MXene / MoS2 nano composite material modification-based high-performance fluorocarbon finish paint and preparation method thereof

Abstract

The invention relates to the technical field of anticorrosive paint, in particular to high-performance fluorocarbon finish paint modified based on an MXene / MoS2 nanocomposite and a preparation method of the high-performance fluorocarbon finish paint. The high-performance fluorocarbon finishing paint is prepared from the following components in parts by weight: 45 to 63 parts of fluorocarbon resin, 5 to 12 parts of MXene / MoS2 nano composite material, 10 to 20 parts of titanium dioxide color paste, 8 to 14 parts of diluent, 0.5 to 0.8 part of wetting dispersant, 0.3 to 0.5 part of flatting agent, 0.3 to 0.5 part of light stabilizer, 0.3 to 0.5 part of mildew preventive, 0.3 to 0.5 part of fumed silica, 0.2 to 0.7 part of defoaming agent and 6 to 11 parts of curing agent. According to the technology, the nano composite material formed by intercalation of nano MXene and nano MoS2 is prepared and used for modifying fluorocarbon resin, the weather resistance, corrosion resistance and mechanical performance of fluorocarbon finish paint can be remarkably improved, and the fluorocarbon finish paint is suitable for long-acting protection in severe environments such as ocean engineering and bridge construction.

Description

Technical Field

[0001] This invention relates to the field of anti-corrosion coating technology, specifically to a high-performance fluorocarbon topcoat modified with MXene / MoS2 nanocomposite materials and its preparation method. Background Technology

[0002] Fluorocarbon resins (such as FEVE and PVDF) are high-performance polymer materials formed by copolymerizing fluoroolefins (such as trifluorochloroethylene and tetrafluoroethylene) with vinyl ethers / esters. In their molecular structure, fluorine atoms replace hydrogen atoms to form stable CF bonds (bond energy up to 485 kJ / mol), a structural characteristic that endows fluorocarbon resins with excellent comprehensive properties. Specifically, fluorocarbon resins possess advantages such as superior weather resistance (service life up to 15-20 years), excellent corrosion resistance (able to withstand strong acid and alkali media), wide temperature range stability (applicable temperature range from -40℃ to 260℃), self-cleaning properties (contact angle >110°), and high decorative properties, making them the preferred material for extreme environments such as cross-sea bridges and spacecraft. However, in harsh environments with high salt spray, high humidity, and drastic temperature differences, fluorocarbon resin coatings are still prone to cracking and decreased adhesion, severely affecting their application performance and service life, thus limiting their widespread application in more extreme scenarios.

[0003] To address these issues, researchers have employed various techniques to modify fluorocarbon resins, with nanomaterial modification being a particularly promising area of ​​research. MXene, a novel two-dimensional transition metal carbon / nitride material, is prepared by etching and exfoliating MAX phases (such as Ti3AlC2) with hydrofluoric acid. Its general chemical formula is M... n+1 X n T x (Where M is a transition metal element, X is C or N element, and T is T) x These are surface end groups, such as -O, -F, -OH, etc. Since 2011, Ti3C2T x Since its initial discovery, more than 50 types of MXene materials have been successfully synthesized, covering monometallic types (such as Ti3C2T). x ) and multimetallic types (such as (TiNb)2CT) x MXene materials are available in various types, including -O and -OH groups. Their surface is rich in polar groups, which can form a strong interfacial bond with fluorocarbon resins. Simultaneously, their layered structure forms a dense physical barrier layer, effectively delaying the penetration of corrosive media. Furthermore, the layered structure of MXene can disperse stress, significantly improving the tensile strength, toughness, and adhesion of fluorocarbon resins, providing a new approach to fluorocarbon resin modification.

[0004] However, nano-MXene materials have a clear tendency to stack between layers, and are prone to agglomeration during application, which limits their modification effect and restricts their practical application in the field of fluorocarbon resin modification. Summary of the Invention

[0005] (a) Purpose of the invention This invention provides a high-performance fluorocarbon topcoat modified with MXene / MoS2 nanocomposite material and its preparation method, which is mainly used to solve the problems of coating cracking, decreased adhesion and poor weather resistance of existing fluorocarbon resins under high salt spray, high humidity and drastic temperature difference environments.

[0006] Secondly, nano-Mxene used to modify fluorocarbon resins tends to stack between layers, which can easily lead to agglomeration.

[0007] (II) Technical Solution To achieve the above-mentioned objectives, the present invention adopts the following technical solution: A high-performance fluorocarbon topcoat modified based on MXene / MoS2 nanocomposite material comprises the following components by weight: 45-63 parts fluorocarbon resin, 5-12 parts MXene / MoS2 nanocomposite material, 10-20 parts titanium dioxide paste, 8-14 parts diluent, 0.5-0.8 parts wetting and dispersing agent, 0.3-0.5 parts leveling agent, 0.3-0.5 parts light stabilizer, 0.3-0.5 parts mildew inhibitor, 0.3-0.5 parts fumed silica, 0.2-0.7 parts defoamer, and 6-11 parts curing agent.

[0008] Preferably, the titanium dioxide powder paste comprises the following components by weight: 40-60 parts fluorocarbon resin, 10-18 parts diluent, 22-31 parts titanium dioxide, 2-4 parts wetting and dispersing agent, and 0.3-0.7 parts defoamer.

[0009] Preferably, the fluorocarbon resin is a fluoroolefin-vinyl ether copolymer (FEVE) with a fluorine content greater than 22% and a hydroxyl value greater than 40 mg KOH / g.

[0010] Preferably, the diluent in the titanium dioxide powder paste is one or more of xylene, butyl acetate, propylene glycol methyl ether acetate, and ethylene glycol ethyl ether acetate; The defoamer is a mineral oil-based, polyether-modified siloxane, or organosilicon defoamer; The diluent is one or more of xylene, butyl acetate, propylene glycol methyl ether acetate, and ethylene glycol ethyl ether acetate.

[0011] Preferably, the titanium dioxide in the titanium dioxide paste is rutile.

[0012] Preferably, the scraper fineness of the fumed silica is less than or equal to 40 μm.

[0013] A method for preparing a high-performance fluorocarbon topcoat modified with MXene / MoS2 nanocomposite materials includes the following steps: Step 1: Preparation of MXene / MoS2 nanocomposites, including: S1: MXene (Ti3C2T) x Preparation of nanosheet dispersion; S2: Preparation of MoS2 nanosheet dispersion; S3: Preparation of MXene / MoS2 nanocomposite materials; Step 2: Preparation of titanium dioxide slurry. Fluorocarbon resin, diluent, titanium dioxide, wetting and dispersing agent, and defoamer are put into a mixing tank and mixed together using a high-speed mixer at 1000-1500 rpm for 30-60 minutes. Then, the processed product is ground using a sand mill at 1000-1700 rpm for 1-2 hours. The fineness of the ground product is ≤15μm. Step 3: Preparation of high-performance fluorocarbon topcoat. Fluorocarbon resin, diluent, wetting and dispersing agent, leveling agent, light stabilizer, mildew inhibitor, defoamer, MXene / MoS2 nanocomposite material, and fumed silica are added to the mixing tank in sequence and mixed together using a high-speed mixer at 1000-1500 rpm for 30-50 minutes. The mixture is then filtered through an 80-mesh nylon filter before use. Before use, a curing agent and an appropriate amount of diluent are added to obtain a high-performance fluorocarbon topcoat modified with MXene / MoS2 nanocomposite material.

[0014] Preferably, S1 includes: S11: Add Ti3AlC2MAX phase powder to HF solution at a mass ratio of Ti3AlC2MAX phase powder:HF = 50-100:1, stir magnetically to obtain mixture A, which is used to etch the Al layer in Ti3AlC2MAX phase; S12: Use a centrifuge to separate the solid and liquid phases of mixture A, take the solid phase and wash it multiple times with deionized water until the pH value of the supernatant is ≤7. S13: Under the protection of argon atmosphere, the product from the previous step is treated with an ultrasonic device to obtain an MXene dispersion, in which MXene nanosheets contain 8 to 15 atomic layers.

[0015] Preferably, S2 includes: S21: Mixing MoS2:AR-grade DMA at a mass ratio of 10-30:1 yields mixture B; S22: Under the protection of argon atmosphere, mixture B is treated with ultrasonic equipment to obtain mixture C. During the treatment, an ice bath is used to control the temperature of mixture B below 25°C. S23: The mixture C was treated with a centrifuge, and then the supernatant was taken to obtain MoS2 nanosheets.

[0016] Preferably, S3 includes: S31: Mix the MXene dispersion obtained in step S13 with the MoS2 nanosheets obtained in step S23 at a mass ratio of 6-10:1, add AR grade ethanol at a mass ratio of 1:1, stir magnetically, and then sonicate under an argon atmosphere to obtain mixture D. S32: The mixture D was treated with a centrifuge to remove the aggregates of MoS2 and MXene that had not been intercalated, and a mixed solution of MXene / MoS2 nanocomposite material was obtained. S33: The MXene / MoS2 mixed solution was filtered by vacuum filtration. The filter paper used for vacuum filtration was made of PTFE. After filtration, the product was placed in a vacuum drying oven at a temperature of 80-120℃ for 5-12 hours. The dried MXene / MoS2 nanocomposite material was ground in an agate mortar and then placed in a glass desiccator for later use.

[0017] (III) Beneficial Effects 1. Significantly Improved Weather and Corrosion Resistance: The intercalated composite structure of MXene and MoS2 nanocomposites forms a dense physical barrier layer within the fluorocarbon topcoat, effectively blocking the penetration of moisture, oxygen, and chloride ions. Experimental data show that this modified material exhibits significantly improved resistance to acids, alkalis, water, damp heat cycling, damp heat, and salt spray.

[0018] 2. Enhanced mechanical properties: Applying MXene / MoS2 nanocomposite materials to fluorocarbon topcoats can improve their adhesion, flexibility and other mechanical properties. Detailed Implementation

[0019] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the invention.

[0020] Example 1: This invention provides a technical solution: a high-performance fluorocarbon topcoat modified with MXene / MoS2 nanocomposite materials and its preparation method, wherein the high-performance fluorocarbon topcoat may be composed of the following formulation: Fluorocarbon resin: 52 parts MXene / MoS2 nanocomposite material: 6 parts Titanium dioxide powder: 10 parts Diluent: 14 parts Wetting and dispersing agent: 0.8 parts Leveling agent: 0.3 parts Light stabilizer: 0.3 parts Antifungal agent: 0.3 parts Fumed silica: 0.3 parts Defoamer: 0.2-0.7 parts Hardener: 7 parts.

[0021] The specific steps of this high-performance fluorocarbon topcoat preparation method are as follows: Step 1: Preparation of MXene / MoS2 nanocomposite materials S1: MXene (Ti3C2T) x Preparation of nanosheet dispersion S11: Add Ti3AlC2MAX phase powder to HF solution at a mass ratio of Ti3AlC2MAX phase powder:HF = 60:1, stir magnetically to obtain mixture A, which is used to etch the Al layer in Ti3AlC2MAX phase; S12: Use a centrifuge to separate the solid and liquid phases of mixture A, take the solid phase and wash it multiple times with deionized water until the pH value of the supernatant is ≤7. S13: Under the protection of argon atmosphere, the product of the previous step is treated with an ultrasonic device to obtain an MXene dispersion, in which MXene nanosheets contain 8 to 15 atomic layers. Preparation of S2:MoS2 nanosheet dispersion: S21: Mixture B is obtained by mixing MoS2 and AR-grade DMA at a mass ratio of 20:1; S22: Under the protection of argon atmosphere, mixture B is treated with ultrasonic equipment to obtain mixture C. During the treatment, an ice bath is used to control the temperature of mixture B below 25°C. S23: The mixture C was treated with a centrifuge, and then the supernatant was taken to obtain a MoS2 nanosheet dispersion; Preparation of S3: MXene / MoS2 nanocomposite materials: S31: Mix the MXene dispersion obtained in step S13 with the MoS2 nanosheets obtained in step S23 at a mass ratio of 6-10:1, add AR grade ethanol at a mass ratio of 1:1, stir magnetically, and then sonicate under an argon atmosphere to obtain mixture D. S32: The mixture D was treated with a centrifuge to remove the aggregates of MoS2 and MXene that had not been intercalated, and a mixed solution of MXene / MoS2 nanocomposite material was obtained. S33: The MXene / MoS2 mixed solution was filtered by vacuum filtration. The filter paper used for vacuum filtration was made of PTFE. After filtration, the product was placed in a vacuum drying oven at a drying temperature of 80℃ for 6 hours. The dried MXene / MoS2 nanocomposite material was ground in an agate mortar and then placed in a glass desiccator for later use. Step 2: Preparation of Titanium Dioxide Powder Paste (1) The formula for titanium dioxide paste is as follows: Fluorocarbon resin: 43 parts Diluent: 12 parts Titanium dioxide: 26 parts Wetting and dispersing agent: 2 parts Defoamer: 0.5 parts (2) According to the formula, fluorocarbon resin, diluent, titanium dioxide, wetting and dispersing agent and defoamer are put into the cylinder and mixed together using a high-speed mixer at 1000 rpm for 30 minutes. Then, the processed product is ground using a sand mill at 1000 rpm for 1 hour. The fineness of the ground product is ≤15μm. Step 3: Preparation of high-performance fluorocarbon topcoat (1) According to the formula, fluorocarbon resin, diluent, wetting and dispersing agent, leveling agent, light stabilizer, mildew inhibitor, defoamer, MXene / MoS2 nanocomposite material and fumed silica are added into the cylinder in sequence and mixed together using a high-speed mixer at 1000 rpm for 30 minutes. The mixed product can be used after being filtered through an 80-mesh nylon filter. Before use, add the curing agent and an appropriate amount of diluent specified in the formula to obtain a high-performance fluorocarbon topcoat modified based on MXene / MoS2 nanocomposite material.

[0022] Comparative Example 1: Unlike Example 1, step one is not included, and MXene / MoS2 nanocomposite material is not added in step three.

[0023] Comparative Example 2: Unlike Example 1, step one only includes S1, and the MXene / MoS2 nanocomposite material in step three is replaced with the MXene dispersion obtained in step S1.

[0024] Comparative Example 3: Unlike Example 1, step one only includes S2, and the MXene / MoS2 nanocomposite material in step three is replaced with the MoS2 nanosheet dispersion obtained in step S1.

[0025] Performance testing: The following tests were conducted on Example 1 and Comparative Examples 1-3 according to the following standards, and the test results are shown in the table below: As shown in the table above, the synergistic effect of the MXene / MoS2 nanocomposite material is key to improving the overall performance of fluorocarbon topcoats (especially adhesion, resistance to damp heat, and salt spray resistance). Using MXene or MoS2 alone yields limited performance improvements, and in some aspects (such as resistance to damp heat cycling), it is even inferior to the blank control group without nanocomposite materials. The introduction of the nanocomposite material did not impair the chemical resistance and impact resistance of the fluorocarbon topcoat; on the contrary, it demonstrated superior long-term weather resistance.

Claims

1. A high-performance fluorocarbon finish based on MXene / MoS2 nanocomposite modification, characterized in that, The high-performance fluorocarbon topcoat is prepared by the following steps: step one: preparation of MXene / MoS2 nanocomposite, including:

2. The high-performance fluorocarbon finish based on MXene / MoS2 nanocomposite modification according to claim 1, characterized in that, The titanium white color paste comprises the following components by weight parts: 40-60 parts of fluorocarbon resin, 10-18 parts of diluent, 22-31 parts of titanium white, 2-4 parts of wetting dispersant, and 0.3-0.7 parts of defoaming agent. 3.The high-performance fluorocarbon finish modified with MXene / MoS 2 nanocomposite according to claim 2, characterized in that, The fluorocarbon resin is a fluorine-containing olefin-vinyl ether copolymer with a fluorine content greater than 22% and a hydroxyl value greater than 40 mg KOH / g. 4.The high-performance fluorocarbon finish based on MXene / MoS2 nanocomposite modification according to claim 2, characterized in that, The diluent in the titanium white color paste is one or more of xylene, butyl acetate, propylene glycol methyl ether acetate, and ethylene glycol ethyl ether acetate; the defoaming agent is a mineral oil-based or polyether-modified silicone defoaming agent or an organic silicon defoaming agent; and the diluent is one or more of xylene, butyl acetate, propylene glycol methyl ether acetate, and ethylene glycol ethyl ether acetate. 5.The high-performance fluorocarbon topcoat modified with MXene / MoS2 nanocomposite according to claim 2, characterized in that, The titanium white in the titanium white color paste is rutile type.

6. The high-performance fluorocarbon topcoat modified with MXene / MoS2 nanocomposite according to claim 2, characterized in that, The gas phase silica has a doctor blade fineness value of ≤40 μm.

7. A method for preparing a high-performance fluorocarbon finish modified by a MXene / MoS2 nanocomposite, applied to the high-performance fluorocarbon finish modified by a MXene / MoS2 nanocomposite according to any one of claims 1-6, characterized in that, The method comprises the following steps: Step one: preparation of MXene / MoS2 nanocomposite, including: S1: Preparation of MXene (Ti3C2T x ) nanoplatelet dispersion liquid; S2: Preparation of MoS2 nanosheet dispersion; S3: Preparation of MXene / MoS2 nanocomposite; Step two: preparation of titanium white color paste, the fluorocarbon resin, diluent, titanium white, wetting dispersant, and defoaming agent are put into a cylinder, mixed together using a high-speed mixer at a speed of 1000-1500 rpm for 30-60 minutes, then the treated product is ground using a sand mill at a grinding speed of 1000-1700 rpm for 1-2 hours, and the grinding product has a fineness of ≤15 μm; Step three: preparation of high-performance fluorocarbon topcoat, the fluorocarbon resin, diluent, wetting dispersant, leveling agent, light stabilizer, mildew-proof agent, defoaming agent, MXene / MoS2 nanocomposite, and gas phase silica are sequentially put into a cylinder, mixed together using a high-speed mixer at a speed of 1000-1500 rpm for 30-50 minutes, and the mixed product is filtered through an 80-mesh nylon filter screen before use; before use, a curing agent and an appropriate amount of diluent are added to obtain a high-performance fluorocarbon topcoat based on MXene / MoS2 nanocomposite modification. 8.The method for preparing high-performance fluorocarbon topcoat modified by MXene / MoS 2 nanocomposite according to claim 7, characterized in that, The S1 comprises: S11: Ti3AlC2 MAX phase powder is added to HF solution in a mass ratio of Ti3AlC2 MAX phase powder:HF=50-100:1, and magnetic stirring is used to obtain a mixed solution A for etching the Al layer in the Ti3AlC2 MAX phase; S12: solid-liquid separation of the mixed solution A is performed using a centrifuge, and the solid phase is then washed with deionized water for multiple times until the pH value of the supernatant is ≤7. S13: The product of the previous step is treated using an ultrasonic device under an argon atmosphere to obtain a MXene dispersion liquid, and the MXene nanosheets in the dispersion liquid contain 8-15 atomic layers. 9.The method for preparing high-performance fluorocarbon topcoat modified by MXene / MoS 2 nanocomposite according to claim 7, characterized in that, The S2 comprises: S21: A mixed liquid B is obtained by mixing MoS2 and AR grade DMA according to a mass ratio of 10-30:1; S22: The mixed liquid B is treated using an ultrasonic device under an argon atmosphere to obtain a mixed liquid C, and an ice bath is used to control the temperature of the mixed liquid B below 25 DEG C during the treatment process; S23: The mixed liquid C is treated using a centrifuge, and then the supernatant is taken to obtain MoS2 nanosheets. 10.The method for preparing high-performance fluorocarbon topcoat modified by MXene / MoS 2 nanocomposite according to claim 7, characterized in that, The S3 comprises: S31: The MXene dispersion liquid obtained in step S13 and the MoS2 nanosheets obtained in step S23 are mixed according to a mass ratio of 6-10:1, AR grade ethanol is added according to a mass ratio of 1:1, and then magnetic stirring is performed, followed by ultrasonic treatment under an argon atmosphere to obtain a mixed liquid D; S32: The mixed liquid D is treated using a centrifuge to remove the aggregates composed of MoS2 and MXene that have not been intercalated to obtain a MXene / MoS2 nanocomposite mixed solution; S33: The MXene / MoS2 mixed solution is subjected to suction filtration, the filter paper used for suction filtration is made of PTFE, and after suction filtration, the product is placed in a vacuum drying oven, the drying temperature is 80-120 DEG C, and the drying time is 5-12 h; after drying, the MXene / MoS2 nanocomposite is placed in a glass drying cabinet after being ground by an agate mortar and is ready for use.

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