A silicone-modified fluorocarbon resin with antifouling performance, an antifouling coating thereof, a composite coating, and a preparation method and application thereof

Abstract

The application discloses a kind of organic silicon modified fluorocarbon resin with antifouling performance, its antifouling coating, composite coating and preparation method and application, wherein the organic silicon modified fluorocarbon resin is made by using diisocyanate, fluorocarbon resin, monohydroxy end-capped polydimethylsiloxane and catalyst in organic solvent for condensation polymerization reaction.The obtained organic silicon modified fluorocarbon resin after reaction is coated on substrate to obtain organic silicon modified fluorocarbon resin coating;Composite coating can be mixed from A component and B component to generate composite coating containing organic silicon modified fluorocarbon resin as main component.The organic silicon modified fluorocarbon resin of the application has the characteristics of low surface energy, strong antifouling adhesion capacity, good hydrophobicity, small friction coefficient, good mechanical toughness and small ice adhesion strength.

Description

Technical Field

[0001] This invention belongs to the field of antifouling materials technology, specifically relating to an organosilicon-modified fluorocarbon resin with antifouling properties, its antifouling coating, composite coating, preparation method and application. Background Technology

[0002] Developing the marine economy, accelerating marine science and technology innovation, protecting the marine ecological environment, promoting the construction of the 21st Century Maritime Silk Road, and building a maritime community with a shared future all depend on ships and marine equipment and facilities. In recent years, with the increase in marine resource development activities, researchers have discovered that polar regions are rich in chemical energy, biological resources, and mineral resources. Consequently, ships traveling between temperate and cold regions are more frequent. The protection of ship surfaces cannot be limited to inhibiting the attachment of fouling organisms; it must also take into account the damage caused by icing of the ship surface due to waves during navigation in low-temperature regions and the friction caused by sea ice on the hull surface.

[0003] Fluorocarbon resins are widely used in composite coatings due to their heat resistance, chemical resistance, cold resistance, and low-temperature flexibility. Coatings made from fluorocarbon resins typically have a contact angle of 85-95°. Although they offer some protection, their anti-fouling and anti-icing effects are generally poor. Modifying fluorocarbon resin coatings with silicon-based additives can reduce the surface tension of the coating and increase its contact angle. The contact angle of the modified fluorocarbon resin coating is now 100-115°.

[0004] Chinese Patent Application No. 202310015847.6 discloses a high-strength anti-icing coating, a high-strength anti-icing coating layer, its preparation method, and its application. The high-strength anti-icing coating, by weight, comprises the following raw materials: 100 parts of a skeleton material, 0-40 parts of a solid lubricant, 0.2-0.8 parts of a leveling agent, 0.2-0.8 parts of a defoamer, 0.2-1 parts of a catalyst, and 100-10000 parts of an organic solvent. The skeleton material consists of a coating precursor and a curing agent. The coating precursor includes a resin precursor and an organosilicon precursor. This invention forms a low-ice-adhesion interpenetrating polymer network coating by using an organosilicon precursor combined with a curing agent.

[0005] Chinese Patent Application No. 202311777179.7 discloses an antifouling membrane for wastewater treatment and its preparation method. The antifouling membrane is composed of the following raw materials in parts by weight: 80-100 parts PVC, 20-30 parts fluorocarbon resin, 30-60 parts deionized water, 3-13 parts titanium dioxide nanoparticles, 5-10 parts polysiloxane, 5-10 parts titanium nitrate, 5-10 parts organosilane, 1-2 parts curing agent, 5-8 parts defoamer, 1-3 parts stabilizer, 0.01-0.05 parts antioxidant, 1-3 parts crosslinking agent, 1-3 parts hydrophobic agent, 4-6 parts silicone-acrylic emulsion, 6-10 parts polytetrafluoroethylene dispersion emulsion, 5-8 parts toughening agent, and 0.5-1 parts thickener. This invention obtains an antifouling membrane by mixing fluorocarbon resin and organosilane through stirring. This membrane has good non-adhesion properties against common stains.

[0006] Based on different inventive concepts, it is still necessary to develop a material with comprehensive properties such as low surface energy, strong anti-fouling adhesion, good hydrophobicity, low coefficient of friction, good mechanical toughness, and low ice adhesion strength. Summary of the Invention

[0007] In view of this, the purpose of this invention is to provide an antifouling silicone-modified fluorocarbon resin, its antifouling coating, composite coating, its preparation method, and its application. The antifouling silicone-modified fluorocarbon resin is produced by a polycondensation reaction, using isocyanate as a bridge to link silicone and fluorocarbon resins to form a highly cross-linked silicone-modified fluorocarbon resin. The resulting silicone-modified fluorocarbon resin is coated onto a substrate and cured to obtain the silicone-modified fluorocarbon resin coating. The composite coating can be generated by mixing its A and B components to produce a composite coating containing silicone-modified fluorocarbon resin as the main component. It has self-lubricating properties, specifically characterized by low surface energy, strong ability to inhibit marine fouling bioadhesion, low underwater friction coefficient, good mechanical flexibility, low ice adhesion, and high cycle stability. It is particularly suitable for the protection of ship hull surfaces traveling between temperate and cold zones.

[0008] The technical solution adopted is as follows:

[0009] The present invention discloses an organosilicon-modified fluorocarbon resin with antifouling properties, which is prepared by polycondensation reaction of diisocyanate, fluorocarbon resin, monohydroxy-terminated polydimethylsiloxane and catalyst in an organic solvent.

[0010] A method for preparing the organosilicon-modified fluorocarbon resin with antifouling properties according to the present invention includes the following steps:

[0011] S1. Preparation of organosilicon-modified isocyanate prepolymer:

[0012] A monohydroxy-terminated polydimethylsiloxane was added to a reaction vessel at 100°C and dehydrated under vacuum stirring. After the temperature dropped below 45°C, diisocyanate was added dropwise. After the addition was complete, an organic solvent and a catalyst were added to the system and stirred until homogeneous. The temperature was then raised to 60-80°C to allow for complete reaction, thus obtaining an organosilicon-modified isocyanate prepolymer.

[0013] S2. Preparation of organosilicon-modified fluorocarbon resin:

[0014] The silicone-modified isocyanate prepolymer obtained in S1 was added to fluorocarbon resin and stirred evenly to obtain silicone-modified fluorocarbon resin.

[0015] Furthermore, the diisocyanate includes, but is not limited to, one or more of, for example, toluene diisocyanate (TDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMD I), hexamethylene diisocyanate (HDI), and lysine diisocyanate (LDI);

[0016] And / or, the catalyst is one or more of triethylamine and dibutyltin dilaurate;

[0017] And / or, the organic solvent is one or more of xylene, propylene glycol methyl ether, and propylene glycol methyl ether acetate.

[0018] Further, the relative molecular weight of the monohydroxyl-terminated polydimethylsiloxane is 2000-2500; and / or, the general structural formula of the monohydroxyl-terminated polydimethylsiloxane is as follows:

[0019]

[0020] Wherein: R4 is hydrogen or methyl, R5 is a C1-8 alkyl group; n is an integer from 24 to 31.

[0021] The CAS number for monohydroxy-terminated polydimethylsiloxane is 102782-86-5.

[0022] Further, the fluorocarbon resin is FEVE fluorocarbon resin with a relative molecular weight of 1000-2000; or the general structural formula of the fluorocarbon resin is as follows:

[0023]

[0024] R1 is hydrogen or methyl, R2 is a C1-8 alkyl group, R3 is a C2-3 olefin, and X is a chlorinated hydrocarbon.

[0025] Further, the mixture contains 35-50 parts by weight of monohydroxy-terminated polydimethylsiloxane, 40-140 parts by weight of fluorocarbon resin, 0.1-0.3 parts by weight of catalyst, and 20-60 parts by weight of diisocyanate.

[0026] The present invention provides an organosilicon-modified fluorocarbon resin antifouling coating, which is prepared by coating the organosilicon-modified fluorocarbon resin onto a substrate and curing it.

[0027] Furthermore, the substrate includes, but is not limited to, one of the following: glass, wood, epoxy board, steel sheet, tinplate, and aluminum sheet.

[0028] The present invention provides a composite coating comprising separately packaged component A and component B. Component A comprises the following components in parts by weight: organosilicon-modified isocyanate prepolymer, a first organic solvent, pigments and fillers, and coating additives; the coating additives include one or more of dispersants, leveling agents, and defoamers.

[0029] Component B comprises the following components in parts by weight: fluorocarbon resin, catalyst, anti-settling agent, and second organic solvent.

[0030] The organosilicon-modified isocyanate prepolymer is prepared as follows:

[0031] A monohydroxy-terminated polydimethylsiloxane was added to a reaction vessel at 100°C and dehydrated under vacuum stirring. After the temperature dropped below 45°C, diisocyanate was added dropwise. After the addition was complete, an organic solvent and a catalyst were added to the system and stirred until homogeneous. The temperature was then raised to 60-80°C to allow for complete reaction, resulting in an organosilicon-modified isocyanate prepolymer.

[0032] Furthermore, the time for a full reaction is 2.5-4 hours.

[0033] Further, component A comprises the following components in parts by weight: 8-15 parts of organosilicon-modified isocyanate prepolymer, 7-16 parts of first organic solvent, 6-12 parts of pigments and fillers, and 0.1-1 parts of coating additives;

[0034] Component B comprises the following components in parts by weight: 10-40 parts of fluorocarbon resin, 0.1-1 parts of catalyst, 0.2-0.8 parts of anti-settling agent, and 6-14 parts of second organic solvent.

[0035] Furthermore, the pigments and fillers are one or more of titanium dioxide, talc, silica fume, wollastonite, and sericite.

[0036] Furthermore, the dispersant is one or more of the following: polyether-modified polyorganosiloxane, anionic wetting and dispersing agent, and low molecular weight unsaturated polycarboxylic acid polymer. The dispersant can be selected from the German BYK series 163.

[0037] Furthermore, the leveling agent is one of EFKA3777, BYK-333, and EFKA-3888.

[0038] Furthermore, the defoamer is one of BYK066 and BYK052.

[0039] Furthermore, the first organic solvent includes, but is not limited to, one or more of, for example, xylene and propylene glycol methyl ether acetate;

[0040] Furthermore, the second organic solvent includes, but is not limited to, one or more of, for example, xylene, tetrahydrofuran, and propylene glycol methyl ether acetate;

[0041] Furthermore, the anti-settling agent includes, but is not limited to, one or more of, for example, organic bentonite, polyamide wax, and BYK 410.

[0042] The method for preparing the composite coating of the present invention includes the following steps:

[0043] Step 1. Preparation of Component A:

[0044] The prepared organosilicon-modified isocyanate prepolymer, the first organic solvent, and pigments and fillers are mixed for the first time to obtain the first mixture;

[0045] The first mixture and the coating additives are mixed a second time to obtain the second mixture;

[0046] The second mixture is thoroughly mixed until homogeneous using a high-speed disperser to obtain component A.

[0047] Step 2. Preparation of Component B:

[0048] The fluorocarbon resin, catalyst, anti-settling agent, and second organic solvent were thoroughly mixed and stirred using a high-speed disperser to obtain component B.

[0049] Furthermore, in step S1, the first mixing is carried out in a dispersion tank, and the first mixing is carried out under stirring conditions. The stirring speed is preferably 3000 rpm, and the time is 10-20 min.

[0050] Further, in step S1, the second mixing is preferably the addition of a coating additive to the first mixture, the second mixing is carried out under stirring conditions, and the second mixing time is preferably 10-15 minutes. The high-speed disperser can be selected as the FS-2.2 model.

[0051] The present invention provides a composite coating, which is obtained by mixing component A and component B of the composite coating, coating it onto a substrate, and then curing it.

[0052] Further, component B is added to component A and stirred for mixing. The stirring speed is preferably 3000 rpm and the time is 10-20 min.

[0053] Further, the A and B components of the composite coating are mixed to obtain a mixture;

[0054] The mixture is coated onto the surface of a substrate to obtain a wet film;

[0055] The obtained wet film is cured until completely dry, and a composite coating is obtained on the substrate surface.

[0056] Furthermore, the coating includes, but is not limited to, one of the following: brushing, rolling, dripping, and spraying. Brushing is preferred.

[0057] Furthermore, the curing can preferably be carried out in a constant temperature room, with the curing temperature preferably being 25°C, the relative humidity preferably being 50%, and the curing time preferably being 7 days.

[0058] The application of the organosilicon-modified fluorocarbon resin, the organosilicon-modified fluorocarbon resin antifouling coating, or the composite coating of the present invention in the protection of ship hull surfaces, wherein the surface protection includes surface protection for ships operating in temperate and low-temperature regions.

[0059] In the above technical solutions:

[0060] Organosilicon-modified fluorocarbon resin with antifouling properties is produced by a polycondensation reaction in which isocyanate groups are grafted into fluorocarbon resin to introduce organosilicon segments, forming a highly cross-linked organosilicon-modified fluorocarbon resin that uses isocyanate as a bridge to link organosilicon and fluorocarbon resin.

[0061] Therefore, this invention provides an organosilicon-modified fluorocarbon resin, composed of organosilicon segments, diisocyanate, and fluorocarbon resin. The organosilicon segments are monohydroxy-terminated polydimethylsiloxanes, which, based on the flexibility of their molecular segments, impart self-lubricating properties to the coating, thus improving the surface lubrication performance of the composite coating and reducing ice adhesion strength. Furthermore, the monohydroxy-terminated polydimethylsiloxanes, in a "molecular brush" state, are free on the coating surface, reducing surface friction and lowering the coefficient of friction. Simultaneously, the isocyanate groups exhibit good thermal stability and weather resistance, giving the coating excellent weather resistance and temperature alternation stability. The fluorocarbon resin is a monohydroxy-containing fluorocarbon resin, providing the coating with low surface energy properties, thus imparting hydrophobic and anti-fouling adhesion functions. The hydroxyl-containing structural units enable the resin to chemically react with the curing agent components, forming a dense cross-linked network and improving resin adhesion. The results of the embodiments show that the silicone-modified fluorocarbon resin provided by the present invention, after being coated onto the substrate and cured, has the characteristics of low surface energy, strong anti-fouling adhesion, good hydrophobicity, low coefficient of friction, good mechanical toughness, and low ice adhesion strength.

[0062] The composite coating provided by this invention mainly consists of the aforementioned organosilicon-modified fluorocarbon resin, and is also formulated with different pigments, fillers, and additives to achieve antifouling, self-lubrication, and anti-icing effects. Therefore, after room temperature curing, the composite coating provided by this invention exhibits excellent anti-icing and anti-marine fouling adhesion effects in actual low-temperature environments and marine testing. The results of the examples demonstrate that the organosilicon-modified fluorocarbon resin composite coating with antifouling properties provided by this invention is durable and has low ice adhesion. It retains good antifouling performance even after undergoing actual low-temperature environmental testing. It achieves the purpose of preventing fouling adhesion through the self-lubricating properties of the coating surface, and its surface also possesses anti-icing, ice-repellent, and cycle stability, making it suitable for the protection of ship hull surfaces in temperate and low-temperature regions. Attached Figure Description

[0063] Figure 1 These are water contact angle data for the silicone-modified fluorocarbon resin coatings of Examples 1-8 and Comparative Example 1.

[0064] Figure 2 These are stress-strain curve data graphs of the silicone-modified fluorocarbon resin coatings in Examples 1-8;

[0065] Figure 3 These are adhesion data graphs of the silicone-modified fluorocarbon resin coatings of Examples 1-8 and Comparative Example 1.

[0066] Figure 4 The friction coefficient data of the organosilicon-modified fluorocarbon resin coatings of Examples 1-8 and Comparative Example 1 are shown in the graph (load 200g): (a) friction coefficient in air and (b) friction coefficient in seawater.

[0067] Figure 5 The figures show experimental results data on the (a) inhibition ratio of *Nyctaginus simonii* and (b) *Diatomum bisporum* of the organosilicon-modified fluorocarbon resin coatings of Examples 1-8 and Comparative Example 1.

[0068] Figure 6 This is a schematic diagram of an ice adhesion device;

[0069] Figure 7 Examples 1-8 Comparative Example 1: (a) ice adhesion strength of silicone-modified fluorocarbon resin coating; (b) ice adhesion strength data after 20 freezing-de-icing cycles.

[0070] Figure 8 Graphs showing the ice adhesion strength of Examples 1-4 and Comparative Example 1 after 20 freezing-de-icing cycles following soaking in *Rhizophora pygmaea* for seven days;

[0071] Figure 9 Examples 1-6 show the actual outdoor anti-icing test data of the silicone-modified fluorocarbon resin composite coating and the blank epoxy board prepared within 30 days at an average temperature of -25℃.

[0072] Figure 10 The graph shows the data from four months of real-sea testing conducted immediately after Application Examples 1-6 underwent a 30-day -25℃ outdoor anti-icing test. Detailed Implementation

[0073] The present invention will now be described in detail through specific embodiments and application examples. However, the uses and purposes of these exemplary embodiments are only for illustrating the present invention and do not constitute any limitation on the actual protection scope of the present invention, nor are they intended to limit the protection scope of the present invention to these embodiments.

[0074] Example 1

[0075] The method for preparing an organosilicon-modified fluorocarbon resin antifouling coating according to this embodiment includes the following steps:

[0076] Step 1: Preparation of organosilicon-modified isocyanate prepolymer:

[0077] 35g of monohydroxy-terminated polydimethylsiloxane was added to a reaction vessel and vacuum stirred for 2 hours at 100°C to remove water. After the temperature dropped below 45°C, 38.43g of IPD I was added dropwise. After the addition was complete, 10g of xylene and 0.11g of dibutyltin dilaurate were added to the system and stirred until homogeneous. The temperature was then raised to 80°C and the reaction was carried out for 3.5 hours to obtain the organosilicon-modified isocyanate prepolymer, PI1.

[0078] Step 2: Preparation of silicone-modified fluorocarbon resin antifouling coating:

[0079] Weigh 10g of silicone-modified isocyanate prepolymer and 5g of xylene and stir them evenly in a high-power mechanical stirrer; then add 40g of fluorocarbon resin to the above solution and continue stirring until uniform. After stirring, silicone-modified fluorocarbon resin is obtained. Coat it onto a substrate and cure it to obtain silicone-modified fluorocarbon resin antifouling coating, denoted as PI5F4.

[0080] Comparative Example 1

[0081] In this comparative example, fluorocarbon resin was directly coated onto the substrate during the sample preparation process to obtain a fluorocarbon resin coating, denoted as FEVE.

[0082] The coating performance was tested in Example 1 and / or Comparative Example 1 as follows:

[0083] Contact angle performance test: The coating was made into a 7.5cm×2.5cm sample. The water contact angle of the coating surface was tested using a contact angle tester. Specifically, 5μL of deionized water was dropped onto the coating surface, and the contact angle was photographed and calculated using an optical microscope. Five different locations were measured for each sample, and the average value of the test results was taken. Figure 1The image shows the water contact angle data of the silicone-modified fluorocarbon resin coatings in Examples 1-8 and Comparative Example 1.

[0084] The water contact angle of PI5F4 in Example 1 was tested to be 91.94 ± 3.29°.

[0085] Tensile property test: The sample is made into a dumbbell shape and the mechanical properties of the sample are tested using a universal testing machine. Three sets of parallel samples are tested for each sample. Figure 2 The stress-strain curves of the silicone-modified fluorocarbon resin coatings in Examples 1-8 are shown.

[0086] The calculated elongation at break of PI5F4 in Example 1 was 120.12%, and the tensile strength was 3.53 MPa.

[0087] Adhesion test:

[0088] The coating size was 20cm×15cm (the substrate was a steel plate). Ergo 5180 surface treatment agent was sprayed onto the coating surface. After waiting for 1 minute for the coating surface to dry, six 2×2cm diameter pull rods were then attached to the coating surface to be tested using Ergo 5210 general-purpose quick-drying adhesive. After being placed at 25℃ for 48 hours to allow the adhesive to fully cure, the pull adhesion tester was used to test the adhesion. The values ​​were recorded and the average value was calculated as the adhesion of the coating. Figure 3 The image shows the adhesion data of the silicone-modified fluorocarbon resin coatings of Examples 1-8 and Comparative Example 1.

[0089] The adhesion of PI5F4 in Example 1 was calculated to be 4.93 ± 0.10 MPa.

[0090] Friction coefficient test:

[0091] The coating was prepared in 2.5cm × 2.5cm dimensions, and the coefficient of friction of the coating surface was tested using a tribological testing machine. Three parallel samples were tested for each sample, with the test parameters being a load of 200g and a friction radius of 3mm. Furthermore, the method for testing the coefficient of friction of the coating in water was the same as described above, except that the coating was completely immersed in water for the friction coefficient test. Figure 4 The friction coefficient data of the silicone-modified fluorocarbon resin coatings of Examples 1-8 and Comparative Example 1 are shown in (a) air and (b) water.

[0092] The friction coefficient of PI5F4 in Example 1 was tested and found to be stable at 0.29; the friction coefficient of PI5F4 in water was stable at 0.09.

[0093] Seaweed adhesion inhibition performance test:

[0094] The coating was prepared in the shape of 2.5cm × 2.5cm. A blank glass slide was selected as the control sample. The blank glass slide and the sample were immersed in two model algae species (N. closterium and Halamphora sp.) for 7 days, respectively. After removal, the unattached algae on the surface were gently shaken in deionized water. The number of algae attached to the coating was observed and recorded under an optical microscope. Five areas of each coating were randomly selected for photography. The algae adhesion inhibition rate (R) was calculated using the following formula:

[0095]

[0096] Where R represents the inhibition rate of seaweed attachment, and X represents the inhibition rate of seaweed attachment. B X represents the average number of algae adhering to the surface of the blank glass slide, while X represents the average number of algae adhering to the surface of the sample coating. Figure 5 The figures show the experimental results of (a) inhibiting the adhesion rate of *Nyctaginosa simulans* and (b) *Diatomata* of the organosilicon-modified fluorocarbon resin coatings of Examples 1-8 and Comparative Example 1.

[0097] Tests and calculations showed that PI5F4 inhibited the attachment rate of *Nyctaginea microphylla* by 96.15±3.6% and the attachment rate of *Dysplasia spp.* by 96.59±6.6% in Example 1.

[0098] Ice adhesion strength test:

[0099] The ice adhesion strength testing device was homemade. Figure 6 This is a schematic diagram of the adhesion device, which mainly includes a thrust sensor (NK-200), a platform, and acrylic tubes (1 cm in diameter and 3 cm in height). First, the coating sample to be tested (7.5 cm × 2.5 cm) is fixed on the platform, and nine acrylic 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 an environment of -20°C for 4 hours to ensure the water is completely frozen into ice columns. The maximum force (F) exerted by the thrust sensor to push the ice columns... max The force (W) is denoted as the force that removes ice from the sample surface. The above process is repeated at least three times to ensure repeatability. Ice adhesion strength (W) ice It can be calculated using the following formula:

[0100]

[0101] S ice This represents the area of ​​the icicle. The ice adhesion strength test is performed by repeating the 20-cycle freezing-de-icing cycle test. Figure 7 The graph shows (a) ice adhesion strength and (b) ice adhesion strength data of the silicone-modified fluorocarbon resin coatings of Examples 1-8 and Comparative Example 1 after 20 freezing-de-icing cycles.

[0102] The ice adhesion strength W of PI5F4 in Example 1 was determined through testing and calculation. ice = 9.03 ± 0.59 kPa, ice adhesion strength W after 20 freezing-de-icing cycles ice =48.06±2.37kPa

[0103] Cyclic stability test:

[0104] The coated sample (7.5cm×2.5cm) was first soaked in small crescent-shaped algae for 7 hours and then taken out. After taking it out, it was gently shaken in deionized water to remove the algae that were not attached to the surface. The sample was then placed in a 40℃ oven for 6 hours to remove the surface moisture. The dried sample was then subjected to an ice adhesion strength test, and the specific steps were the same as those for the ice adhesion strength test. Figure 6 The graph shows the ice adhesion strength data of Examples 1-8 and Comparative Example 1 after 20 freezing-de-icing cycles following soaking in *Rhizophora microcarpa* for seven days.

[0105] Tests and calculations showed that the ice adhesion strength of PI5F4 in Example 1 after 20 freezing-de-icing cycles following a seven-day soaking in *Nyctaginosa* was W. ice =49.37±2.37kPa.

[0106] Example 2

[0107] Referring to Example 1, the difference from Example 1 is that in the preparation process of the organosilicon modified fluorocarbon resin coating in this example, the amount of IPD I added in step one is 30.82g to obtain prepolymer PI2, and 30g of fluorocarbon resin is added in step two. The rest of the methods remain unchanged, as shown in Example 1, and Example 2 is referred to as PI5F3.

[0108] The tests were conducted according to the test methods of Example 1 and / or Comparative Example 1 described above. See [link to relevant documentation]. Figures 1-8 The results are as follows: water contact angle 97.87±1.93°; elongation at break and tensile strength 139.96% and 5.41 MPa, respectively; adhesion 4.70±0.12 MPa; coefficient of friction stable at 0.28, and coefficient of friction in water stable at 0.16; inhibition rate of *Nyctaginea microcarpa* 97.77±1.9%, inhibition rate of *Dysplasia spp.* 97.71±2.6%; ice adhesion strength W ice =7.65±0.64kPa, ice adhesion strength W after 20 freezing-de-icing cycles ice = 43.60 ± 3.68 kPa; the ice adhesion strength after 20 freezing-de-icing cycles following 10 days of soaking in *Nyctaginosa* was W. ice =44.37±1.26kPa.

[0109] Example 3

[0110] Referring to Example 1, the difference from Example 1 is that in the preparation process of the organosilicon modified fluorocarbon resin coating in this example, the amount of IPD I added in step one is 26.09g to obtain prepolymer PI3, and 20g of fluorocarbon resin is added in step two. The rest of the methods remain unchanged, as shown in Example 1, and Example 3 is referred to as PI5F2.

[0111] The test was conducted according to the test method in Example 1, see [link / reference]. Figures 1-8 The results are as follows: water contact angle 100.93±1.67°; elongation at break and tensile strength 169.52% and 5.15 MPa, respectively; adhesion 3.89±0.19 MPa; coefficient of friction stable at 0.24, and coefficient of friction in water stable at 0.04; inhibition rate of *Nyctaginea microcarpa* 98.25±1.8%, inhibition rate of *Dysplasia spp.* 98.29±2.5%; ice adhesion strength W ice = 9.08 ± 0.81 kPa, ice adhesion strength W after 20 freezing-de-icing cycles ice =33.75±1.13kPa; the ice adhesion strength after 20 freezing-de-icing cycles following 10 days of soaking in *Nyctaginosa* was W. ice =35.69±2.70kPa.

[0112] Example 4

[0113] Referring to Example 1, the difference from Example 1 is that in the preparation process of the organosilicon modified fluorocarbon resin coating in this example, the amount of IPD I added in step one is 19.27g to obtain prepolymer PI4, and 15g of fluorocarbon resin is added in step two. The rest of the methods remain unchanged, as shown in Example 1, and Example 4 is denoted as P2 I5F3.

[0114] The tests were conducted according to the test methods of Example 1 and / or Comparative Example 1 described above. See [link to relevant documentation]. Figures 1-8 The results are as follows: water contact angle was 104.11±1.31°; elongation at break and tensile strength were 213.78% and 3.93 MPa, respectively; adhesion was 1.56±0.41 MPa; the coefficient of friction remained stable at 0.35, and the coefficient of friction in water remained stable at 0.13; the inhibition rate of *Nyctaginea microcarpa* was 97.37±1.2%, and the inhibition rate of *Dysplasia cerana* was 94.01±3.7%; ice adhesion strength W... ice =8.89±1.00kPa, ice adhesion strength W after 20 freezing-de-icing cycles ice =58.70±1.85kPa; the ice adhesion strength after 20 freezing-de-icing cycles following 10 days of soaking in *Nyctaginata* was W. ice =60.26±1.37kPa.

[0115] Example 5

[0116] Referring to Example 1, the difference from Example 1 is that in the preparation process of the organosilicon modified fluorocarbon resin coating in this example, the amount of IPD I added in step one is 48.07g, and the prepolymer PI5 is obtained. The rest of the methods remain unchanged, as shown in Example 1, and Example 5 is denoted as PI7F4.

[0117] The tests were conducted according to the test methods of Example 1 and / or Comparative Example 1 described above. See [link to relevant documentation]. Figures 1-8 The results are as follows: water contact angle 90.83±3.72°; elongation at break and tensile strength 235.43% and 3.66 MPa, respectively; adhesion 5.52±0.09 MPa; coefficient of friction stable at 0.07, and coefficient of friction in water stable at 0.03; inhibition rate of *Nyctaginea microcarpa* 96.58±5.2%, inhibition rate of *Dysplasia spp.* 97.14±3.2%; ice adhesion strength W ice =8.97±0.49kPa, ice adhesion strength W after 20 freezing-de-icing cycles ice = 44.71 ± 1.07 kPa; the ice adhesion strength after 20 freezing-de-icing cycles following 10 days of soaking in *Nyctaginosa* was W. ice =45.62±2.37kPa.

[0118] Example 6

[0119] Referring to Example 1, the difference from Example 1 is that in the preparation process of the organosilicon modified fluorocarbon resin coating in this example, the amount of IPD I added in step one is 38.53g to obtain prepolymer PI6, and in step two, 30g of fluorocarbon resin is added and the rest of the method remains unchanged, as shown in Example 1, and Example 6 is denoted as PI7F3.

[0120] The tests were conducted according to the test methods of Example 1 and / or Comparative Example 1 described above. See [link to relevant documentation]. Figures 1-8 The results are as follows: water contact angle 98.35±1.42°; elongation at break and tensile strength 203.92% and 7.92 MPa, respectively; adhesion 5.02±0.36 MPa; coefficient of friction stable at 0.05, and coefficient of friction in water stable at 0.02; inhibition rate of *Nyctaginea microcarpa* 97.45±9.0%, inhibition rate of *Dysplasia spp.* 97.71±3.2%; ice adhesion strength W ice =8.85±0.53kPa, ice adhesion strength W after 20 freezing-de-icing cycles ice = 45.43 ± 1.06 kPa; the ice adhesion strength after 20 freezing-de-icing cycles following 10 days of soaking in *Nyctaginosa* was W. ice =46.02±3.25kPa.

[0121] Example 7

[0122] Referring to Example 1, unlike Example 1, in the preparation process of the organosilicon modified fluorocarbon resin coating in this example, the amount of IPD I added in step one is 31.92g to obtain prepolymer PI7, and in step two, 20g of fluorocarbon resin is added, and the rest of the method remains unchanged, as shown in Example 1, and Example 7 is denoted as PI7F2.

[0123] The tests were conducted according to the test methods of Example 1 and / or Comparative Example 1 described above. See [link to relevant documentation]. Figures 1-8 The results are as follows: water contact angle 99.45±2.89°; elongation at break and tensile strength 150.01% and 9.13 MPa, respectively; adhesion 4.84±0.29 MPa; coefficient of friction stable at 0.04, and coefficient of friction in water stable at 0.01; inhibition rate of *Nyctaginea microcarpa* 98.96±1.8%, inhibition rate of *Dysporum tobira* 98±2.0%; ice adhesion strength W ice =7.95±0.94kPa, ice adhesion strength W after 20 freezing-de-icing cycles ice =25.77±1.87kPa; the ice adhesion strength after 20 freezing-de-icing cycles following 10 days of soaking in *Nyctaginata* was W. ice =26.35±1.40kPa.

[0124] Example 8

[0125] Referring to Example 1, the difference from Example 1 is that in the preparation process of the organosilicon modified fluorocarbon resin coating in this example, the amount of IPD I added in step one is 24.09g to obtain prepolymer PI8, and 15g of fluorocarbon resin is added in step two, with the rest of the method remaining unchanged, as shown in Example 1, and Example 8 is denoted as P2I7F3.

[0126] The tests were conducted according to the test methods of Example 1 and / or Comparative Example 1 described above. See [link to relevant documentation]. Figures 1-8 The results are as follows: water contact angle 104.88±1.23°; elongation at break and tensile strength 180.89% and 7.74 MPa, respectively; adhesion 3.52±0.36 MPa; coefficient of friction stable at 0.19, and coefficient of friction in water stable at 0.11; inhibition rate of *Nyctaginea microcarpa* 96.09±4.1%, inhibition rate of *Dysporum tobira* 95.71±5.8%; ice adhesion strength W ice =6.85±0.53kPa, ice adhesion strength W after 20 freezing-de-icing cycles ice = 48.99 ± 2.70 kPa; the ice adhesion strength after 20 freezing-de-icing cycles following 10 days of soaking in *Nyctaginosa* was W. ice =51.03±1.99kPa.

[0127] The tests were conducted according to the test methods of Example 1 and / or Comparative Example 1 described above. See [link to relevant documentation]. Figures 1-8 The results are as follows: the water contact angle is 90.24±1.61°; the sample of Comparative Example 1 cannot meet the requirements for testing elongation at break and tensile strength; the adhesion is 4.57±0.09MPa; the coefficient of friction is stable at 0.13, and the coefficient of friction in water is stable at 0.25; the inhibition rate of *Nyctaginea microcarpa* is 73.21±2.2%, and the inhibition rate of *Dysplasia cerana* is 78.57±6.9%; the ice adhesion strength W... ice =45.50±2.74kPa, ice adhesion strength W after 20 freezing-de-icing cycles ice = 91.25 ± 2.84 kPa; the ice adhesion strength after 20 freezing-de-icing cycles following a seven-day soaking in *Nyctaginosa* was W. ice =103.58±1.26kPa.

[0128] Application Example 1

[0129] The preparation of a composite coating of organosilicon-modified fluorocarbon resin in this application example includes component A and component B; wherein the composition of component A is as follows:

[0130]

[0131] The above-mentioned organosilicon-modified isocyanate prepolymer, titanium dioxide and xylene were added to the dispersion tank at one time and dispersed at 3000 r / min for 15 min. Then, the coating additives (BYK163, BYK066, EFKA3777) were added and dispersed at 3000 r / min for 20 min. After the dispersion was completed, the material was discharged after inspection to find that there were no particulate substances. Component A of the composite coating was obtained.

[0132] Group B's allocation is as follows:

[0133]

[0134] Component B is added to component A in sequence and dispersed evenly using a high-speed disperser at 3000 r / min for 10 min. After dispersion, the material is discharged after inspection to find no particulate matter, thus obtaining a composite coating. This coating is then applied to an epoxy board and, after complete curing, is designated as PI5F3C.

[0135] Real-world outdoor anti-icing test:

[0136] The fully cured PI5F3C was placed in an outdoor environment with an average temperature of -25℃. Photos were taken every ten days to record the surface freezing or frosting. The cycle was 30 days. Figure 9Examples 1-6 show the actual outdoor anti-icing test data of the silicone-modified fluorocarbon resin composite coating and the blank epoxy board prepared within 30 days at an average temperature of -25℃.

[0137] Sea testing:

[0138] After undergoing 30 days of low-temperature testing, the PI5F3C was placed in the sea area of ​​Xiaochangshan Island Town, Changhai County, Dalian City, Liaoning Province for a real-sea test. The coating was immersed in the sea and periodically removed for photographic recording. Figure 10 The graph shows the data from four months of real-sea testing conducted immediately after Application Examples 1-6 underwent a 30-day -25℃ outdoor anti-icing test.

[0139] Application Example 2-6

[0140] Referring to Application Example 1, the difference between Application Examples 2-6 and Application Example 1 is that the amounts of some substances in components A and B are different, while the other operations are the same. Table 1 shows the amounts of different raw materials used in Application Examples 2-6 compared to Application Example 1.

[0141] Referring to Application Example 1, the actual outdoor anti-icing test data of Application Examples 2-6 are shown in the figure below. Figure 9 The actual sea test data is shown in the figure. Figure 10 .

[0142] Table 1

[0143]

[0144]

[0145] Depend on Figure 9 It can be seen that, compared with the blank epoxy board, the silicone-modified fluorocarbon resin composite coating exhibits good anti-icing ability after 30 days of low temperature. The area of ​​frost and snow on the surface of different silicone-modified fluorocarbon resin composite coatings is smaller than that of the blank epoxy board, especially PI7F3C, PI7F2C and P2I7F3C.

[0146] Figure 10 In the study, after 30 days of low temperature and four months of actual sea testing, the results showed that the organosilicon-modified fluorocarbon resin composite coating still had excellent ability to inhibit fouling and bioadhesion. This indicates that the prepared organosilicon-modified fluorocarbon resin composite coating not only has good antifouling and anti-icing capabilities, but also good temperature alternation stability, and has certain practical application value.

[0147] In summary, as can be seen from the above application examples, existing protective coatings for ships operating over large temperature ranges generally cannot simultaneously provide both anti-icing and anti-fouling properties. These coatings suffer from problems such as high friction coefficient, high resistance, poor stain resistance, difficulty in cleaning, and easy retention of water droplets, leading to the adhesion of contaminants and icing on the coating surface. The organosilicon-modified fluorocarbon resin composite coating provided by this invention has advantages such as a low friction coefficient, a large water contact angle (104.88±1.23°), a hard, dense, and smooth texture, and low ice adhesion (25.77±1.87kPa). It can achieve surface anti-fouling through the special physicochemical properties of the coating surface in temperate and cold environments, while also possessing anti-icing and anti-icing properties.

[0148] Although the above embodiments and application examples have provided a detailed description of the present invention, they are only some embodiments of the present invention, not all embodiments. Other embodiments can be obtained based on these embodiments without creative intent, and these embodiments all fall within the protection scope of the present invention.

Claims

1. A composite coating, characterized by, The A component and the B component are independently packed, the A component comprises the following components by mass fraction: silicone modified isocyanate prepolymer 8-15 parts, first organic solvent 7-16 parts, pigment and filler 6-12 parts and coating additive 0.1-1 part; the coating additive comprises one or more of dispersant, leveling agent and defoaming agent; The B component comprises the following components by mass fraction: fluorocarbon resin 10-40 parts, catalyst 0.1-1 part, anti-settling agent 0.2-0.8 part and second organic solvent 6-14 parts; The silicone modified isocyanate prepolymer is prepared as follows: In a reaction container, monohydroxyl terminated polydimethylsiloxane is dehydrated under vacuum stirring at 100 DEG C, and then diisocyanate is added dropwise when the temperature is lower than 45 DEG C; after the dropwise addition is completed, organic solvent and catalyst are added into the system, and then the system is stirred uniformly and heated to 60-80 DEG C for sufficient reaction, to obtain silicone modified isocyanate prepolymer.

2. The composite coating of claim 1, wherein, The diisocyanate is one or more of toluene diisocyanate, isophorone diisocyanate, diphenyl methane diisocyanate, dicyclohexyl methane diisocyanate, hexamethylene diisocyanate and lysine diisocyanate; And / or, the catalyst is one or more of triethylamine and dibutyl tin dilaurate; And / or, the organic solvent is one or more of xylene, propylene glycol methyl ether and propylene glycol methyl ether acetate.

3. The composite coating of claim 1, wherein, The monohydroxyl terminated polydimethylsiloxane has a relative molecular weight of 2000-2500; and / or, the monohydroxyl terminated polydimethylsiloxane has the following general structure: ； In the formula, R4 is hydrogen or methyl, R5 is C1-8 alkylene, and n is an integer of 24-31.

4. The composite coating of claim 1, wherein, The fluorocarbon resin is FEVE fluorocarbon resin, and has a relative molecular weight of 1000-2000; or the fluorocarbon resin has the following general structure: ； In the formula, R1 is hydrogen or methyl, R2 is C1-8 alkyl, R3 is C2-3 olefin, and X is chlorohydrocarbon.

5. Use of the composite coating according to claim 1 for the protection of ship hull surfaces, characterized in that The surface protection includes surface protection for ships running in temperate and low temperature areas.

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