Organic silicon modified fluorocarbon resin with antifouling property, antifouling coating thereof, composite coating and preparation method and application of organic silicon modified fluorocarbon resin

Abstract

The invention discloses organic silicon modified fluorocarbon resin with antifouling property, an antifouling coating thereof, a composite coating and a preparation method and application of the organic silicon modified fluorocarbon resin. The organic silicon modified fluorocarbon resin is prepared by carrying out condensation polymerization on diisocyanate, fluorocarbon resin, monohydroxyl-terminated polydimethylsiloxane and a catalyst in an organic solvent. Coating a substrate with the organic silicon modified fluorocarbon resin obtained after the reaction, and curing to obtain an organic silicon modified fluorocarbon resin coating; the component A and the component B are mixed to generate the composite coating containing the organic silicon modified fluorocarbon resin as a main component. The organic silicon modified fluorocarbon resin disclosed by the invention has the characteristics of low surface energy, strong anti-fouling adhesion capacity, good hydrophobicity, small friction coefficient, good mechanical toughness and small ice adhesion strength.

Description

Technical Field

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

[0002] Developing the marine economy, accelerating the pace of marine science and technology innovation, protecting the marine ecological environment, promoting the construction of the 21st Century Maritime Silk Road, and building a community with a shared future for the ocean all rely on the ships and marine equipment and facilities. In recent years, with the increase in the development of marine resources, researchers have found that the polar regions are rich in chemical energy, biological resources, and mineral resources. As a result, ships travel frequently between temperate and cold regions. The protection of the ship surface cannot be limited to inhibiting the attachment of fouling organisms to its surface. It is also necessary to consider the damage caused by the ice on the ship surface caused by the ice of the waves when sailing in low-temperature areas and the friction of the 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. The contact angle of coatings made from fluorocarbon resin-containing coatings is usually 85-95°. Although they have certain protective effects, their anti-fouling and anti-icing effects are generally poor. Modification of fluorocarbon resin coatings with silicon-based modified additives can reduce the surface tension of fluorocarbon resin coatings and increase the contact angle of fluorocarbon resin coatings. The contact angle of the modified fluorocarbon resin coating is 100-115°.

[0004] The Chinese patent with application number 202310015847.6 discloses a high-strength anti-icing coating, a high-strength anti-icing coating, and a preparation method and application thereof, wherein the high-strength anti-icing coating, by weight, includes the following preparation raw materials: 100 parts of skeleton material, 0-40 parts of solid lubricant, 0.2-0.8 parts of leveling agent, 0.2-0.8 parts of defoaming agent, 0.2-1 parts of catalyst, 100-10000 parts of organic solvent; the skeleton material is a coating precursor and a curing agent; the coating precursor includes a resin precursor and an organosilicon precursor. The invention forms an interpenetrating polymer network coating with low ice adhesion by using an organosilicon precursor compounded with a curing agent.

[0005] The Chinese patent application number 202311777179.7 discloses an anti-fouling membrane for sewage treatment and a preparation method thereof, wherein the anti-fouling membrane for sewage treatment is composed of the following raw materials in parts by weight: 80-100 parts of PVC, 20-30 parts of fluorocarbon resin, 30-60 parts of deionized water, 3-13 parts of titanium dioxide nanoparticles, 5-10 parts of polysiloxane, 5-10 parts of titanium nitrate, 5-10 parts of organosilane, 1-2 parts of curing agent, 5-8 parts of defoaming agent, 1-3 parts of stabilizer, 0.01-0.05 parts of antioxidant, 1-3 parts of cross-linking agent, 1-3 parts of hydrophobic agent, 4-6 parts of silicone-acrylic emulsion, 6-10 parts of polytetrafluoroethylene dispersion emulsion, 5-8 parts of toughening agent, and 0.5-1 parts of thickener. The invention obtains an anti-fouling membrane by stirring and mixing fluorocarbon resin and organosilane, which has a good non-adhesive effect on common stains.

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

[0007] In view of this, the purpose of the present invention is to propose an organosilicon-modified fluorocarbon resin with antifouling properties, an antifouling coating thereof, a composite coating and a preparation method and application thereof, wherein the organosilicon-modified fluorocarbon resin with antifouling properties is formed by a polycondensation reaction, using isocyanate as a bridge to link organosilicon and fluorocarbon resin to form an organosilicon-modified fluorocarbon resin with a high degree of crosslinking, and the organosilicon-modified fluorocarbon resin obtained after the reaction is coated on a substrate and cured to obtain an organosilicon-modified fluorocarbon resin coating; the composite coating can be generated by mixing its A component and B component to form a composite coating containing the organosilicon-modified fluorocarbon resin as a main component, which has self-lubricating properties, specifically manifested in low surface energy, strong ability to inhibit adhesion of marine fouling organisms, small underwater friction coefficient, good mechanical flexibility, low ice adhesion, and high cyclic stability, and is particularly suitable for protecting the surface of hulls traveling between temperate and cold zones.

[0008] The technical solutions adopted are:

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

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

[0011] S1. Preparation of silicone modified isocyanate prepolymer:

[0012] Add monohydroxy-terminated polydimethylsiloxane to a reaction vessel at 100°C, stir and dehydrate under vacuum, and when the temperature is lower than 45°C, drop diisocyanate therein, add organic solvent and catalyst to the system after the dropwise addition is complete, stir evenly, and then heat to 60-80°C to fully react to obtain silicone-modified isocyanate prepolymer;

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

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

[0015] Further, the diisocyanate includes, but is not limited to, one or more of toluene diisocyanate (TDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMDI), 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 of monohydroxy-terminated polydimethylsiloxane is 102782-86-5.

[0022] Furthermore, the fluorocarbon resin is a FEVE fluorocarbon resin with a relative molecular weight of 1000 to 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 group; and X is a chlorinated hydrocarbon.

[0025] Furthermore, 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 organosilicon-modified fluorocarbon resin antifouling coating of the invention comprises coating the organosilicon-modified fluorocarbon resin on a substrate and curing the substrate to obtain the organosilicon-modified fluorocarbon resin antifouling coating.

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

[0028] A composite coating of the present invention comprises independently packaged component A and component B, wherein the component A comprises the following components in parts by weight: an organosilicon-modified isocyanate prepolymer, a first organic solvent, a pigment and a filler, and a coating additive; the coating additive comprises one or more of a dispersant, a leveling agent, and a defoaming agent;

[0029] The B component includes the following components in parts by weight: a fluorocarbon resin, a catalyst, an anti-settling agent, and a second organic solvent;

[0030] The preparation of the organosilicon-modified isocyanate prepolymer is as follows:

[0031] Add monohydroxy-terminated polydimethylsiloxane to a reaction container at 100°C, stir and dehydrate under vacuum, and when the temperature is lower than 45°C, drop diisocyanate thereinto. After the dropwise addition is completed, add an organic solvent and a catalyst to the system, stir evenly, and then heat to 60-80°C for sufficient reaction to obtain an organosilicon-modified isocyanate prepolymer.

[0032] Furthermore, the time for sufficient reaction is 2.5-4h.

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

[0034] The B component includes the following components in parts by mass: 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 pigment filler is one or more of titanium dioxide, talc, silica powder, wollastonite and sericite.

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

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

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

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

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

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

[0042] The preparation method of the composite coating of the present invention comprises the following steps:

[0043] Step 1. Preparation of component A:

[0044] The prepared organosilicon-modified isocyanate prepolymer, the first organic solvent and the pigment and filler are mixed for the first time to obtain a first mixed material;

[0045] Mixing the first mixed material and the coating additive for a second time to obtain a second mixed material;

[0046] The second mixed material is fully mixed with a high-speed disperser until it is uniform, to obtain component A;

[0047] Step 2. Preparation of component B:

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

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

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

[0051] The composite coating of the present invention is obtained by mixing component A and component B in the composite coating, coating the mixture on a substrate and curing the mixture.

[0052] Furthermore, component B is added into component A and stirred and mixed. The stirring speed is preferably 3000 rpm and the stirring time is 10-20 min.

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

[0054] coating the mixture on the surface of a substrate to obtain a wet film;

[0055] The obtained wet film is cured until it is completely dry to obtain a composite coating on the surface of the substrate.

[0056] Further, the coating includes but is not limited to one of brush coating, roller coating, drip coating and spray coating. Brush coating may be preferred.

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

[0058] The organosilicon-modified fluorocarbon resin, the organosilicon-modified fluorocarbon resin antifouling coating, or the composite coating of the present invention is used for hull surface protection, and the surface protection includes surface protection for ships traveling in temperate and low-temperature areas.

[0059] In the above technical solution:

[0060] The anti-fouling silicone-modified fluorocarbon resin is prepared by polycondensation reaction, using isocyanate groups to introduce silicone segments into the fluorocarbon resin by grafting, thereby forming a highly cross-linked silicone-modified fluorocarbon resin with isocyanate as a bridge to link the silicone and the fluorocarbon resin.

[0061] Therefore, the present invention provides an organosilicon-modified fluorocarbon resin, which is composed of an organosilicon segment, a diisocyanate and a fluorocarbon resin. The organosilicon segment is a monohydroxy-terminated polydimethylsiloxane. Based on the characteristic flexibility of its molecular segment, the coating is endowed with self-lubricating properties, which is beneficial to improving the lubrication performance of the composite coating surface and reducing the ice adhesion strength. The exterior of the monohydroxy-terminated polydimethylsiloxane is free on the coating surface in the state of a "molecular brush", which can reduce the friction force on the coating surface and reduce the friction coefficient. At the same time, the isocyanate group has good thermal stability and weather resistance, which gives the coating good weather resistance and temperature alternating stability. The fluorocarbon resin is a monohydroxy-containing fluorocarbon resin, which provides low surface energy properties for the coating, and gives the coating hydrophobic and anti-fouling adhesion functions. The structural unit containing hydroxyl groups can cause the resin to react chemically with the curing agent component to form a dense cross-linked network, thereby improving the resin adhesion. The results of the examples show that the silicone-modified fluorocarbon resin provided by the present invention has the characteristics of low surface energy, strong anti-fouling adhesion ability, good hydrophobicity, low friction coefficient, good mechanical toughness and low ice adhesion strength after being coated on a substrate and cured.

[0062] The composite coating provided by the present invention has the above-mentioned organosilicon-modified fluorocarbon resin as the main component, and is compounded with different pigments, fillers and additives to achieve the effects of anti-fouling, self-lubrication and anti-icing. Therefore, after being cured at room temperature, the composite coating provided by the present invention has good anti-icing and anti-marine fouling adhesion effects in actual low-temperature environments and actual sea tests. The results of the embodiments show that the organosilicon-modified fluorocarbon resin composite coating with anti-fouling properties provided by the present invention is durable and has low ice adhesion, and can still have good anti-fouling properties after being tested in actual low-temperature environments. The purpose of preventing fouling adhesion is achieved through the self-lubricating properties of the coating surface, and its surface has both anti-icing, ice-repellent and cyclic stability, and is suitable for the protection of hull surfaces in temperate and low-temperature regions. BRIEF DESCRIPTION OF THE DRAWINGS

[0063] Figure 1 is a water contact angle data graph of the organosilicon-modified fluorocarbon resin coatings of Examples 1-8 and Comparative Example 1;

[0064] Figure 2 is a stress-strain curve data diagram of the organosilicon-modified fluorocarbon resin coating of Examples 1-8;

[0065] Figure 3 is a graph showing the adhesion data of the organosilicon-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 (load 200 g) (a) friction coefficient in air (b) friction coefficient in seawater;

[0067] Figure 5 1 is a data graph showing the experimental results of the ratio of (a) inhibiting Nitzschia closterium and (b) dichaete of the organosilicon-modified fluorocarbon resin coatings of Examples 1-8 and Comparative Example 1;

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

[0069] Figure 7 Examples 1-8 Comparative Example 1 (a) Ice adhesion strength of organosilicon-modified fluorocarbon resin coating (b) Ice adhesion strength data graph of 20 icing-deicing cycles;

[0070] Figure 8 Ice adhesion strength data of Examples 1-4 and Comparative Example 1 after 20 ice-deicing cycles after being soaked in Nitzschia closterium for seven days;

[0071] Fig. 9 Application Examples 1-6 are actual outdoor environment anti-icing test data of the organosilicon-modified fluorocarbon resin composite coating and a blank epoxy board prepared within 30 days at an average temperature of -25°C;

[0072] Fig.10 This is a graph of data from a four-month actual sea test conducted immediately after Application Example 1-6 underwent a 30-day -25°C outdoor anti-icing test. DETAILED DESCRIPTION

[0073] 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.

[0074] Example 1

[0075] The method for preparing a silicone-modified fluorocarbon resin antifouling coating of this embodiment comprises the following steps:

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

[0077] 35 g of monohydroxy-terminated polydimethylsiloxane was added to a reaction container at 100 ° C, and vacuum-stirred for dehydration for 2 h. After the temperature was lower than 45 ° C, 38.43 g of IPD I was added dropwise therein. After the addition was completed, 10 g of xylene and 0.11 g of dibutyltin dilaurate were added to the system, stirred evenly, and then heated to 80 ° C and reacted for 3.5 h to obtain a silicone-modified isocyanate prepolymer, PI1.

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

[0079] Weigh 10 g of organosilicon-modified isocyanate prepolymer and 5 g of xylene and stir them evenly in a strong mechanical stirrer; then add 40 g of fluorocarbon resin to the above solution and continue stirring until it is evenly mixed. After the stirring is completed, an organosilicon-modified fluorocarbon resin is obtained, which is coated on a substrate and cured to obtain an organosilicon-modified fluorocarbon resin antifouling coating, which is recorded as PI5F4;

[0080] Comparative Example 1

[0081] In this comparative example, the fluorocarbon resin is directly coated on the substrate during the sample preparation process to obtain a fluorocarbon resin coating, which is recorded as FEVE.

[0082] The following experiments were performed to test the coating properties in Example 1 and / or Comparative Example 1:

[0083] Contact angle performance test: The coating was made into 7.5cm×2.5cm, and the water contact angle of the coating surface was tested using a contact angle tester. Specifically, 5μL of deionized water was dropped on the coating surface, and an optical microscope was used to take pictures and calculate the contact angle. Five different positions were taken for each sample, and the test results were averaged. Figure 1The water contact angle data of the organosilicon-modified fluorocarbon resin coatings of Examples 1-8 and Comparative Example 1 are shown;

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

[0085] 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 2 1 is the stress-strain curve of the organosilicon-modified fluorocarbon resin coating of Examples 1-8;

[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 is 20cm×15cm (the substrate is a steel plate). Ergo 5180 surface treatment agent is sprayed on the coating surface. After waiting for 1 minute, the coating surface is dry. Then, ergo 5210 general quick-drying glue is used to stick 6 pulling ingots with a diameter of 2×2cm on the surface of the coating to be tested. After being placed at 25°C for 48 hours and the glue is completely cured, it is tested with a pulling adhesion tester. The values ​​are recorded and the average value is calculated as the adhesion of the coating. Figure 3 It is a graph showing the adhesion data of the organosilicon-modified fluorocarbon resin coatings of Examples 1-8 and Comparative Example 1;

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

[0090] Friction coefficient test:

[0091] 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. In addition, the test method for the friction coefficient of the coating in water was similar to the above, except that the coating was completely immersed in water for the friction coefficient test. Figure 4 The friction coefficient data of the organosilicon-modified fluorocarbon resin coatings of Examples 1-8 and Comparative Example 1 are (a) in air and (b) in water;

[0092] After testing, the friction coefficient of PI5F4 in Example 1 was stabilized at 0.29; the friction coefficient of PI5F4 in water was stabilized at 0.09.

[0093] Test on the performance of inhibiting algae adhesion:

[0094] 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:

[0095]

[0096] 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 5 The data graphs are experimental results of the silicone-modified fluorocarbon resin coatings of Examples 1-8 and Comparative Example 1 for inhibiting the adhesion rate of (a) Nitzschia closterium and (b) Diplocoriella serrata;

[0097] Through testing and calculation, it was found that the inhibition rate of PI5F4 in Example 1 was 96.15±3.6% for the attachment of Nitzschia closterium, and 96.59±6.6% for the attachment of Dictyophora closterium.

[0098] Ice adhesion strength test:

[0099] The ice adhesion strength test device was made by ourselves. Figure 6 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:

[0100]

[0101] S ice is the area of ​​the icicle. The 20 icing-deicing cycle test is the ice adhesion strength test repeated 20 times Figure 7 Graphs showing (a) ice adhesion strength and (b) ice adhesion strength after 20 icing-deicing cycles of the organosilicon-modified fluorocarbon resin coatings of Examples 1-8 and Comparative Example 1.

[0102] The ice adhesion strength W of PI5F4 in Example 1 is obtained through testing and calculation. ice =9.03±0.59kPa, 20 icing-deicing cycles Ice adhesion strength W ice =48.06±2.37kPa

[0103] Cyclic stability test:

[0104] The coating sample (7.5cm×2.5cm) was first soaked in Nitzschia closterium for 7 hours 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 It is a data graph of ice adhesion strength after 20 ice-deicing cycles of Examples 1-8 and Comparative Example 1 after being soaked in Nitzschia closterium for seven days.

[0105] Through testing and calculation, it is found that the ice adhesion strength of PI5F4 in Example 1 after 20 ice-deicing cycles after being soaked in Nitzschia closterium for seven days is 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 a silicone-modified fluorocarbon resin coating in this example, the amount of IPD I added in step one is 30.82 g to obtain prepolymer PI2, and 30 g of fluorocarbon resin is added in step two. The rest of the method remains unchanged, as shown in Example 1, and Example 2 is recorded as PI5F3.

[0108] The test was performed according to the test method of the above-mentioned Example 1 and / or Comparative Example 1, see Figure 1-Figure 8 The results are as follows: the water contact angle is 97.87±1.93°; the elongation at break and the tensile strength are 139.96% and 5.41MPa respectively; the adhesion is 4.70±0.12MPa; the friction coefficient is stable at 0.28, and the friction coefficient in water is stable at 0.16; the inhibition rate of Nitzschia closterium is 97.77±1.9%, and the inhibition rate of Bletilla striata is 97.71±2.6%; the ice adhesion strength W ice =7.65±0.64kPa, 20 icing-deicing cycles Ice adhesion strength W ice =43.60±3.68kPa; after 20 icing-deicing cycles of soaking in Nitzschia closterium for ten days, the ice adhesion strength is 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 a silicone-modified fluorocarbon resin coating in this example, the amount of IPD I added in step one is 26.09 g to obtain prepolymer PI3, and 20 g of fluorocarbon resin is added in step two. The rest of the method remains unchanged, as shown in Example 1, and Example 3 is recorded as PI5F2.

[0111] Test according to the test method of Example 1, see Figure 1-Figure 8 The results are as follows: the water contact angle is 100.93±1.67°; the elongation at break and the tensile strength are 169.52% and 5.15MPa respectively; the adhesion is 3.89±0.19MPa; the friction coefficient is stable at 0.24, and the friction coefficient in water is stable at 0.04; the inhibition rate of Nitzschia closterium is 98.25±1.8%, and the inhibition rate of Bletilla striata is 98.29±2.5%; the ice adhesion strength W ice =9.08±0.81kPa, 20 icing-deicing cycles Ice adhesion strength W ice =33.75±1.13kPa; after 20 icing-deicing cycles of soaking in Nitzschia closterium for ten days, the ice adhesion strength is 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 a silicone-modified fluorocarbon resin coating in this example, the amount of IPD I added in step one is 19.27 g to obtain prepolymer PI4, and 15 g of fluorocarbon resin is added in step two. The rest of the method remains unchanged, as shown in Example 1, and Example 4 is recorded as P2 I5F3.

[0114] The test was performed according to the test method of the above-mentioned Example 1 and / or Comparative Example 1, see Figure 1-Figure 8 The results are as follows: the water contact angle is 104.11±1.31°; the elongation at break and the tensile strength are 213.78% and 3.93MPa respectively; the adhesion is 1.56±0.41MPa; the friction coefficient is stable at 0.35, and the friction coefficient in water is stable at 0.13; the inhibition rate of Nitzschia closterium is 97.37±1.2%, and the inhibition rate of Bletilla striata is 94.01±3.7%; the ice adhesion strength W ice =8.89±1.00kPa, 20 icing-deicing cycles Ice adhesion strength W ice =58.70±1.85kPa; after 20 icing-deicing cycles of soaking in Nitzschia closterium for ten days, the ice adhesion strength is 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 a silicone-modified fluorocarbon resin coating in this example, the amount of IPD I added in step one is 48.07 g to obtain a prepolymer PI5, and the rest of the method remains unchanged, as shown in Example 1, and Example 5 is recorded as PI7F4.

[0117] The test was performed according to the test method of the above-mentioned Example 1 and / or Comparative Example 1, see Figure 1-Figure 8 The results are as follows: the water contact angle is 90.83±3.72°; the elongation at break and the tensile strength are 235.43% and 3.66MPa respectively; the adhesion is 5.52±0.09MPa; the friction coefficient is stable at 0.07, and the friction coefficient in water is stable at 0.03; the inhibition rate of Nitzschia closterium is 96.58±5.2%, and the inhibition rate of Bletilla striata is 97.14±3.2%; the ice adhesion strength W ice =8.97±0.49kPa, 20 icing-deicing cycles Ice adhesion strength W ice =44.71±1.07 kPa; after 20 icing-deicing cycles of soaking in Nitzschia closterium for ten days, the ice adhesion strength is 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 a silicone-modified fluorocarbon resin coating in this example, the amount of IPD I added in step one is 38.53 g to obtain prepolymer PI6, and 30 g of fluorocarbon resin is added in step two, and the rest of the method remains unchanged, as shown in Example 1, and Example 6 is recorded as PI7F3.

[0120] The test was performed according to the test method of the above-mentioned Example 1 and / or Comparative Example 1, see Figure 1-Figure 8 The results are as follows: the water contact angle is 98.35±1.42°; the elongation at break and the tensile strength are 203.92% and 7.92MPa respectively; the adhesion is 5.02±0.36MPa; the friction coefficient is stable at 0.05, and the friction coefficient in water is stable at 0.02; the inhibition rate of Nitzschia closterium is 97.45±9.0%, and the inhibition rate of Bletilla striata is 97.71±3.2%; the ice adhesion strength W ice =8.85±0.53kPa, 20 icing-deicing cycles Ice adhesion strength W ice =45.43±1.06kPa; after 20 ice-deicing cycles of soaking in Nitzschia closterium for ten days, the ice adhesion strength is W ice =46.02±3.25kPa.

[0121] Example 7

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

[0123] The test was performed according to the test method of the above-mentioned Example 1 and / or Comparative Example 1, see Figure 1-Figure 8 The results are as follows: the water contact angle is 99.45±2.89°; the elongation at break and the tensile strength are 150.01% and 9.13MPa respectively; the adhesion is 4.84±0.29MPa; the friction coefficient is stable at 0.04, and the friction coefficient in water is stable at 0.01; the inhibition rate of Nitzschia closterium is 98.96±1.8%, and the inhibition rate of Bletilla striata is 98±2.0%; the ice adhesion strength W ice =7.95±0.94kPa, 20 icing-deicing cycles Ice adhesion strength W ice =25.77±1.87 kPa; after 20 ice-deicing cycles of soaking in Nitzschia closterium for ten days, the ice adhesion strength is 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 a silicone-modified fluorocarbon resin coating in this example, the amount of IPD I added in step one is 24.09 g to obtain prepolymer PI8, and 15 g of fluorocarbon resin is added in step two, and the rest of the method remains unchanged, as shown in Example 1, and Example 8 is recorded as P2I7F3.

[0126] The test was performed according to the test method of the above-mentioned Example 1 and / or Comparative Example 1, see Figure 1-Figure 8 The results are as follows: the water contact angle is 104.88±1.23°; the elongation at break and the tensile strength are 180.89% and 7.74MPa respectively; the adhesion is 3.52±0.36MPa; the friction coefficient is stable at 0.19, and the friction coefficient in water is stable at 0.11; the inhibition rate of Nitzschia closterium is 96.09±4.1%, and the inhibition rate of Bletilla striata is 95.71±5.8%; the ice adhesion strength W ice =6.85±0.53kPa, 20 icing-deicing cycles Ice adhesion strength W ice =48.99±2.70kPa; after 20 ice-deicing cycles of soaking in Nitzschia closterium for ten days, the ice adhesion strength is W ice =51.03±1.99kPa.

[0127] The test was performed according to the test method of the above-mentioned Example 1 and / or Comparative Example 1, see Figure 1-Figure 8 As shown, the results are: the water contact angle is 90.24±1.61°; the sample of comparative example 1 cannot meet the requirements of the test elongation at break and tensile strength; the adhesion is 4.57±0.09MPa; the friction coefficient is stable at 0.13, and the friction coefficient in water is stable at 0.25; the inhibition rate of small crescent algae is 73.21±2.2%, and the inhibition rate of double eyelid algae is 78.57±6.9%; the ice adhesion strength W ice =45.50±2.74kPa, 20 icing-deicing cycles Ice adhesion strength W ice =91.25±2.84 kPa; after 20 ice-deicing cycles of soaking in Nitzschia closterium for seven days, the ice adhesion strength is W ice =103.58±1.26kPa.

[0128] Application Example 1

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

[0130]

[0131] The above-mentioned organosilicon-modified isocyanate prepolymer, titanium dioxide and xylene are added into a dispersion tank at one time, fully dispersed at a speed of 3000 r / min for 15 minutes, and then the coating additives (BYK163, BYK066, EFKA3777) are added and dispersed at a speed of 3000 r / min for 20 minutes. After the dispersion is completed, the material can be discharged after inspection to obtain component A of the composite coating if there is no granular matter.

[0132] The allocation of Group B is as follows:

[0133]

[0134] The B component materials were added to the A component in sequence and dispersed evenly using a high-speed disperser at a speed of 3000r / min for 10 minutes. After the dispersion was completed, the material could be discharged after inspection without any granular material to obtain a composite coating, which was applied to an epoxy board and recorded as PI5F3C after complete curing.

[0135] Actual outdoor environment anti-icing test:

[0136] Place the fully cured PI5F3C in an outdoor environment with an average temperature of -25°C and take photos every ten days to record the ice or frost state of the surface. The cycle is 30 days. Fig. 9Application Examples 1-6 are actual outdoor environment anti-icing test data of the organosilicon-modified fluorocarbon resin composite coating and a blank epoxy board prepared within 30 days at an average temperature of -25°C;

[0137] Real sea test:

[0138] After the 30-day low-temperature test, the PI5F3C was placed in the sea area of ​​Xiaochangshan Island Town, Changhai County, Dalian City, Liaoning Province for real sea testing. The coating was immersed and taken out regularly to take photos and record. Fig.10 This is a graph of data from a four-month actual sea test conducted immediately after Application Example 1-6 underwent a 30-day -25°C outdoor anti-icing test.

[0139] Application Example 2-6

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

[0141] Refer to Application Example 1, Application Examples 2-6 Actual outdoor environment anti-icing test data as shown in the figure Fig. 9 , the actual sea test data is shown in the figure Fig.10 .

[0142] Table 1

[0143]

[0144]

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

[0146] Fig.10 In the test, after experiencing 30 days of low temperature, the results of another 4 months of actual sea testing showed that the silicone-modified fluorocarbon resin composite coating still has an excellent ability to inhibit the adhesion of fouling organisms, indicating that the prepared silicone-modified fluorocarbon resin composite coating not only has good anti-fouling and anti-icing capabilities, but also has good temperature alternating stability, and has certain practical application value.

[0147] In summary, it can be seen from the above application examples that the existing protection for the surface of the hull traveling over a large temperature range generally cannot have both anti-icing and anti-fouling properties at the same time, and has problems of fouling organisms adhering to the coating surface and ice formation due to comprehensive factors such as high friction coefficient, large resistance, low resistance to fouling, difficulty in cleaning, and easy retention of water droplets. The present invention provides a silicone-modified fluorocarbon resin composite coating with the advantages of low friction coefficient, large water contact angle (104.88±1.23°), hard, dense and smooth texture, low ice adhesion (25.77±1.87kPa), etc. It can achieve the purpose of surface anti-fouling through the special physical and chemical properties of the coating surface in temperate and cold environments, and has both anti-icing and ice-repellent properties.

[0148] 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. A silicone-modified fluorocarbon resin having antifouling properties, It is characterized in that The invention is prepared by polycondensation reaction of diisocyanate, fluorocarbon resin, monohydroxyl-terminated polydimethylsiloxane and a catalyst in an organic solvent.

2. A method for preparing the organosilicon-modified fluorocarbon resin with antifouling properties according to claim 1, It is characterized in that The steps include: S1. Preparation of silicone modified isocyanate prepolymer: Add monohydroxy-terminated polydimethylsiloxane to a reaction vessel at 100°C, stir and dehydrate under vacuum, and when the temperature is lower than 45°C, drop diisocyanate therein, add organic solvent and catalyst to the system after the dropwise addition is complete, stir evenly, and then heat to 60-80°C to fully react to obtain silicone-modified isocyanate prepolymer; S2. Preparation of silicone-modified fluorocarbon resin: The organosilicon-modified isocyanate prepolymer obtained in S1 is added with fluorocarbon resin and stirred evenly to obtain organosilicon-modified fluorocarbon resin.

3. The method for preparing the organosilicon-modified fluorocarbon resin having antifouling properties according to claim 2, It is characterized in that The diisocyanate is one or more of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, and lysine diisocyanate; And / or, the catalyst is one or more of triethylamine and dibutyltin dilaurate; And / or, the organic solvent is one or more of xylene, propylene glycol methyl ether, and propylene glycol methyl ether acetate.

4. The method for preparing the organosilicon-modified fluorocarbon resin having antifouling properties according to claim 2, It is characterized in that 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: Wherein: R4 is hydrogen or methyl, R5 is a C1-8 alkyl group; n is an integer from 24 to 31.

5. The method for preparing the organosilicon-modified fluorocarbon resin having antifouling properties according to claim 2, It is characterized in that The fluorocarbon resin is FEVE fluorocarbon resin, and the relative molecular weight is 1000-2000; or the general structural formula of the fluorocarbon resin is as follows: R1 is hydrogen or methyl, R2 is a C1-8 alkyl group, R3 is a C2-3 olefin group; and X is a chlorinated hydrocarbon.

6. The method for preparing the organosilicon-modified fluorocarbon resin having antifouling properties according to claim 2, It is characterized in that 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.

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

8. A composite coating, It is characterized in that The invention comprises independently packaged component A and component B, wherein the component A comprises the following components in parts by weight: an organosilicon-modified isocyanate prepolymer, a first organic solvent, a pigment and a filler, and a coating additive; the coating additive comprises one or more of a dispersant, a leveling agent, and a defoaming agent; The B component includes the following components in parts by weight: a fluorocarbon resin, a catalyst, an anti-settling agent, and a second organic solvent; The preparation of the organosilicon-modified isocyanate prepolymer is as follows: Add monohydroxy-terminated polydimethylsiloxane to a reaction container at 100°C, stir and dehydrate under vacuum, and when the temperature is lower than 45°C, drop diisocyanate thereinto. After the dropwise addition is completed, add an organic solvent and a catalyst to the system, stir evenly, and then heat to 60-80°C for sufficient reaction to obtain an organosilicon-modified isocyanate prepolymer.

9. The composite coating according to claim 8, It is characterized in that The component A comprises the following components in parts by weight: 8-15 parts of organosilicon-modified isocyanate prepolymer, 7-16 parts of a first organic solvent, 6-12 parts of a pigment and filler, and 0.1-1 parts of a coating additive; The B component includes the following components in parts by mass: 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.

10. Use of the organosilicon-modified fluorocarbon resin according to claim 1, the organosilicon-modified fluorocarbon resin antifouling coating according to claim 7, or the composite coating according to claim 8 in protecting the surface of a ship. It is characterized in that The surface protection includes surface protection for ships traveling in temperate and low-temperature areas.

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