Isocyanate-modified fluorocarbon resin with antifouling properties, antifouling coating thereof, preparation method thereof, and application thereof

Abstract

The invention discloses a kind of isocyanate-modified fluorocarbon resin with antifouling performance, its antifouling coating and its preparation method and application, wherein isocyanate-modified fluorocarbon resin is that it is under inert gas protection, mercaptan is mixed with acrylic monomer, photoinitiator, mercapto-vinyl click reaction is carried out at room temperature, modified acrylic monomer is obtained, then diisocyanate is added dropwise to anhydrous fluorocarbon resin, modified acrylic monomer is then added dropwise, and the isocyanate-modified fluorocarbon resin polymer obtained by adding solvent and catalyst reaction. The isocyanate-modified fluorocarbon resin of the present invention has the characteristics of lower surface energy, strong ability to suppress marine fouling bioadhesion (bacteria, seaweed etc.), small friction coefficient, good mechanical flexibility, low ice adhesion, high cyclic stability, and is particularly suitable for hull surface protection.

Description

Technical Field

[0001] The present invention belongs to the technical field of antifouling materials, and in particular relates to an isocyanate-modified fluorocarbon resin with antifouling properties, an antifouling coating thereof, and a preparation method and application thereof. Background Art

[0002] Biofilms, bacteria, algae, and large shellfish are unavoidable fouling organisms in the marine environment. These fouling organisms can form large biofilms, resulting in rough hulls and unstable centers of gravity. This can negatively impact shipping efficiency, aquaculture, equipment corrosion, and maintenance, disrupting the ecosystem. Vessels operating in both temperate and cold climates face two major challenges: marine fouling adhesion and icing. Protecting these vessels requires not only anti-fouling but also anti-icing efforts. Ice is a common natural phenomenon, primarily caused by waves forming ice, and poses a safety hazard to the shipping industry. For example, it can reduce a vessel's maneuverability, stability, and other safety features, threatening crew safety. Currently, a common approach to anti-fouling and anti-icing is to apply anti-fouling paint in temperate climates and then switch to anti-icing paint when sailing to cold climates. While this alternating coating method is well-established, it requires significant human and material resources.

[0003] Chinese patent document CN118064052A discloses a low-surface-energy anticorrosion and antifouling coating and its preparation method. The coating comprises a low-surface-energy liquid matrix, a base paint, and additives, wherein the mass ratio of the low-surface-energy liquid matrix, base paint, and additives is 5:3:2. The low-surface-energy liquid matrix comprises polydimethylsiloxane, a fluorocarbon resin, an initiator, a pH buffer, and an organic solvent. The invention uses polydimethylsiloxane as the main component of the low-surface-energy liquid matrix to improve the overall fluidity of the coating and enhance the anti-adhesion effect of the pusher. Furthermore, a polymer is used as an auxiliary agent to enhance the corrosion resistance of the paint surface.

[0004] Chinese patent document CN118256119A discloses a two-component anti-icing coating, its preparation method, and application. The two-component anti-icing coating comprises separately packaged components A and B. Component A comprises the following components by weight: 20-25 parts of organosilicon-modified fluorocarbon resin, 0.8-1.5 parts of carbon black particles, 2-3 parts of nano-modified particles, 10-15 parts of modified polyurethane, 3-5 parts of nano-alumina, 50-60 parts of a first organic solvent, and 1-5 parts of an additive. The modified polyurethane is organosilicon-modified polyurethane, and a polysiloxane modified with a benzothiazole derivative is introduced during the modification process. The nano-modified particles comprise nano-rare earth oxide and nano-titanium dioxide, and are modified with a silane coupling agent. Component B is a polyisocyanate curing agent. The anti-icing coating prepared using this two-component anti-icing coating exhibits a contact angle greater than 150° and a long-lasting anti-icing effect.

[0005] The present invention is based on different inventive concepts and aims to design a marine antifouling coating that can combine anti-icing performance with excellent antifouling / anti-icing stability. Summary of the Invention

[0006] In view of this, the purpose of the present invention is to propose an isocyanate-modified fluorocarbon resin with antifouling properties, its antifouling coating, and its preparation method and application. The isocyanate-modified fluorocarbon resin provided by the present invention is a polymer made of diisocyanate and anhydrous fluorocarbon resin as main reaction raw materials, with an appropriate amount of antifouling modified acrylic monomer (such as isobornyl acrylate) added. It has the characteristics of low surface energy, strong ability to inhibit the adhesion of marine fouling organisms (bacteria, seaweed, etc.), low friction coefficient, good mechanical flexibility, low ice adhesion, and high cyclic stability, and is particularly suitable for hull surface protection.

[0007] The technical solutions adopted are:

[0008] The present invention discloses an isocyanate-modified fluorocarbon resin with antifouling properties. The isocyanate-modified fluorocarbon resin is prepared by mixing a thiol with an acrylic monomer and a photoinitiator under inert gas protection, performing a mercapto-vinyl click reaction at room temperature to obtain a modified acrylic monomer, then dropping a diisocyanate into an anhydrous fluorocarbon resin, then dropping the modified acrylic monomer, and adding a solvent and a catalyst to react to obtain an isocyanate-modified fluorocarbon resin polymer.

[0009] A method for preparing the isocyanate-modified fluorocarbon resin having antifouling properties according to the present invention comprises the following steps:

[0010] S1. Preparation of modified acrylic monomer:

[0011] Preparation of modified acrylic monomer: Under inert gas protection, thiol, acrylic monomer, and photoinitiator are mixed in sequence, stirred evenly, and a thiol-vinyl click reaction is carried out at room temperature to obtain a modified acrylic monomer after 1-3 hours;

[0012] S2. Fluorocarbon resin dehydration: The fluorocarbon resin is dehydrated at 80-100 ° C under vacuum stirring for 1-2.5 h to obtain anhydrous fluorocarbon resin;

[0013] S3. Add the diisocyanate dropwise to the anhydrous fluorocarbon resin in step 2, and then add the modified acrylic monomer in step 1 dropwise. After the addition is complete, add a solvent and a catalyst. The reaction temperature is 80-85°C and the reaction is carried out for 3-5 hours to obtain an isocyanate-modified fluorocarbon resin polymer.

[0014] Furthermore, in step S1, the acrylic acid monomer is one or more of isobornyl acrylate, zinc acrylate, benzyl acrylate, phenyl acrylate, 1-adamantyl acrylate and 2-bromoethyl acrylate;

[0015] and / or, the thiol is one or more of β-mercaptoethanol, 6-mercaptohexanol, 11-mercaptoundecanol, 3-mercapto-1-propanol and 3-mercaptohexanol;

[0016] And / or, the photoinitiator is one or more of 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methylphenylpropiophenone and 2-hydroxy-4′-(2-hydroxyethoxy)-2-methylpropiophenone.

[0017] And / or, in step S2, the fluorocarbon resin is a FEVE type fluorocarbon resin.

[0018] FEVE-type fluorocarbon resins are typically alternating copolymers of fluoroolefins and alkyl vinyl ethers, or fluoroolefins and alkyl vinyl esters, with a relative molecular weight of 1000-2000. They typically contain a monohydroxyl group and are commercially available.

[0019] Furthermore, in step S3, the diisocyanate is one or more of toluene diisocyanate (TDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMDI), hexamethylene diisocyanate (HDI), and lysine diisocyanate (LDI).

[0020] and / or, the solvent is one or more of tetrahydrofuran, xylene, propylene glycol methyl ether acetate and n-butyl acetate;

[0021] And / or, the catalyst is one or more of triethylamine and dibutyltin dilaurate.

[0022] Furthermore, in step S1, the thiol and the acrylic acid monomer are mixed in a molar ratio of 1:1, and the content of the photoinitiator is 1%-3% of the total mass of the thiol and the acrylic acid monomer.

[0023] Furthermore, in step S3, diisocyanate, fluorocarbon resin and modified acrylic monomer are reacted according to a molar ratio of 2:1:0.5-3, and the solvent accounts for 10%-50% of the total mass.

[0024] Furthermore, in step S1, the inert gas is one or more of nitrogen, argon and helium, and more preferably nitrogen.

[0025] The mercapto-vinyl click reaction is carried out at room temperature by irradiating an ultraviolet LED light source at room temperature, and the wavelength range of the ultraviolet LED light source is 250-420 nm.

[0026] The isocyanate-modified fluorocarbon resin antifouling coating of the present invention is prepared by coating the isocyanate-modified fluorocarbon resin on a substrate and curing the substrate.

[0027] The present invention provides a method for preparing an isocyanate-modified fluorocarbon resin antifouling coating, which includes the method for preparing an isocyanate-modified fluorocarbon resin, and further includes the following steps: S4. coating the prepared isocyanate-modified fluorocarbon resin polymer on the surface of a substrate, and curing it to obtain an isocyanate-modified fluorocarbon resin antifouling coating.

[0028] Furthermore, in step S4, the coating includes one or more of brushing, rolling, dripping, and spraying;

[0029] and / or, the curing temperature is 80-85° C.;

[0030] And / or, the substrate is one or more of glass, epoxy board, copper sheet, iron sheet, steel sheet and aluminum sheet.

[0031] The isocyanate-modified fluorocarbon resin of the present invention or the isocyanate-modified fluorocarbon resin antifouling coating according to claim 7 is used for protecting the surface of a ship.

[0032] In the above technical solution:

[0033] The isocyanate-modified fluorocarbon resin with antifouling properties and the antifouling coating thereof provided by the present invention introduce a modified acrylic monomer with antifouling function to give the system active antifouling ability, introduce isocyanate groups to improve the mechanical properties of the system, and the fluorocarbon resin as the main component of the system with low surface energy can reduce the adhesion strength of ice on the coating.

[0034] The present invention provides an isocyanate-modified fluorocarbon resin with antifouling properties and a method for preparing an antifouling coating thereof. A hydroxyl-terminated monomer (i.e., a modified acrylic monomer) is prepared by a simple mercapto-vinyl click reaction between a thiol and an acrylic monomer. The hydroxyl-terminated monomer is introduced into an anhydrous fluorocarbon resin system, and diisocyanate is added simultaneously to obtain an isocyanate-modified fluorocarbon resin coating.

[0035] The prepared isocyanate-modified fluorocarbon resin is rich in urethane bonds and hydrogen bonds and can be coated on most substrates with good adhesion.

[0036] The prepared isocyanate-modified fluorocarbon resin antifouling coating has good cyclic stability. After being soaked in the small crescent algae, it was subjected to a cyclic icing-deicing test. The lowest deicing adhesion strength after 20 cycles was only 45.1 kPa.

[0037] In summary, the present invention obtains an isocyanate-modified fluorocarbon resin and its antifouling coating with antifouling, wear-resistant, anti-icing and high cyclic stability. The introduction of isocyanate groups enhances the mechanical properties and wear resistance of the system, and the combined effect with the fluorocarbon resin can enable the system to have stable de-icing stability. The coating is a high-performance marine antifouling coating with both anti-icing properties, which can meet the practical application needs in complex marine environments. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] Figure 1 1 is a graph showing stress-strain curves of the isocyanate-modified fluorocarbon resin coatings of Examples 1-4 and Comparative Example 1;

[0039] Figure 2 1-4 and Comparative Examples 1-2 show the coefficient of friction data of the isocyanate-modified fluorocarbon resin coatings (load 200 g).

[0040] Figure 3 Graphs showing experimental results of the isocyanate-modified fluorocarbon resin coatings of Examples 1-4 and Comparative Examples 1-2 for the inhibition of (a) Nitzschia closterium and (b) Diplocarpus spp.;

[0041] Figure 4 is a schematic diagram of the ice adhesion device;

[0042] Figure 5 Graphs showing (a) ice adhesion strength and (b) ice adhesion strength after 20 icing-deicing cycles of the isocyanate-modified fluorocarbon resin coatings of Examples 1-4 and Comparative Examples 1-2;

[0043] Figure 6 This is a graph showing ice adhesion strength data for Examples 1-4 and Comparative Examples 1-2 after 20 ice-freezing and de-icing cycles after being soaked in Nitzschia closterium for ten days. DETAILED DESCRIPTION

[0044] The present invention is described in detail below through specific embodiments and application examples, but the use and purpose of these exemplary embodiments are only used to illustrate the present invention and do not constitute any form of limitation on the actual protection scope of the present invention, nor do they limit the protection scope of the present invention to them.

[0045] Example 1

[0046] The method for preparing an isocyanate-modified fluorocarbon resin coating of this embodiment includes the following steps:

[0047] Step 1: Preparation of isocyanate-modified fluorocarbon resin polymer:

[0048] Under nitrogen protection, 0.5 mol of isobornyl acrylate, 0.5 mol of β-mercaptoethanol and an appropriate amount of 2,2-dimethoxy-2-phenylacetophenone were added to the reaction vessel respectively and stirred evenly. The mercapto-vinyl click reaction was carried out at room temperature under ultraviolet LED light source, and modified isobornyl acrylate was obtained after 1 hour. In another reactor, 1 mol of FEVE-type fluorocarbon resin was added and dehydrated at 100°C under vacuum stirring for 2 hours. After the temperature was lower than 45°C, 2 mol of diisocyanate and modified isobornyl acrylate were added dropwise thereto. After the addition was completed, 10 g of xylene and 60 μL of dibutyltin dilaurate were added to the system, stirred evenly, and then the temperature was raised to 80°C and reacted for 3.5 hours to obtain an isocyanate-modified fluorocarbon resin polymer.

[0049] Step 2: Preparation of isocyanate-modified fluorocarbon resin coating:

[0050] The isocyanate-modified fluorocarbon resin polymer obtained in step 1 was coated on the substrate and placed in an oven at 85°C for 6 hours to obtain a cyanate-modified fluorocarbon resin coating, which was recorded as FIB. 0.5 .

[0051] The following experiments were performed to test the coating performance:

[0052] Tensile property test: The samples were made into dumbbell shapes and the mechanical properties of the samples were tested using a universal testing machine. Three sets of parallel samples were tested for each sample. Figure 1 is the stress-strain curve of the isocyanate-modified fluorocarbon resin coating;

[0053] The FIB in Example 1 was calculated 0.5 The elongation at break is 989% and the tensile strength is 6.42MPa.

[0054] Friction coefficient test:

[0055] The coating size was made into 2.5cm×2.5cm, and the friction coefficient of the coating surface was tested using a friction and wear tester. Three sets of parallel samples were tested for each sample. The test parameters were a load of 200g and a friction radius of 3mm. Figure 2 This is the friction coefficient data diagram of the isocyanate-modified fluorocarbon resin coating;

[0056] The FIB in Example 1 was tested 0.5 The friction coefficient is stable at 0.18.

[0057] Test on the performance of inhibiting algae adhesion:

[0058] The coating was made into a 2.5 cm × 2.5 cm size. A blank glass slide was selected as a control sample. The blank glass slide and the sample were immersed in two model algae species (N. closterium and Halamphora.sp) for 7 days. After removal, the unattached algae were gently shaken in deionized water to remove the surface. The number of algae attached to the coating was observed and recorded under an optical microscope. Five areas of each coating were randomly selected and photographed. The algae attachment inhibition rate (R) was calculated using the following formula:

[0059]

[0060] Among them, R is the inhibition rate of seaweed attachment, X B is the average number of seaweed adhered to the surface of the blank glass sheet, and X is the average number of seaweed adhered to the surface of the sample coating. Figure 3 The experimental data graphs of the inhibition of the adhesion rate of (a) Nitzschia closterium and (b) Diplocarpus spp. by isocyanate-modified fluorocarbon resin coatings are shown;

[0061] After testing and calculation, it is known that the FIB of Example 1 0.5 The inhibition rate of the attachment of Nitzschia closterium was 95.7±2.6%, and the inhibition rate of the attachment of Achyranthes bidentata was 92.4±4.6%.

[0062] Ice adhesion strength test:

[0063] The ice adhesion strength test device was made by ourselves. Figure 4 The diagram of the adhesion force device mainly includes a thrust sensor (NK-200), a platform, and a plexiglass tube (1 cm diameter, 3 cm height). First, the coating sample to be tested (7.5 cm × 2.5 cm) is fixed on the platform, and nine plexiglass tubes of the above dimensions are randomly placed on the coating surface. 2 mL of deionized water is injected into each tube. The entire device and sample are placed in a -20°C environment for 4 hours to ensure that the water is completely frozen into icicles. The maximum force (F) of the thrust sensor pushing the icicle is max) is recorded as the force required to remove ice from the sample surface. The above process was repeated at least three times to ensure its repeatability. The ice adhesion strength (W ice ) can be calculated using the following formula:

[0064]

[0065] S ice is the area of ​​icicles. The 20 icing-deicing cycle test is the ice adhesion strength test repeated 20 times. Figure 5 Graphs showing (a) ice adhesion strength and (b) ice adhesion strength after 20 icing-deicing cycles of the isocyanate-modified fluorocarbon resin coatings of Examples 1-4 and Comparative Examples 1-2.

[0066] After testing and calculation, it is known that the FIB of Example 1 0.5 Ice adhesion strength W ice =19.76±2.4kPa, 20 icing-deicing cycles, ice adhesion strength W ice =50.87±1.6kPa.

[0067] Cyclic stability test:

[0068] The coating sample (7.5 cm × 2.5 cm) was first soaked in Nitzschia closterium for 10 days and then taken out. After being taken out, it was gently shaken in deionized water to remove the seaweed not attached to the surface. The sample was placed in a 40°C oven for 6 hours to remove the surface moisture. The dried sample was then subjected to an ice adhesion strength test. The specific steps were consistent with the above ice adhesion strength test. Figure 6 This is a graph showing ice adhesion strength data for Examples 1-4 and Comparative Examples 1-2 after 20 ice-freezing and de-icing cycles after being soaked in Nitzschia closterium for ten days.

[0069] After testing and calculation, it is known that the FIB of Example 1 0.5 The ice adhesion strength after 20 ice-deicing cycles after soaking in Nitzschia closterium for ten days is W ice =55.86±1.9kPa.

[0070] Example 2

[0071] Referring to Example 1, the difference from Example 1 is that in the preparation process of an isocyanate-modified fluorocarbon resin coating in this embodiment, 1 mol of isobornyl acrylate and 1 mol of β-mercaptoethanol are used, and the rest of the method remains unchanged, as shown in Example 1, and Example 2 is recorded as FIB1.

[0072] Test according to the test method of Example 1, see Figures 1-6The results are as follows: tensile strength and elongation at break are 6.23 MPa and 785% respectively; the friction coefficient is stable at 0.23; the inhibition rate of Nitzschia closterium is 97.4±3.1%, and the inhibition rate of Asteraceae is 95.7±2.6%; the ice adhesion strength W ice =18.19±3.9kPa, 20 icing-deicing cycles, ice adhesion strength W ice =50.87±1.6kPa; after 20 ice-deicing cycles of soaking in Nitzschia closterium for ten days, the ice adhesion strength is W ice =47.31±1.3kPa.

[0073] Example 3

[0074] Referring to Example 1, the difference from Example 1 is that in the preparation process of an isocyanate-modified fluorocarbon resin coating in this embodiment, 2 mol of isobornyl acrylate and 2 mol of β-mercaptoethanol are used, and the rest of the method remains unchanged, as shown in Example 1, and Example 3 is recorded as FIB2.

[0075] Test according to the test method of Example 1, see Figures 1-6 The results are as follows: tensile strength and elongation at break were 7.84 MPa and 767% respectively; the friction coefficient was stable at 0.16; the inhibition rate of Nitzschia closterium was 97.4±3.1% and that of Ampelopsis glomerata was 97.4±3.1%; the ice adhesion strength W ice =8.80±1.9kPa, 20 icing-deicing cycles, ice adhesion strength W ice =39.26±3.5kPa; after 20 ice-deicing cycles of soaking in Nitzschia closterium for ten days, the ice adhesion strength is W ice =45.13±4.2kPa.

[0076] Example 4

[0077] Referring to Example 1, the difference from Example 1 is that in the preparation process of an isocyanate-modified fluorocarbon resin coating in this example, 3 mol of isobornyl acrylate and 3 mol of β-mercaptoethanol are used, and the rest of the method remains unchanged, as shown in Example 1, and Example 4 is recorded as FIB3.

[0078] Test according to the test method of Example 1, see Figures 1-6 The results are as follows: tensile strength and elongation at break were 2.81 MPa and 483% respectively; the friction coefficient was stable at 0.41; the inhibition rate of Nitzschia closterium was 95.7±0.6% and that of Ampelopsis glomerata was 96.2±3.4%; the ice adhesion strength W ice =6.60±0.5kPa, 20 icing-deicing cycles, ice adhesion strength W ice=61.01±3.9kPa; after 20 ice-deicing cycles of soaking in Nitzschia closterium for ten days, the ice adhesion strength is W ice =66.55±2.9kPa.

[0079] Comparative Example 1

[0080] Referring to Example 1, the difference from Example 1 is that in the preparation process of an isocyanate-modified fluorocarbon resin coating in Comparative Example 1, 0 mol of isobornyl acrylate and 0 mol of β-mercaptoethanol were used. Specifically, 1 mol of FEVE-type fluorocarbon resin was added to a reactor at 100°C and dehydrated under vacuum with stirring for 2 hours. After the temperature dropped below 45°C, 2 mol of diisocyanate was added dropwise. After the addition was complete, 10 g of xylene and 60 μL of dibutyltin dilaurate were added to the system, stirred evenly, and then the temperature was raised to 80°C and reacted for 3.5 hours to obtain an isocyanate-modified fluorocarbon resin polymer. 2 mol of 1,4-butanediol was then added to the system to completely react the isocyanate groups. After curing, it was recorded as an FI coating.

[0081] Test according to the test method of Example 1, see Figures 1-6 The results are as follows: tensile strength and elongation at break were 2.17 MPa and 1040%, respectively; the friction coefficient was stable at 0.08; the inhibition rate of Nitzschia closterium was 94.6±1.2%, and the inhibition rate of Asteraceae was 89.3±0.9%; the ice adhesion strength W ice =18.54±7.8kPa, 20 icing-deicing cycles, ice adhesion strength W ice =52.78±3.6kPa; after 20 ice-deicing cycles of soaking in Nitzschia closterium for ten days, the ice adhesion strength is W ice =56.82±2.1kPa.

[0082] Comparative Example 2

[0083] Referring to Example 1, the difference from Example 1 is that in Comparative Example 2, FEVE is directly coated on the substrate, placed in an oven at 85° C., and cured for 6 hours to obtain a fluorocarbon resin coating, which is recorded as FEVE.

[0084] Test according to the test method of Example 1, see Figures 1-6 The results are shown as follows: no tensile strength test data was obtained for this comparative example because no qualified test sample could be obtained after curing; the friction coefficient was stable at 0.15; the inhibition rate of Nitzschia closterium was 81.9±0.9%, and the inhibition rate of Asteraceae was 88.9±0.9%; the ice adhesion strength W ice =45.49±11.7kPa, 20 icing-deicing cycles, ice adhesion strength W ice=91.25±2.8kPa; after 20 ice-deicing cycles of soaking in Nitzschia closterium for ten days, the ice adhesion strength is W ice =101.26±1.9kPa.

[0085] Although the above embodiments and application examples provide a detailed description of the present invention, they are only part of the embodiments of the present invention, not all of the embodiments. Other embodiments can be obtained based on this embodiment without creativity, and these embodiments all fall within the scope of protection of the present invention.

Claims

1. An isocyanate-modified fluorocarbon resin with antifouling properties, characterized in that: The method comprises the following steps: under the protection of an inert gas, mixing a thiol with an acrylic monomer and a photoinitiator, carrying out a mercapto-vinyl click reaction at room temperature to obtain a modified acrylic monomer at a hydroxyl end; then, adding a diisocyanate dropwise to an anhydrous fluorocarbon resin, followed by adding a modified acrylic monomer at a hydroxyl end; and adding a solvent and a catalyst to react to obtain an isocyanate-modified fluorocarbon resin; wherein the fluorocarbon resin is a FEVE-type fluorocarbon resin.

2. A method for preparing the isocyanate-modified fluorocarbon resin with antifouling properties according to claim 1, characterized in that: The steps include: S1. Preparation of modified acrylic monomer: Preparation of modified acrylic monomer: Under inert gas protection, thiol, acrylic monomer, and photoinitiator are mixed in sequence, stirred evenly, and a thiol-vinyl click reaction is carried out at room temperature to obtain a modified acrylic monomer after 1-3 hours; S2. Fluorocarbon resin dehydration: Dehydrate the fluorocarbon resin under vacuum stirring at 80-100°C for 1-2.5 hours to obtain anhydrous fluorocarbon resin; S3. Add diisocyanate dropwise to the anhydrous fluorocarbon resin in step 2, and then add the modified acrylic monomer in step 1 dropwise. After the addition is complete, add solvent and catalyst. The reaction temperature is 80-85°C and the reaction is carried out for 3-5 hours to obtain an isocyanate-modified fluorocarbon resin.

3. The method for preparing an isocyanate-modified fluorocarbon resin having antifouling properties according to claim 2, wherein: In step S1, the acrylic acid monomer is one or more of isobornyl acrylate, zinc acrylate, benzyl acrylate, phenyl acrylate, 1-adamantyl acrylate and 2-bromoethyl acrylate; and / or, the thiol is one or more of β-mercaptoethanol, 6-mercaptohexanol, 11-mercaptoundecanol, 3-mercapto-1-propanol and 3-mercaptohexanol; And / or, the photoinitiator is one or more of 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methylphenylpropiophenone and 2-hydroxy-4′-(2-hydroxyethoxy)-2-methylpropiophenone.

4. The method for preparing an isocyanate-modified fluorocarbon resin having antifouling properties according to claim 2, wherein: In step S3, the diisocyanate is one or more of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate and lysine diisocyanate; and / or, the solvent is one or more of tetrahydrofuran, xylene, propylene glycol methyl ether acetate and n-butyl acetate; And / or, the catalyst is one or more of triethylamine and dibutyltin dilaurate.

5. The method for preparing an isocyanate-modified fluorocarbon resin having antifouling properties according to claim 2, wherein: In step S1, the thiol and the acrylic acid monomer are mixed in a molar ratio of 1:1, and the content of the photoinitiator is 1%-3% of the total mass of the thiol and the acrylic acid monomer.

6. The method for preparing an isocyanate-modified fluorocarbon resin having antifouling properties according to claim 2, wherein: In step S3, diisocyanate, fluorocarbon resin and modified acrylic monomer are reacted in a molar ratio of 2:1:0.5-3, and the solvent accounts for 10%-50% of the total mass.

7. An isocyanate-modified fluorocarbon resin antifouling coating, characterized in that: The isocyanate-modified fluorocarbon resin according to claim 1 is coated on a substrate and cured to obtain an isocyanate-modified fluorocarbon resin antifouling coating.

8. A method for preparing an isocyanate-modified fluorocarbon resin antifouling coating, characterized in that: The method for preparing the isocyanate-modified fluorocarbon resin according to any one of claims 2 to 6 further comprises the following step: S4. coating the prepared isocyanate-modified fluorocarbon resin on the surface of a substrate, and curing the substrate to obtain an isocyanate-modified fluorocarbon resin antifouling coating.

9. The method for preparing an isocyanate-modified fluorocarbon resin antifouling coating according to claim 8, characterized in that: In step S4, the coating includes one or more of brushing, rolling, dripping, and spraying; and / or, the curing temperature is 80-85° C.; And / or, the substrate is one or more of glass, epoxy board, copper sheet, iron sheet, steel sheet and aluminum sheet.

10. Use of the isocyanate-modified fluorocarbon resin according to claim 1 or the isocyanate-modified fluorocarbon resin antifouling coating according to claim 7 for protecting the surface of a ship.

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