Isocyanate group modified fluorocarbon resin with antifouling property, antifouling coating of isocyanate group modified fluorocarbon resin and preparation method and application of isocyanate group modified fluorocarbon resin

Abstract

The invention discloses isocyanate group modified fluorocarbon resin with antifouling performance, an antifouling coating thereof, a preparation method and application of the antifouling coating, and the isocyanate group modified fluorocarbon resin is prepared by the following steps: under the protection of inert gas, mixing mercaptan with an acrylic monomer and a photoinitiator, carrying out sulfydryl-vinyl click reaction at normal temperature, and then adding an initiator, so as to obtain the isocyanate group modified fluorocarbon resin. The preparation method comprises the following steps: adding an acrylic monomer into anhydrous fluorocarbon resin to obtain a modified acrylic monomer, dropwise adding diisocyanate into the anhydrous fluorocarbon resin, dropwise adding the modified acrylic monomer, and adding a solvent and a catalyst to react to obtain the isocyanate-based modified fluorocarbon resin polymer. The isocyanate group modified fluorocarbon resin disclosed by the invention has the characteristics of low surface energy, strong adhesion capability (bacteria, seaweed and the like) for inhibiting marine fouling organisms, small friction coefficient, good mechanical flexibility, low ice accumulation adhesion and high cycle stability, and is particularly suitable for ship surface protection.

Description

Technical Field

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

[0002] In the marine environment, there are inevitably some biofilms, bacteria, algae and large shell fouling organisms, which further form large-scale fouling biological communities, causing the hull to be rough and the center of gravity to be unstable. It will also have some adverse effects on shipping efficiency, aquaculture, equipment corrosion and maintenance, and disrupt the ecosystem. There are two major types of problems faced by ships that need to go through temperate and low-temperature areas: marine fouling adhesion and hull ice. For the protection of such ships, it is necessary not only to pay attention to the anti-fouling problem on the hull surface, but also to focus on the anti-icing of the hull surface. Ice is a very common natural phenomenon. Most of the reasons for the hull ice are the ice of the waves, which will bring safety hazards to the natural shipping industry. For example, it may reduce the safety performance of the ship's maneuverability, stability and other safety performance, threatening the safety of the crew. The current common method for protection against fouling and ice is to apply anti-fouling paint in temperate areas and replace it with anti-icing paint when sailing to low-temperature areas. Although this alternating coating method is mature, it requires a lot of manpower, material resources and other resources.

[0003] Chinese patent document CN118064052A discloses a low surface energy anticorrosion and antifouling coating and a preparation method thereof, wherein the antifouling coating comprises a low surface energy liquid matrix, a base paint, and an additive, wherein the components of the low surface energy liquid matrix, the base paint, and the additive are recorded as 5:3:2 by mass ratio, wherein the low surface energy liquid matrix comprises polydimethylsiloxane, fluorocarbon resin, an initiator, a pH buffer, and an organic solution. In the invention, polydimethylsiloxane is used as the main body of the low surface energy liquid matrix to improve the overall fluidity of the coating, improve the anti-adhesion effect of the pusher, and use a high molecular polymer as an auxiliary to improve the anti-corrosion ability of the paint surface.

[0004] Chinese patent document CN118256119A discloses a two-component anti-icing coating and its preparation method and application. The two-component anti-icing coating includes independently packaged components A and B; component A includes 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 the first organic solvent, and 1-5 parts of auxiliary agent, wherein the modified polyurethane is organosilicon-modified polyurethane, and polysiloxane modified by benzothiazole derivatives is introduced during the modification process; wherein the nano-modified particles include nano rare earth oxides and nano titanium dioxide, and the nano-modified particles are modified by silane coupling agents; component B is a polyisocyanate curing agent. The contact angle of the anti-icing coating prepared by the two-component anti-icing coating of the invention is greater than 150°, and the anti-icing effect of the anti-icing coating is long-lasting.

[0005] The present invention is based on different inventive concepts and aims to design a marine antifouling coating that can combine anti-icing performance and 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. The polymer has the characteristics of low surface energy, strong ability to inhibit the adhesion of marine fouling organisms (bacteria, seaweed, etc.), small 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 invention discloses an isocyanate-modified fluorocarbon resin with antifouling performance. The isocyanate-modified fluorocarbon resin polymer is obtained by mixing thiol, acrylic monomer and photoinitiator under the protection of inert gas, carrying out mercapto-vinyl click reaction at room temperature to obtain modified acrylic monomer, then dropping diisocyanate into anhydrous fluorocarbon resin, then dropping modified acrylic monomer, and adding solvent and catalyst to react.

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

[0010] S1. Preparation of modified acrylic monomer:

[0011] Preparation of modified acrylic monomer: Under the protection of inert gas, 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: dehydrate the fluorocarbon resin at 80-100°C under vacuum stirring for 1-2.5h to obtain anhydrous fluorocarbon resin;

[0013] 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 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] Further, 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-methylphenylpropionone and 2-hydroxy-4′-(2-hydroxyethoxy)-2-methylpropionone.

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

[0018] FEVE type fluorocarbon resin is generally an alternating copolymer formed by copolymerization of fluoroolefin and alkyl vinyl ether, or fluoroolefin and alkyl vinyl ester, with a relative molecular weight of 1000 to 2000. It is generally a fluorocarbon resin containing a monohydroxyl group. FEVE type fluorocarbon resin is already a commercially available product.

[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 in 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 thiol-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 250-420nm.

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

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

[0028] Further, in step S4, the coating includes one or more of brush coating, roller coating, drip coating, and spray coating;

[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 of claim 7 is used in protecting the surface of a ship.

[0032] In the above technical solution:

[0033] In the isocyanate-modified fluorocarbon resin with antifouling performance and the antifouling coating thereof provided by the present invention, a modified acrylic monomer with antifouling function is introduced to give the system active antifouling ability, and the isocyanate group is introduced to improve the mechanical properties of the system. 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] In the preparation method of an isocyanate-modified fluorocarbon resin with antifouling performance and an antifouling coating thereof provided by the present invention, a hydroxyl-terminated monomer (i.e., a modified acrylic monomer) is prepared by a simple mercapto-vinyl click reaction between thiol and acrylic monomers, which is introduced into an anhydrous fluorocarbon resin system, and diisocyanate is added at the same time to obtain an isocyanate-modified fluorocarbon resin coating.

[0035] The prepared isocyanate-modified fluorocarbon resin is rich in a large number of 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 immersed in Nitzschia closterium, the cyclic icing-deicing test was carried out. 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 which are anti-fouling, wear-resistant, anti-icing and have 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 anti-icing properties, which can meet the practical application requirements in complex marine environments. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] Figure 1 is a stress-strain curve data diagram of the isocyanate-modified fluorocarbon resin coating of Examples 1-4 and Comparative Example 1;

[0039] Figure 2 It is a friction coefficient data diagram of the isocyanate-modified fluorocarbon resin coating of Examples 1-4 and Comparative Examples 1-2 (load 200g);

[0040] Figure 3 1 is a data graph showing the experimental results of the isocyanate-modified fluorocarbon resin coatings of Examples 1-4 and Comparative Examples 1-2 for the inhibition ratios of (a) Nitzschia closterium and (b) Diplocoriella;

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

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

[0043] Figure 6 This is a data graph of ice adhesion strength after 20 ice-deicing cycles of Examples 1-4 and Comparative Examples 1-2 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 implementation modes 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 limit the protection scope of the present invention to this.

[0045] Example 1

[0046] The method for preparing an isocyanate-modified fluorocarbon resin coating of this embodiment comprises 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 container respectively and stirred evenly, and a mercapto-vinyl click reaction was carried out at room temperature under the irradiation of an ultraviolet LED light source to obtain modified isobornyl acrylate after 1 hour; 1 mol of FEVE type fluorocarbon resin was added to another reactor at 100°C, and vacuum stirred and dehydrated 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, placed in an oven at 85°C, and cured 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 is 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 size was made into 2.5 cm × 2.5 cm, and a blank glass sheet was selected as a control sample. The blank glass sheet and the sample were immersed in two model algae species (N. closterium and Halamphora.sp) for 7 days, respectively. After being taken out, they were gently shaken in deionized water to remove the seaweed not attached to the surface. The number of seaweed attached to the coating was observed and recorded under an optical microscope. Five areas of each coating were randomly selected for photography. The seaweed inhibition rate (R) was calculated by 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 results of isocyanate-modified fluorocarbon resin coatings on the inhibition of adhesion rates of (a) Nitzschia closterium and (b) Diplocoriella sphenanthera;

[0061] Through 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 Dictyophora divaricata was 92.4±4.6%.

[0062] Ice adhesion strength test:

[0063] The ice adhesion strength test device was made by ourselves. Figure 4 The schematic diagram of the adhesion device mainly includes a thrust sensor (NK-200), a platform and a plexiglass tube (1 cm in diameter, 3 cm in 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 size are randomly placed on the coating surface, and 2 mL of ionized water is injected into them. The entire device and the sample are placed in an environment of -20°C for 4 hours to ensure that the water is completely frozen into icicles. The maximum force (F) of the thrust sensor pushing the icicle 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 by the following formula:

[0064]

[0065] S ice is the area of ​​the icicle. 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] Through 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 (7.5cm×2.5cm) 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, and then the dried sample was subjected to an ice adhesion strength test. The specific steps are consistent with the above-mentioned ice adhesion strength test. Figure 6 This is a data graph of ice adhesion strength after 20 ice-deicing cycles of Examples 1-4 and Comparative Examples 1-2 after being soaked in Nitzschia closterium for ten days.

[0069] Through testing and calculation, it is known that the FIB of Example 1 0.5 After 20 ice-deicing cycles of soaking in Nitzschia closterium for ten days, the ice adhesion strength 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 example, 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 Figure 1-Figure 6The results are as follows: the 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 Aglaonema closterium 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 icing-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 of this example, 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 Figure 1-Figure 6 The results are as follows: the tensile strength and elongation at break are 7.84 MPa and 767% respectively; the friction coefficient is stable at 0.16; the inhibition rate of Nitzschia closterium is 97.4±3.1%, and the inhibition rate of Ampelopsis glomerata is 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 of 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 Figure 1-Figure 6 The results are as follows: the tensile strength and elongation at break are 2.81 MPa and 483%, respectively; the friction coefficient is stable at 0.41; the inhibition rate of Nitzschia lunulata is 95.7±0.6%, and the inhibition rate of Aglaonema lunulata is 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±3.9 kPa; 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. Specifically, 1 mol of FEVE-type fluorocarbon resin is added to the reactor at 100°C, and vacuum-stirred and dehydrated for 2 hours. After the temperature is lower than 45°C, 2 mol of diisocyanate is added dropwise thereto. After the addition is complete, 10 g of xylene and 60 μL of dibutyltin dilaurate are added to the system, stirred evenly, and then heated to 80°C and reacted for 3.5 hours to obtain an isocyanate-modified fluorocarbon resin polymer. Then 2 mol of 1,4-butanediol is added thereto to completely react the isocyanate group, and after curing, it is recorded as FI coating.

[0081] Test according to the test method of Example 1, see Figure 1-Figure 6 The results are as follows: the tensile strength and elongation at break are 2.17 MPa and 1040%, respectively; the friction coefficient is stable at 0.08; the inhibition rate of Nitzschia closterium is 94.6±1.2%, and the inhibition rate of Aglaonema closterium is 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 icing-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 Figure 1-Figure 6 As shown, the results are 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 Aglaonema serrata 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 have described the present invention in detail, they are only part of the embodiments of the present invention, not all of the embodiments. Other embodiments can be obtained based on the embodiments without creativity, and these embodiments all fall within the protection scope of the present invention.

Claims

1. An isocyanate-modified fluorocarbon resin having antifouling properties, characterized in that: The method comprises mixing thiol with acrylic monomer and photoinitiator under the protection of inert gas, carrying out mercapto-vinyl click reaction at room temperature to obtain modified acrylic monomer, then dropping diisocyanate into anhydrous fluorocarbon resin, followed by dropping modified acrylic monomer, and adding solvent and catalyst to react to obtain isocyanate-modified fluorocarbon resin polymer.

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 the protection of inert gas, 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 at 80-100°C under vacuum stirring for 1-2.5h 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 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.

3. The method for preparing the isocyanate-modified fluorocarbon resin with antifouling properties according to claim 1, characterized in that: 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. And / or, in step S2, the fluorocarbon resin is a FEVE type fluorocarbon resin.

4. The method for preparing the isocyanate-modified fluorocarbon resin with antifouling performance according to claim 1, characterized in that: 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 the isocyanate-modified fluorocarbon resin with antifouling performance according to claim 1, characterized in that: 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 the isocyanate-modified fluorocarbon resin with antifouling performance according to claim 1, characterized in that: 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 2-6 further comprises the following step: S4. coating the prepared isocyanate-modified fluorocarbon resin polymer on the surface of a substrate, and curing the substrate to obtain an isocyanate-modified fluorocarbon resin antifouling coating.

9. The method for preparing the isocyanate-modified fluorocarbon resin antifouling coating according to claim 8, characterized in that: In step S4, the coating includes one or more of brush coating, roller coating, drip coating, and spray coating; 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 in protecting the surface of a ship.

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