasonically mixing the auxiliary agent and the acrylic ester monomer II to make them completely dissolved, obtaining a mixture II; and ultrasonically mixing the acrylic ester resin oligomer and the acrylic ester monomer III to make them completely dissolved, obtaining a mixture III;

[0020] S4, mixing the mixture I, the mixture II and the mixture III, and heating in a water bath until completely dissolved, and filtering out bubbles and impurities to obtain a composite resin coating.

[0021] Further, in the step S1, the ultrasonic treatment time is 30 minutes; and in the step S4, the water bath heating temperature is 60-70 DEG C.

[0022] The application has the following beneficial effects:

[0023] (1) The self-migration strong solidification moderate corrosion prevention wave-absorbing UV coating based on MXene has excellent corrosion prevention performance and self-repairing ability, and can use ultraviolet light to initiate the migration and crosslinking of free radicals or cations in the coating, thereby improving the durability and stability of the coating.

[0024] (2) The MXene-based self-migration strong curing medium corrosion absorption UV paint provided by the application utilizes silicone-modified MXene to form a structure with one end being a leveling agent and the other end being MXene, and after rapid leveling, curing starts; on one hand, the modified MXene is helpful to leveling of the paint film and migrates to the surface of the paint film in the leveling process, so that the MXene can act with ultraviolet light to a greater extent; on the other hand, the modified MXene migrated to the surface is anchored on the surface of the paint film together with the resin, which not only improves the strength of the surface paint film, saves time for multi-pass spraying and improves the curing efficiency, but also helps to promote curing of the underlying paint film and improve the thickness of the paint film.

[0025] (3) The MXene-based self-migration strong curing medium corrosion absorption UV paint provided by the application introduces graphene in the preparation of the paint, and the graphene and MXene are both dielectric loss to form absorption, and the absorption performance of the graphene will be greatly improved after being compounded with magnetic fillers. DETAILED DESCRIPTION

[0026] To make the purpose, technical solutions and advantages of the embodiments of the application clearer, the technical solutions in the embodiments of the application will be described clearly and completely below in combination with the embodiments of the application. Obviously, the described embodiments are part of the embodiments of the application, rather than all the embodiments of the application. Based on the embodiments in the application, all other embodiments obtained by those skilled in the art without creative work fall within the protection scope of the application.

[0027] Embodiment 1

[0028] The embodiment of the application provides a preparation method of MXene, comprising the following steps:

[0029] (1) LiF is weighed and added into a polytetrafluoroethylene beaker, 9 mol·L -1 of HCl solution is added while stirring until complete dissolution, to obtain a mixed solution.

[0030] (2) Ti3AlC2 is placed in the mixed solution, the beaker mouth is covered with a preservative film, a plurality of small holes are punched on the preservative film by using a syringe, the beaker is placed in a water bath, the temperature of the water bath is adjusted to 45 DEG C, the rotor speed is adjusted to 400 rpm, the reaction time is 24 hours, and after the reaction, the beaker is placed for 2 hours, to obtain a suspension.

[0031] (3) The suspension is filtered, the lower precipitate is taken and added into 11 mol·L -1 of HCl solution until complete dissolution, and magnetic stirring is performed at a speed of 200 rpm at room temperature for 30 min, to obtain a mixed solution.

[0032] (4) In a four-necked flask, 1.1 mol of acrylate (n-butyl methacrylate) and 1 mol of low hydrogen-containing silicone oil (silicone oil with a hydrogen content of 0.2%) were added, and the temperature was slowly raised to 100°C. 1.5% of the total mass of the reaction product isopropanol solution of the Karstedt catalyst (the mass fraction of the Karstedt catalyst in the isopropanol solution is 1%). The temperature was controlled at 100-110°C, and the reaction was carried out for 6h. After that, the low-boiling substances were removed by vacuum distillation to obtain acrylate-modified polysiloxane.

[0033] (5) The mixed solution of step (3) and the acrylate-modified polysiloxane prepared in step (4) were mixed by ultrasonic treatment to form a uniform dispersion liquid. The dispersion liquid was centrifuged twice, with a centrifuge speed of 8000rmp and a centrifugation time of 10min each time. After centrifugation, the precipitate was filtered and washed with deionized water, and the precipitate was centrifuged and washed three times. Finally, the obtained MXene was freeze-dried to obtain the MXene material.

[0034] In this embodiment, the mass ratio of LiF, Ti3AlC2 and acrylate-modified polysiloxane is 1:1:0.5.

[0035] Example 2

[0036] The UV coating provided by the embodiment of the present application is based on MXene and has self-migration, strong curing, moderate corrosion resistance and wave absorption. The UV coating comprises 35 parts of dimethyl acrylate urethane, 45 parts of methyl methacrylate, 10 parts of MXene prepared in Example 1, 15 parts of graphene, 0.5 parts of polyvinyl alcohol, 0.25 parts of silicone oil and 0.2 parts of polyurethane.

[0037] The preparation method of the UV coating comprises the following steps:

[0038] S1, dispersing MXene and graphene in water and ultrasonically treating with an ultrasonic instrument for 30 minutes to obtain a uniform nanodispersion liquid.

[0039] S2, dividing 45 parts of methyl methacrylate into three equal parts by weight, and numbering them as acrylate monomer I, acrylate monomer II and acrylate monomer III.

[0040] S3, ultrasonically mixing the nanodispersion liquid with the acrylate monomer I to make it completely dissolved, to obtain mixture I; ultrasonically mixing the adjuvants (polyvinyl alcohol, silicone oil and polyurethane) with the acrylate monomer II to make it completely dissolved, to obtain mixture II; and ultrasonically mixing the acrylate resin oligomer with the acrylate monomer III to make it completely dissolved, to obtain mixture III.

[0041] S4, mix mixture I, mixture II and mixture III, heat in a water bath to complete dissolution at 60-70 DEG C, filter out bubbles and impurities, and obtain a composite resin coating.

[0042] S5, use a wire bar coater to uniformly coat the composite resin on a glass sheet, press tightly with a clean quartz glass sheet, and obtain the MXene-based self-migration strong solidification medium corrosion absorption UV coating by curing at room temperature.

[0043] Example 3

[0044] The MXene-based self-migration strong solidification medium corrosion absorption UV coating provided by the embodiment of the application comprises: 45 parts of dimethyl acrylate urethane, 55 parts of methyl methacrylate, 10 parts of MXene prepared in Example 1, 15 parts of graphene, 0.7 parts of polyvinyl alcohol, 0.26 parts of silicone oil and 0.31 parts of polyurethane.

[0045] The preparation method of the UV coating comprises the following steps:

[0046] S1, disperse MXene and graphene in water, and use an ultrasonic instrument to ultrasonically treat for 30 minutes to obtain a uniform nanodispersion.

[0047] S2, divide 55 parts of methyl methacrylate into three equal parts by weight, and number them as acrylic ester monomer I, acrylic ester monomer II and acrylic ester monomer III.

[0048] S3, ultrasonically mix the nanodispersion with the acrylic ester monomer I to completely dissolve it, and obtain mixture I; ultrasonically mix the additives (polyvinyl alcohol, silicone oil and polyurethane) with the acrylic ester monomer II to completely dissolve it, and obtain mixture II; ultrasonically mix the acrylic ester resin oligomer with the acrylic ester monomer III to completely dissolve it, and obtain mixture III.

[0049] S4, mix mixture I, mixture II and mixture III, heat in a water bath to complete dissolution at 60-70 DEG C, filter out bubbles and impurities, and obtain a composite resin coating.

[0050] S5, use a wire bar coater to uniformly coat the composite resin on a glass sheet, press tightly with a clean quartz glass sheet, and obtain the MXene-based self-migration strong solidification medium corrosion absorption UV coating by curing at room temperature.

[0051] Example 4

[0052] The embodiment of the present application provides a self-migration strong solidification moderate anti-corrosion wave-absorbing UV coating based on MXene, the coating comprises: dimethyl acrylate urethane 45 parts, methyl methacrylate 45 parts, MXene prepared in example 1 10 parts, graphene 10 parts, polyvinyl alcohol 0.8 parts, silicone oil 0.28 parts, and polyurethane 0.32 parts.

[0053] The preparation method of the UV coating comprises the following steps:

[0054] S1, dispersing MXene and graphene in water, and treating with an ultrasonic instrument for 30 minutes to obtain a uniform nanodispersion.

[0055] S2, 45 parts of methyl methacrylate are divided into three equal parts, numbered as acrylate monomer I, acrylate monomer II and acrylate monomer III.

[0056] S3, the nanodispersion is ultrasonically mixed with the acrylate monomer I to make it completely dissolved, to obtain mixture I; the adjuvant (polyvinyl alcohol, silicone oil and polyurethane) is ultrasonically mixed with the acrylate monomer II to make it completely dissolved, to obtain mixture II; the acrylate resin oligomer is ultrasonically mixed with the acrylate monomer III to make it completely dissolved, to obtain mixture III.

[0057] S4, the mixture I, the mixture II and the mixture III are mixed, and a water bath is heated to complete dissolution at 60-70 DEG C by using a water bath kettle, and bubbles and impurities are filtered out, to obtain a composite resin coating.

[0058] S5, the composite resin is uniformly coated on a glass sheet by using a wire bar applicator, and then compressed by using a clean quartz glass sheet, and cured at room temperature, to obtain the self-migration strong solidification moderate anti-corrosion wave-absorbing UV coating based on MXene.

[0059] Example 5

[0060] The embodiment of the present application provides a self-migration strong solidification moderate anti-corrosion wave-absorbing UV coating based on MXene, the coating comprises: dimethyl acrylate urethane 35 parts, methyl methacrylate 45 parts, MXene prepared in example 1 0.5 parts, graphene 15 parts, polyvinyl alcohol 0.6 parts, silicone oil 0.23 parts, and polyurethane 0.3 parts.

[0061] The preparation method of the UV coating comprises the following steps:

[0062] S1, dispersing MXene and graphene in water, and treating with an ultrasonic instrument for 30 minutes to obtain a uniform nanodispersion.

[0063] S2, 45 parts of methyl methacrylate are divided into three equal parts by weight, numbered as acrylic ester monomer I, acrylic ester monomer II, and acrylic ester monomer III.

[0064] S3, the nanodispersion is mixed with acrylic ester monomer I by ultrasonic mixing to make it completely dissolved, obtaining mixture I; the adjuvants (polyvinyl alcohol, silicone oil and polyurethane) are mixed with acrylic ester monomer II by ultrasonic mixing to make it completely dissolved, obtaining mixture II; the acrylic ester resin oligomer is mixed with acrylic ester monomer III by ultrasonic mixing to make it completely dissolved, obtaining mixture III.

[0065] S4, mixture I, mixture II and mixture III are mixed, and heated in a water bath at 60-70℃ until completely dissolved, and filtered to remove bubbles and impurities, obtaining a composite resin coating.

[0066] S5, the composite resin is uniformly coated on the glass sheet with a wire bar applicator, and then pressed with a clean quartz glass sheet, and cured at room temperature, obtaining the self-migration strong curing medium corrosion resistant wave-absorbing UV coating based on MXene.

[0067] Comparative Example 1

[0068] The preparation method of this comparative example is the same as that of Example 2, except that Comparative Example 1 does not add MXene material.

[0069] Comparative Example 2

[0070] The preparation method of this comparative example is the same as that of Example 2, except that Comparative Example 2 does not add graphene material.

[0071] Performance test:

[0072] Examples 2-5 and Comparative Examples 1-2 are tested for performance.

[0073] The measured parameters are corrosion resistance, wave-absorbing performance and curing time.

[0074] (1) Corrosion resistance

[0075] Examples 2-5 and Comparative Examples 1-2 are coated on aluminum alloy substrates, then sprayed with NaCl solution (mass fraction 5%, pH 6.5-7.2) at 35℃ for several hours, then placed at 40℃ and 80% humidity for 2500 hours.

[0076] (2) Wave-absorbing performance

[0077] The wave-absorbing performance of the coating is tested by the coaxial ring method, and the test standard is GB / T-35680-2017.

[0078] (3) Curing time

[0079] The curing time of the paint was tested using the filter paper method.

[0080] The test results are shown in Table 1.

[0081] Table 1 - Test results for paint properties

[0082]

[0083] The above merely is the preferred embodiment of the present application, the protection scope of the present application is not only limited to the above-mentioned examples, all technical solutions belonging to the idea of the present application are within the protection scope of the present application, it should be pointed out that, for the ordinary skilled in the art, some improvements and decorations without departing from the principle of the present application should be considered as the protection scope of the present application.

Claims

1. A MXene-based self-migration strong solidification medium corrosion absorbing UV paint, characterized in that, the paint comprises: 35-45 parts of acrylate resin oligomer, 45-55 parts of acrylate monomer, 0.5-10 parts of MXene, 10-15 parts of graphene, and 0.5-1.8 parts of additives; the preparation method of the MXene comprises the following steps: (1) weigh LiF and add it to a polytetrafluoroethylene container, while stirring, add HCl solution until completely dissolved to obtain a mixed solution; (2) place Ti3AlC2 in the mixed solution, seal the container opening with plastic wrap, and tie several small holes in the plastic wrap, then place the container in a water bath, and after the reaction, a suspension is obtained; (3) filter the suspension, take the lower precipitate and add it to HCl solution until completely dissolved, then magnetically stir at room temperature to obtain a mixed solution; (4) mix the mixed solution of step (3) with acrylate modified polysiloxane, treat with ultrasonic waves to form a dispersion, centrifuge the dispersion and wash the precipitate, freeze-dry the precipitate to obtain MXene material.

2. The MXene-based self-migration strong solidification medium corrosion absorbing UV paint according to claim 1, characterized in that, the acrylate resin oligomer is urethane acrylate; the acrylate monomer is methyl methacrylate.

3. The MXene-based self-migration strong solidification medium corrosion absorbing UV paint according to claim 1, characterized in that, the additives include wetting dispersant, defoamer and thickening agent, and the mass ratio is 10:(2-5):(3-6).

4. The MXene-based self-migration strong solidification medium corrosion absorbing UV paint according to claim 3, characterized in that, the wetting dispersant is polyvinyl alcohol, the defoamer is silicone oil, and the thickening agent is polyurethane.

5. The MXene-based self-migration strong solidification medium corrosion absorbing UV paint according to claim 1, characterized in that, the mass ratio of LiF, Ti3AlC2 and acrylate modified polysiloxane is 1:1:0.

5.

6. The MXene-based self-migration strong solidification medium corrosion absorbing UV paint according to claim 1, characterized in that, the preparation method of the acrylate modified polysiloxane is: in a reaction vessel, add acrylate and low hydrogen-containing silicone oil, slowly heat to 100℃, add isopropyl alcohol solution of Karstedt catalyst, control the temperature at 100-110℃, after the reaction is completed, remove the low boiling point substance under reduced pressure to obtain acrylate modified polysiloxane.

7. The MXene-based self-migration strong solidification medium corrosion absorbing UV paint according to claim 6, characterized in that, the molar ratio of acrylate to low hydrogen-containing silicone oil is 1.1:1; the mass fraction of Karstedt catalyst in the isopropyl alcohol solution is 1%; the mass of the added isopropyl alcohol solution of Karstedt catalyst accounts for 1.5% of the total mass of the reactants; the reaction time is 6h.

8. The MXene-based self-migration strong solidification medium corrosion absorbing UV paint according to claim 1, characterized in that, In the step (1), the concentration of the HCl solution is 9 mol L -1 ; In the step (2), the temperature of the water bath is adjusted to 45 DEG C, the rotation speed of the rotor is adjusted to 400 rpm, and the reaction time is 24 hours. After the reaction, the mixture is left to stand for 2 hours to obtain a suspension; The concentration of the HCl solution in the step (3) is 11 mol L -1 ; the magnetic stirring speed is 200 rpm, and the stirring time is 30 min. In the step (4), the centrifugation is performed twice, the rotation speed of the centrifuge is 8000 rpm, and the centrifugation time is 10 minutes each time. After centrifugation, the precipitate is filtered and washed with deionized water, and the centrifugation is repeated three times. After freeze-drying, the MXene material is obtained.

9. The method for preparing a self-migrating, strongly curing, moderately anti-corrosion and UV-absorbing coating based on MXene according to any one of claims 1 to 8, characterized in that, The method comprises the following steps: S1, dispersing MXene and graphene in water and ultrasonic treatment to obtain a uniform nanodispersion; S2, dividing the acrylic ester monomer into three equal parts by weight, and numbering them as acrylic ester monomer I, acrylic ester monomer II, and acrylic ester monomer III; S3, ultrasonic mixing the nanodispersion with the acrylic ester monomer I to completely dissolve it, obtaining mixture I; ultrasonic mixing the auxiliary agent with the acrylic ester monomer II to completely dissolve it, obtaining mixture II; and ultrasonic mixing the acrylic ester resin oligomer with the acrylic ester monomer III to completely dissolve it, obtaining mixture III; S4, mixing mixture I, mixture II, and mixture III, and heating in a water bath until completely dissolved. Filtering out bubbles and impurities to obtain a composite resin coating.

Images