An ultraviolet-curable silicone hydrophobic coating, its preparation method and application

Abstract

The present invention relates to the technical field of silicone materials, and discloses an ultraviolet-curable silicone hydrophobic coating, a preparation method and an application thereof. The coating comprises component C1, component C2 and component C3; the structures of component C1 and C2 are shown in Formula I and Formula II respectively, the mass of component C2 is 5-50% of that of C1, and C3 is a photoinitiator; after mixing component C1, component C2 and component C3, gas is removed under vacuum, and an ultraviolet-curing is carried out under the protection of an inert gas to obtain the silicone hydrophobic coating. The present invention copolymerizes and crosslinks polydimethylsiloxane capped with a single-terminal acryloxy functional group and linear polydimethylsiloxane containing multiple acryloxy functional groups at both ends, which can not only achieve the hydrophobicity of the material, but also have an appropriate crosslinking density. It can be used for preparing antifouling materials, hydrophobic materials or anticorrosive materials.

Description

Technical Field

[0001] The present invention relates to the technical field of silicone materials, and particularly relates to an ultraviolet-curable silicone hydrophobic coating, a preparation method thereof, and an application thereof. Background Art

[0002] Most traditional silicone materials are prepared by thermal curing methods, which have problems such as high energy consumption, long time, and cumbersome operation during the curing process. With the enhancement of people's environmental awareness and the implementation of increasingly stringent environmental protection regulations in various countries, the ultraviolet-curing technology with the advantages of low energy consumption, rapid curing, and environmental friendliness has received extensive attention in the academic and industrial fields.

[0003] Benefiting from the characteristics of high bond energy, long bond length, and large Si-O-Si bond angle of the Si-O bond in the molecule, the silicone polymer material composed of Si-O-Si bonds has excellent high and low temperature resistance, weather resistance, heat and cold shock resistance, and low surface energy. Polysiloxane can absorb the energy of light waves in the near-ultraviolet region and is not prone to yellowing or degradation. Therefore, UV-cured polysiloxane transparent materials have been widely used, such as being used as antifouling materials, hydrophobic materials, anticorrosive materials, etc.

[0004] Classified according to the curing mechanism, the UV-curable organic material system can be divided into two major categories: cationic curing and free radical curing. In the silicone polymer based on the cationic UV curing mechanism, there are usually styryl or epoxy functional groups containing unsaturated C═C double bonds. The UV cationic photoinitiator generates super strong protonic acid or Lewis acid under the action of the energy of ultraviolet light irradiation, forming a strong acidic active center; the above styryl or epoxy functional groups are crosslinked and cured under the action of these acidic active centers to obtain an ultraviolet-cured silicone material. The silicone material obtained by using the cationic UV curing mechanism has small volume shrinkage and strong adhesion between the cured polymer and the substrate. The cationic UV curing process is greatly affected by moisture in the system or environment, and alcohols and amines will also inhibit the cationic UV curing process of the silicone polymer; in addition, on the other hand, there are fewer characteristic functional groups and polymer types suitable for cationic UV curing, resulting in high prices for such ultraviolet-cured materials.

[0005] The characteristic functional group suitable for the free radical UV curing mechanism is acryloxy. The photoinitiator generates free radicals under ultraviolet light irradiation, and these free radicals attack the silicone polymer containing acryloxy functional groups to carry out reaction steps such as chain initiation, chain transfer, and chain termination. Under UV light irradiation, the photoinitiator is easily decomposed into free radicals containing unpaired electrons, and these free radicals can combine with other compounds at the position of the unpaired electrons, or be added to the double bond of the monomer to generate another active free radical. During the polymerization process, the active center is constantly repositioned at the end of the growing polymer chain. When the silicone polymer chain free radical reacts with another free radical, the polymerization reaction is terminated. Although free radical curing is susceptible to oxygen inhibition, and there are problems such as large volume shrinkage of the polymer before and after curing and poor adhesion between the polymer and the substrate, the free radical UV curing speed is much faster than the cationic UV curing speed, and it has the advantages of high efficiency, rapidity, and low cost, and has occupied a dominant position in the photopolymerization product market.

[0006] The position and content of acryloxy functional groups in the silicone polymer molecule determine the properties of the silicone material obtained by free radical UV curing. The acryloxy functional groups are usually located at both ends of linear silicone polymer molecules with different degrees of polymerization or different molecular weights. As the molecular weight or degree of polymerization of the polymer increases, the content of acryloxy functional groups in the silicone polymer molecule decreases, resulting in a decrease in the crosslinking density of the polymer material formed after UV curing and poor mechanical properties.

[0007] In order to improve the crosslinking density of UV-cured silicone materials, the literature (X Q Li, F Q Bian, J W Hu, et.al. One-step synthesis of novel multifunctional silicone acrylate prepolymers for use in UV-curable coatings. Prog. Org. Coat., 163, (2022), 106601.) discloses that using pentaerythritol tetraacrylate (PETTA) as a raw material, multiple acryloxy functional groups can be introduced at both ends of the silicone polymer through the hydrosilylation reaction between the C=C double bond and the Si-H bond, thereby improving the transparency, oil resistance, and high-temperature resistance of the UV-cured silicone material. However, since the 4 acryloxy groups contained in the pentaerythritol tetraacrylate (PETTA) molecule can all undergo hydrosilylation with the Si-H bond, the structure of the hydrosilylation product is uncertain and there are multiple by-products; adding the above hydrosilylation product to the UV free radical-cured silicone polymer results in unstable batches of the UV-cured product and large performance differences.

[0008] From a molecular structure perspective, the acryloyloxy functional group is a hydrophilic group. Although silicone polymer materials have excellent hydrophobic migration properties and low surface energy, introducing hydrophilic acryloyloxy functional groups at both ends of the silicone polymer molecules reduces the hydrophobic properties of the acryloyloxy-functionalized silicone polymer materials. If a polysiloxane capped with such double-ended acryloyloxy functional groups is used as a silicone prepolymer material and compounded with a crosslinking density modifier prepared from pentaerythritol tetraacrylate (PETTA), and then the compounded product is subjected to UV radical curing, since the resulting UV-cured film contains acryloyloxy functional groups that have not fully participated in the crosslinking reaction, the UV-cured film exhibits hydrophilicity, that is, the surface water contact angle of the UV-cured film is less than 90°, making it difficult to achieve the expected anti-fouling performance. Summary of the Invention

[0009] Aiming at the problem that the UV-cured silicone materials prepared from polydimethylsiloxane capped with double-ended acryloyloxy functional groups or polydimethylsiloxane capped with double-ended acryloyloxyethyl oxypropyl functional groups are hydrophilic and have weak crosslinking density, the present invention provides a UV-curable silicone hydrophobic coating. This coating is prepared by copolymerizing and crosslinking polydimethylsiloxane capped with a single-ended acryloyloxyethyl oxypropyl functional group and a linear polydimethylsiloxane with multiple acryloyloxy functional groups at both ends, which can not only achieve the hydrophobicity of the material but also have an appropriate crosslinking density.

[0010] To achieve the above object, the technical solution adopted by the present invention is:

[0011] A UV-curable silicone hydrophobic coating, comprising raw material components: component C1, component C2, and component C3;

[0012] Component C1 is polydimethylsiloxane capped with a single-ended acryloyloxyethyl oxypropyl functional group having a structure as shown in formula I, and its dosage is 100 parts by weight;

[0013]

[0014] Component C2 is a linear polydimethylsiloxane with multiple acryloyloxy functional groups at both ends having a chemical structural formula as shown in formula II, and its mass is 5-50% of the mass of component C1;

[0015]

[0016] Component C3 is a photoinitiator, and its mass is 0.1-5% of the total mass of component C1 and component C2;

[0017] Where n and m represent the degree of polymerization, n takes natural numbers from 3 to 50, and m takes natural numbers from 30 to 100.

[0018] In the present invention, a composite curing of a poly(dimethylsiloxane) capped with a single-end acryloyloxyethyloxypropyl functional group and a linear poly(dimethylsiloxane) with multiple hydroxyacryloyloxy functional groups at both ends is adopted. On the one hand, the acryloyloxyethyloxypropyl functional group on one side of the poly(dimethylsiloxane) molecule capped with the acryloyloxyethyloxypropyl functional group participates in the UV radical curing reaction, and the inert trimethyl functional group on the other side maintains the hydrophobic property of the silicone material, so that the surface water contact angle after UV curing is greater than 90°, thereby obtaining a hydrophobic silicone coating; on the other hand, the crosslinking density of the product is increased by the linear poly(dimethylsiloxane) with multiple acryloyloxy functional groups at both ends, and a UV-cured thin film material with a hydrophobic surface and an appropriate crosslinking density is obtained.

[0019] The poly(dimethylsiloxane) capped with a single-end acryloyloxyethyloxypropyl functional group can only crosslink on one side, and its reaction activity decreases with the increase of the molecular weight. Preferably, the molecular weight of the component C1 is 370-2500 g / mol;

[0020] The molecular weight of the component C2 is 2900-8500 g / mol.

[0021] The preparation process of the silicone hydrophobic coating includes the steps of: mixing the component C1, the component C2 and the component C3, removing gas under vacuum, and performing UV curing under the protection of an inert gas.

[0022] Preferably, when performing UV curing, the power of the UV light source is 50-200 mW, the electric power is 1-5 kW, and the curing time is 5-200 s.

[0023] Removing gas under vacuum is mainly to remove the residual oxygen, air, etc. in the mixture to avoid affecting the morphology and performance of the material.

[0024] The component C3 is one or a mixture of more of 2-hydroxy-2-methyl-1-phenylpropan-1-one (CAS RN: 7473-98-5), 1-hydroxycyclohexyl phenyl ketone (CAS RN: 947-19-3), 2-methyl-2-(4-morpholinyl)-1-[4-(methylthio)phenyl]propan-1-one (CAS RN: 71868-10-5), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (CAS RN: 75980-60-8), ethyl 2,4,6-trimethylbenzoyl phenylphosphonate (CAS RN: 84434-11-7), 2-dimethylamino-2-benzyl-1-[4-(4-morpholinyl)phenyl]butan-1-one (CAS RN: 119313-12-1), 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propan-1-one (CAS RN: 106797-53-9), methyl benzoylformate (CAS RN: 15206-55-0).

[0025] Preferably, the component C3 is a mixture of 2-hydroxy-2-methyl-1-phenyl-propanone and 1-hydroxycyclohexyl phenyl ketone, and the mass ratio of 2-hydroxy-2-methyl-1-phenyl-propanone to 1-hydroxycyclohexyl phenyl ketone is 1:10 to 10:1. When the composition of the two initiators is within the above range, the degree of copolymerization of each reactant is high, and the gel fraction of the obtained UV-cured film is also above 70%, which is more conducive to improving the crosslinking density of the product.

[0026] More preferably, the component C3 is a mixture of 2-hydroxy-2-methyl-1-phenyl-propanone and 1-hydroxycyclohexyl phenyl ketone with a mass ratio of 1:0.8 to 1:1.2. Experiments have found that when the contents of the two initiators in C3 are within this range, the gel fraction of the prepared UV-cured film is above 80%, and the crosslinking efficiency of the product is higher.

[0027] The preparation of the component C1 includes the steps:

[0028] Step 1-1: Using α-trimethylsilyl-ω-dimethylsiloxy-terminated polydimethylsiloxane and allyl hydroxyethyl ether as raw materials, a hydrosilylation reaction is carried out under the action of a Karstedt catalyst to obtain an intermediate A with the following structure;

[0029]

[0030] Step 1-2: Using the intermediate A and acryloyl chloride as raw materials, a condensation reaction is carried out under the condition of containing an acid-binding agent to obtain the component C1;

[0031] The preparation of the component C2 includes the steps:

[0032] Step 2-1: Using hydrogen-containing silicone oil at both ends and trimethylolpropane allyl ether (CAS RN: 682-11-1) as raw materials, a hydrosilylation reaction is carried out under the action of a Karstedt catalyst to obtain an intermediate B with the following structure;

[0033]

[0034] Step 2-2: Using the obtained intermediate B and acryloyl chloride as raw materials, a condensation reaction is carried out under the condition of containing an acid-binding agent to obtain the component C2.

[0035] The present invention proposes to first carry out a hydrosilylation reaction between bis - terminal hydrogen - containing silicone oil and trimethylolpropane allyl ether to obtain a polymer intermediate B with a clear structure and multiple hydroxyalkyl functional groups at both ends. Then, the polymer intermediate B is subjected to a condensation reaction with acryloyl chloride to obtain a linear polydimethylsiloxane with a clear structure and multiple acryloyloxy functional groups at both ends. It overcomes the defects that in the process of introducing acryloyloxy functional groups on both sides of the organosilicon polymer molecule by hydrosilylation using pentaerythritol tetraacrylate (PETTA) and bis - terminal hydrogen - containing silicone oil as raw materials, the structure of the hydrosilylation product is uncertain, there are multiple by - products, and when using this hydrosilylation product as a cross - linking density modifier for the UV - curing system, there are problems such as poor process reproducibility and unstable batches of UV - cured products. The component C2 obtained by this method has a stable structure, few by - products, and a high yield.

[0036] Step 1 - 1 specifically includes: After activating the Karstedt catalyst and allyl hydroxyethyl ether, dropwise add α - trimethylsilyl - ω - dimethylsiloxy - terminated polydimethylsiloxane thereto for hydrosilylation reaction. After the reaction is completed, add an organic amine to deactivate the catalyst, and rectify and purify the reaction mixture to obtain intermediate A; the reaction formula is as follows:

[0037]

[0038] Step 1 - 2 specifically includes the steps: Under the protection of an inert gas, mix intermediate A, an acid - binding agent, and an organic solution, then dropwise add acryloyl chloride thereto. After the dropping is completed, continue the condensation reaction. After the reaction is completed, purify the reactants to obtain the component C1; the reaction formula is as follows:

[0039]

[0040] Step 2 - 1 specifically includes the steps: After mixing and activating the Karstedt catalyst and trimethylolpropane allyl ether, dropwise add bis - terminal hydrogen - containing silicone oil thereto for hydrosilylation reaction. After the reaction is completed, add an organic amine to deactivate the catalyst, and rectify and purify the reaction mixture to obtain intermediate B; the chemical equation is as follows:

[0041]

[0042] Step 2 - 2 specifically includes the steps: Under the protection of an inert gas, mix intermediate B, an acid - binding agent, and an organic solution, dropwise add acryloyl chloride thereto. After the dropping is completed, continue the condensation reaction. After the reaction is completed, purify the reactants to obtain the component C2. The chemical reaction equation is as follows:

[0043]

[0044] Preferably, in step 1-1, the molar ratio of allyl hydroxyethyl ether to α-trimethylsilyl-ω-dimethylsiloxy-terminated polydimethylsiloxane is 1.0 to 2.5:1; within this molar ratio range, the Si-H bond in the end group of α-trimethylsilyl-ω-dimethylsiloxy-terminated polydimethylsiloxane can fully react with the C═C double bond in the allyl hydroxyethyl ether molecule. Although increasing the amount of allyl hydroxyethyl ether can also completely convert the Si-H bond in the end group of α-trimethylsilyl-ω-dimethylsiloxy-terminated polydimethylsiloxane, more time and more energy consumption will be required to remove or recover the unreacted allyl hydroxyethyl ether in the later stage of the reaction;

[0045] In step 2-1, the molar ratio of trimethylolpropane allyl ether to hydrogen-containing silicone oil with two terminal groups is 1.5 to 5.0:1; within this molar ratio range, the Si-H bond of the hydrogen-containing silicone oil with two terminal groups can fully react with the C═C double bond in the trimethylolpropane allyl ether molecule. Although increasing the amount of trimethylolpropane allyl ether can also completely convert the Si-H bond of the hydrogen-containing silicone oil with two terminal groups, more time and more energy consumption will be required to remove or recover the unreacted trimethylolpropane allyl ether in the later stage of the reaction;

[0046] In step 1-1 or step 2-1, the mass of platinum element in the Karstedt catalyst is (3 to 300)×10 -6 :1;

[0047] In step 1-1 or step 2-1, the activation temperature is 60 to 90 °C and the activation time is 0.25 to 5.0 h;

[0048] In step 1-1, the dropping time of α-trimethylsilyl-ω-dimethylsiloxy-terminated polydimethylsiloxane or in step 2-1, the dropping time of hydrogen-containing silicone oil with two terminal groups is 0.5 to 6.0 h, the continued reaction time after dropping is 1.0 to 10.0 h, and the reaction temperature is 60 - 90 °C; the dropping method can make α-trimethylsilyl-ω-dimethylsiloxy-terminated polydimethylsiloxane in step 1-1 or hydrogen-containing silicone oil with two terminal groups in step 2-1 fully react with allyl hydroxyethyl ether in step 1-1 or trimethylolpropane allyl ether in step 2-1, avoiding the Si-H bond in α-trimethylsilyl-ω-dimethylsiloxy-terminated polydimethylsiloxane in step 1-1 or hydrogen-containing silicone oil with two terminal groups in step 2-1 from being entangled by polymer segments due to too fast feeding speed, resulting in the inability to fully react with allyl hydroxyethyl ether in step 1-1 or trimethylolpropane allyl ether in step 2-1;

[0049] In Step 1-1 or Step 2-1, the organic amine includes at least one of ethylenediamine, triethylamine, n-butylamine, triethanolamine, tetramethylammonium hydroxide, isopropylamine, and diisopropylamine, and the mass ratio of the organic amine to the platinum element in the Kaster catalyst is 50 to 500:1;

[0050] In Step 1-2, the molar ratio of acryloyl chloride to Intermediate A is 0.8 to 5.0:1; within this range of the molar ratio of acryloyl chloride to Intermediate A, the hydroxyl group in the molecule of Intermediate A can fully react with acryloyl chloride, increasing the content of acryloyloxy functional groups in Component C1;

[0051] In Step 2-2, the molar ratio of acryloyl chloride to Intermediate B is 2.0 to 10.0:1; within this range of the molar ratio of acryloyl chloride to Intermediate B, the hydroxyl group in the molecule of Intermediate B can fully react with acryloyl chloride, increasing the content of acryloyloxy functional groups in Component C2;

[0052] In Step 1-2 or Step 2-2, the molar ratio of Intermediate A or Intermediate B to the acid-binding agent is 1:0.75 to 3.0; the mass ratio of the acid-binding agent to the organic solvent is 1:5 to 50; the acid-binding agent is selected from at least one of ethylenediamine, triethylamine, n-butylamine, triethanolamine, tetramethylammonium hydroxide, isopropylamine, and diisopropylamine; the organic solvent includes at least one of dichloromethane, ethyl acetate, acetone, chloroform, carbon tetrachloride, n-pentane, isopentane, n-hexane, and cyclohexane;

[0053] In Step 1-2 or Step 2-2, when acryloyl chloride is added dropwise, the temperature of the reaction mixture is -20 to 15°C, the dropping time is 5 to 180 min, after the dropping is completed, the temperature of the reaction mixture is 15 to 35°C, and the condensation reaction continues for 3 to 12 h.

[0054] Furthermore, Step 1-1 specifically includes the steps of:

[0055] (a1) Charge dry nitrogen into a closed reaction device equipped with a temperature control system, a condenser, and a stirrer, add allyl hydroxyethyl ether and a Kaster catalyst, and then activate the catalyst by mixing under stirring;

[0056] (a2) Add α-trimethylsilyl-ω-dimethylsiloxane-terminated polydimethylsiloxane to the reaction device in a dropping manner, and continue the reaction at this temperature after the dropping is completed;

[0057] (a3) Add an organic amine to the reaction device to deactivate the Kaster catalyst in the system;

[0058] (a4) Subject the obtained reaction mixture to vacuum distillation, and remove the low-boiling substances to obtain α-trimethylsilyl-ω-dimethyl(γ-hydroxyethyloxypropyl)siloxane-terminated polydimethylsiloxane (Intermediate A).

[0059] In step (a4), the reduced pressure distillation pressure is -101.3 kPa to -90 kPa, the reduced pressure distillation temperature is 100 °C to 180 °C, and the reduced pressure distillation time is 1.0 to 10.0 h.

[0060] Furthermore, step 1-2 specifically includes the steps:

[0061] (b1) In a reaction device under the protection of dry nitrogen, add α-trimethylsilyl-ω-dimethyl(γ-hydroxyethyl oxypropyl) siloxy-terminated polydimethylsiloxane (intermediate A), an acid-binding agent and an organic solvent in sequence. While stirring, use the cooling medium in the jacket to lower the temperature of the mixed material to -20 to 5 °C;

[0062] (b2) Add acryloyl chloride to the reactor by dropping method, and control the reaction system at -5 to 15 °C by controlling the dropping rate of acryloyl chloride; after the addition of acryloyl chloride is completed, raise the reaction mixture to 15 to 35 °C and continue to react at this temperature for 3 to 12 h;

[0063] (b3) After the reaction is completed, filter to remove salts, and then subject the obtained filtrate to vacuum flashing to remove the solvent;

[0064] (b4) After the temperature of the filtrate after removing the solvent is lowered to room temperature, wash and extract repeatedly with an organic solvent and a neutralizing agent until the upper layer solution is neutral;

[0065] (b5) Subject the collected upper layer solution to vacuum flashing again to remove the remaining solvent and low-boiling substances, and obtain α-trimethylsiloxy-ω-dimethyl(γ-acryloyloxyethyl oxypropyl) terminated polydimethylsiloxane (component C1) after cooling to room temperature.

[0066] The neutralizing agent is selected from at least one of saturated sodium carbonate solution, saturated sodium bicarbonate solution, saturated disodium hydrogen phosphate solution, saturated lithium hydroxide solution, saturated sodium hydroxide solution, and saturated potassium hydroxide solution;

[0067] The vacuum flashing temperature in step b3 is 20 to 40 °C, and the pressure is -101.3 kPa to -90.0 kPa;

[0068] The vacuum flashing temperature in step b5 is 40 °C to 80 °C, and the pressure is -101.3 kPa to -90.0 kPa.

[0069] Furthermore, step 2-1 includes the steps:

[0070] (c1) Charge dry nitrogen into a closed reaction device equipped with a temperature heating control system, a condenser, and stirring. Add trimethylolpropane allyl ether and a Karstedt catalyst, and then mix and activate the catalyst under stirring.

[0071] (c2) Add hydrogen-containing silicone oil at both ends dropwise into the reaction device. After the dropping is completed, continue the reaction at this temperature.

[0072] (c3) Add an organic amine into the reaction device to deactivate the Karstedt catalyst in the system.

[0073] (c4) Subject the obtained reaction mixture to vacuum distillation to remove low-boiling substances and obtain intermediate B.

[0074] In step (c4), the pressure for vacuum distillation is -101.3 kPa to -90 kPa, the temperature for vacuum distillation is 100 °C to 180 °C, and the time for vacuum distillation is 1.0 to 10.0 h.

[0075] Further preferably, step 2-2 includes the steps:

[0076] (d1) Add intermediate B, an organic amine, and organic solvent III into a reaction device under the protection of dry nitrogen in sequence. Under stirring, use the cooling medium in the jacket to lower the temperature of the mixed material to -20 to 5 °C.

[0077] (d2) Add acryloyl chloride into the reactor by dropwise addition. Control the reaction system at -5 to 15 °C by controlling the dropping rate of acryloyl chloride. After the dropping of acryloyl chloride is completed, raise the reaction mixture to 15 to 35 °C and continue the reaction at this temperature for 3 to 12 h.

[0078] (d3) After the reaction is completed, subject the filtrate obtained by removing salts by filtration to vacuum flashing to remove the solvent.

[0079] (d4) After the temperature of the filtrate after removing the solvent is lowered to room temperature, wash and extract it repeatedly with an organic solvent and a neutralizing agent until the upper layer solution is neutral.

[0080] (d5) Subject the collected upper layer solution to vacuum flashing to remove the remaining solvent and low-boiling substances. After cooling to room temperature, obtain linear polydimethylsiloxane with multiple acryloyloxy functional groups at both ends (component C2).

[0081] The temperature for vacuum flashing in step (d3) is 20 to 40 °C, and the pressure is -101.3 kPa to -90.0 kPa.

[0082] The organic solvent in the step (d4) includes at least one of ethyl acetate, propyl acetate, butyl acetate, isopropyl acetate, and isobutyl acetate; the neutralizing agent is selected from at least one of saturated sodium carbonate solution, saturated sodium bicarbonate solution, saturated disodium hydrogen phosphate solution, saturated lithium hydroxide solution, saturated sodium hydroxide solution, and saturated potassium hydroxide solution;

[0083] In the step (d5), the temperature of vacuum flash evaporation is 40°C to 80°C, and the pressure is -101.3 kPa to -90.0 kPa.

[0084] The present invention also provides a method for preparing the ultraviolet-curable silicone hydrophobic coating, which includes the steps of: mixing component C1, component C2, and component C3, removing gas under vacuum, and performing ultraviolet curing under inert gas protection;

[0085] Preferably, when performing ultraviolet curing, the power of the ultraviolet light source is 50 to 200 mW, the electric power is 1 to 5 kW, and the curing time is 5 to 200 s.

[0086] The present invention also provides the application of the ultraviolet-curable silicone hydrophobic coating in the preparation of antifouling materials, hydrophobic materials, or anticorrosive materials.

[0087] Compared with the prior art, the present invention has the following beneficial effects:

[0088] In the present invention, the molecular structure of the linear polydimethylsiloxane with multiple acryloxy functional groups at both ends (component C2) is clear, the content of acryloxy functional groups that can participate in UV crosslinking curing is high, and the by-products are few; the product obtained by compounding with polydimethylsiloxane (C1) capped with a single acryloxyethyl oxypropyl functional group and a UV free radical photoinitiator has high photo-curing activity. One end of the polydimethylsiloxane (component C1) capped with a single acryloxyethyl oxypropyl functional group is an inert trimethylsilyl functional group, which has the characteristic of high hydrophobicity. The surface water contact angle of the cured material is less than 90°, and it has good hydrophobic and anti-fouling properties. Description of the Drawings

[0089] Figure 1 1H NMR spectrum of the α-trimethylsilyl-ω-dimethyl(γ-hydroxyethyl oxypropyl) siloxy-terminated polydimethylsiloxane (intermediate A) prepared in Example 1 1 1H NMR spectrum.

[0090] Figure 2 1H NMR spectrum of the α-trimethylsiloxy-ω-dimethyl(γ-acryloxyethyl oxypropyl) capped polydimethylsiloxane (component C1) prepared in Example 2 1 1H NMR spectrum.

[0091] Figure 3α-Trimethylsiloxy-ω-dimethyl(γ-acryloyloxyethyl oxypropyl) terminated polydimethylsiloxane (Component C1) prepared for Example 2 13 C NMR spectrum.

[0092] Figure 4 1H NMR spectrum of Intermediate B prepared for Example 3 1 1H NMR spectrum.

[0093] Figure 5 1H NMR spectrum of linear polydimethylsiloxane (Component C2) with multiple acryloxy functional groups at both ends prepared for Example 4 1 1H NMR spectrum. Detailed implementation manners

[0094] In order to make the objectives, technical solutions and advantages of the present invention clearer, the present invention will be further described in detail below in conjunction with embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention. Those skilled in the art make modifications or equivalent replacements based on the understanding of the technical solutions of the present invention, without departing from the spirit and scope of the technical solutions of the present invention, and all should be covered within the protection scope of the present invention.

[0095] Unless otherwise specified, the raw materials used in the present invention can be purchased from the market or are commonly used in the art. Unless otherwise specified, the methods in the following embodiments are all conventional methods in the art.

[0096] The test methods for the finished products in the following specific implementation manners are as follows:

[0097] (1) Water absorption rate test

[0098] Weigh the cured sample that has been pre-dried to constant weight and record it as m a1 ; Immerse it in pure water for 24 h, then dry the surface of the sample with filter paper, and weigh it again and record it as m a2 ; Then put the sample into a blast drying oven and dry it at 80 °C for 1 h and weigh it, record it as m a3 , and calculate the water absorption rate M of the UV-cured sample from formula (1) t .

[0099]

[0100] (2) Crosslinking density v e and the average molecular weight Mc between adjacent crosslinking sites

[0101] Using the equilibrium swelling method, based on the Flory-Rehner theory, calculate the crosslinking density v of the UV-cured film using formula (2) and formula (3) e and the average molecular weight Mc between adjacent crosslinking sites.

[0102]

[0103]

[0104] In equations (2) and (3), ρ is the density of the UV-cured sample, ρ1 is the density of toluene, and V0 is the molar volume of toluene, which is 106.54×10 -3 L·mol -1 ; is the volume fraction of the silicone component in the swollen sample, which is also the inverse of the equilibrium swelling volume; x1 is the interaction parameter between the polymer and the solvent, and its value is 0.465; W0 is the initial mass of the sample, W s is the mass of the sample when swelling equilibrium is reached.

[0105] (3) Water contact angle test

[0106] After a drop of deionized water was dropped on the sample surface for 30 seconds, a water contact angle meter (KRUSS DSA 30, KRUSS, Germany) was used to test each sample. Three points with a distance of 5 mm were measured for each sample. A total of three readings were taken and the arithmetic average was taken.

[0107] Example 1 Preparation of Intermediate A

[0108] 3.73g (0.037mol) of allyl hydroxyethyl ether and 0.24g of 0.1wt% Pt (10ppm) of Karstedt catalyst were added to a 100mL three-necked flask equipped with a thermometer, a condenser, a stirrer and a rubber stopper and filled with nitrogen, and the mixture was stirred and heated to 70°C for activation for 30min. After the activation, 20.00g of α-trimethylsilyl-ω-dimethylsiloxy-terminated polydimethylsiloxane with a number average molecular weight of 550g / mol (0.037mol) was added dropwise to the reaction system within 2h. After the addition of α-trimethylsilyl-ω-dimethylsiloxy-terminated polydimethylsiloxane was completed, the reaction was continued at 70°C for 5h. After the reaction was completed, 0.05g of triethylamine was added to the reaction mixture to quench the catalyst. The reaction mixture was decompressed at 110°C and -100.8 kPa to extract low boiling products, and after cooling, 21.58 g of a transparent light yellow liquid was obtained, which was α-trimethylsilyl-ω-dimethyl(γ-hydroxyethyloxypropyl)siloxy-terminated polydimethylsiloxane (intermediate A), with a yield of 90.9%.

[0109] Intermediate A was sampled and 1 H NMR analysis, the spectrum is listed in Figure 1 .

[0110] Example 2 Preparation of α-trimethylsilyloxy-ω-dimethyl(γ-acryloyloxyethyloxypropyl) terminated polydimethylsiloxane (Component C1)

[0111] The four-necked flask equipped with a thermometer, a condenser, a constant pressure dropping funnel, a stir bar and a rubber stopper was evacuated and purged three times, and the residual air in the system was removed by nitrogen. Then, 15 g (0.023 mol) of α-trimethylsilyl-ω-dimethyl(γ-hydroxyethyloxypropyl) siloxy terminated polydimethylsiloxane (Intermediate A) prepared in Example 1, 2.34 g (0.023 mol) of triethylamine (TA) and 30.00 g (0.023 mol) of dichloromethane were successively added into the four-necked flask, stirred and the temperature of the system was lowered to 0 °C using an ice bath. Then, 2.09 g (0.023 mol) of acryloyl chloride was added dropwise to the reactor over 60 min, controlling the dropping rate so that the system temperature did not exceed 10 °C. After the addition was completed, the material was heated to 25 °C and reacted for 6 h. After the reaction was completed, the salt was removed by filtration, and the solvent was removed under reduced pressure at 30 °C and -100.8 kPa. The concentrated solution was transferred to a separatory funnel and washed repeatedly with ethyl acetate and saturated NaHCO3 solution until the upper layer solution was neutral. The upper layer solution was collected and the solvent and low boilers were removed under reduced pressure at 60 °C and -100.8 kPa to obtain 14.55 g of a slightly yellow transparent solution (α-trimethylsilyloxy-ω-dimethyl(γ-acryloyloxyethyloxypropyl) terminated polydimethylsiloxane, Component C1), with a number average molecular weight of 720 g / mol and a yield of 85.2%.

[0112] The α-trimethylsilyloxy-ω-dimethyl(γ-acryloyloxyethyloxypropyl) terminated polydimethylsiloxane prepared in Example 2 was analyzed by nuclear magnetic resonance spectroscopy (NMR), and its 1 1H NMR spectrum is listed in Figure 2 and its 13 13C NMR spectrum is listed in Figure 3 therein.

[0113] Example 3 Preparation of Intermediate B

[0114] 2.09 g (0.012 mol) of trimethylolpropane allyl ether and 0.16 g of Karstedt catalyst with a platinum content of 0.1 wt% (effective platinum content of 5 ppm) were added to a 100 mL three-necked flask equipped with a thermometer, a condenser, a magnetic stirrer, and a rubber stopper and filled with nitrogen. The mixture was stirred and heated to 70 °C for activation for 30 min. After the activation was completed, 30.0 g (0.0053 mol) of hydrogen-terminated polydimethylsiloxane with a number-average molecular weight of 5680 g / mol was added dropwise to the reaction system within 3 h. After the addition of the hydrogen-terminated polydimethylsiloxane was completed, the reaction mixture continued to react at 70 °C for 3 h. After the reaction was completed, 0.03 g of n-butylamine was added to the reaction mixture to quench the platinum catalyst. Then, the low-boiling substances were removed under reduced pressure at 110 °C and -100.8 kPa from the crude reaction product. After cooling to room temperature, 29.68 g of a colorless transparent liquid was obtained.

[0115] The product obtained in Example 3 was subjected to 1 1H NMR analysis, and its spectrum is as shown in Figure 4 the following.

[0116] Example 4 Preparation of Component C2 (Linear Polydimethylsiloxane with Multiple Acryloxy Functional Groups at Both Ends)

[0117] A four-necked flask equipped with a thermometer, a condenser, a constant-pressure dropping funnel, a magnetic stirrer, and a rubber stopper was evacuated and purged with nitrogen three times to remove the residual air in the system with nitrogen. Then, 4.47×10 -3 mol of Intermediate B prepared in Example 3, 1.82 g (0.018 mol) of triethylamine, and 79.5 g (0.936 mol) of dichloromethane were successively added to the four-necked flask. The mixture was stirred and the system temperature was lowered to -5 °C. Then, 1.59 g (0.018 mol) of acryloyl chloride was added dropwise to the reactor over 105 min, controlling the dropping rate to keep the system temperature not exceeding 5 °C. After the addition was completed, the material was heated to 20 °C and reacted for 3 h. After the reaction was completed, the salts were removed by filtration, and the solvent was removed under reduced pressure at 30 °C and -101.2 kPa. The concentrated solution was transferred to a separatory funnel and washed repeatedly with ethyl acetate and saturated NaHCO3 solution until the upper layer solution was neutral. The upper layer solution was collected and the solvent and low-boiling substances were removed under reduced pressure at 60 °C and -101.2 kPa, obtaining 22.83 g of linear polydimethylsiloxane with multiple acryloxy functional groups at both ends (Component C2). Based on Intermediate B as the key component, the reaction yield was calculated to be 80.0%.

[0118] The linear polydimethylsiloxane with multiple acryloxy functional groups at both ends (Component C2) prepared in Example 4 was subjected to nuclear magnetic resonance spectroscopy (NMR) analysis, and its 1 1H NMR spectrum is listed in Figure 5 the following.

[0119] Example 5 - 7 Preparation of Intermediate A with Different Molecular Weights

[0120] Using α - trimethylsilyl - ω - dimethylsiloxane - terminated polydimethylsiloxane with number - average molecular weights of 960 g / mol, 1440 g / mol, and 2220 g / mol (abbreviated as single - end hydrogen - containing silicone oil, the same below) to replace the single - end hydrogen - containing silicone oil in Example 1 respectively, and preparing Intermediate A with number - average molecular weights of 1060 g / mol, 1550 g / mol, and 2320 g / mol according to the same preparation process as in Example 1. The dosages of each material are shown in Table 1.

[0121] Using the above Intermediate A to replace Intermediate A used in Example 2 respectively, and preparing Component C1 with number - average molecular weights of 1130 g / mol, 1610 g / mol, and 2420 g / mol according to the same preparation process as in Example 2. The dosages of each material are shown in Table 2.

[0122] Table 1 Dosages of Each Component in the Preparation of Intermediate A in Examples 5 - 7

[0123]

[0124] Table 2 Dosages of Each Component in the Preparation of Component C1 in Examples 5 - 7

[0125]

[0126] Example 8 Preparation of UV - Curable Silicone Film

[0127] Mix α - trimethylsiloxy - ω - dimethyl(γ - acryloyloxyethyloxypropyl) - terminated polydimethylsiloxane (Component C1) prepared in Example 2 and linear polydimethylsiloxane with multiple acryloxy functional groups at both ends (Component C2) prepared in Example 4 evenly according to a mass ratio of 70:30 (the sum of their masses is counted as 100 parts by weight), and then add a mixture of 1 part of 2 - hydroxy - 2 - methyl - 1 - phenyl - propanone and 1 part of 1 - hydroxycyclohexyl phenyl ketone as a photo - initiator. After mixing the above components evenly, take 1 g of the above mixture and pour it into a polytetrafluoroethylene mold with a length, width, and thickness of 30 mm, 30 mm, and 6 mm respectively. Put the mold into a vacuum drying oven to evacuate bubbles and adsorbed air, and then put it into a drawer - type ultraviolet light - curing machine (UV light source power 100 mW, electric power 2.2 kW) protected by nitrogen for curing for 30 s to obtain a UV - curable silicone film.

[0128] The UV - curable silicone film prepared in Example 8 was subjected to performance testing. Its water absorption rate was 4.2%, and the cross - link density was 6.5×10 -4 mol / cm 3, the average molecular weight between two adjacent crosslinking sites is 1537 g / mol, and the water contact angle is 95.2°.

[0129] Examples 9 - 11

[0130] Following the steps of Example 8, the component C1 prepared in Examples 5 - 7 and C2 prepared in Example 4 were used to prepare a silicone film. Performance tests showed that the water absorption rate of the film prepared from C1 in Example 5 was 4.6%, and the crosslinking density was 6.0×10 -4 mol / cm 3 , the average molecular weight between two adjacent crosslinking sites is 1413 g / mol, and the water contact angle is 99.6°.

[0131] The water absorption rate of the film prepared from C1 in Example 6 was 2.0%, and the crosslinking density was 5.6×10 -4 mol / cm 3 , the average molecular weight between two adjacent crosslinking sites is 1732 g / mol, and the water contact angle is 106.6°.

[0132] The water absorption rate of the film prepared from C1 in Example 7 was 2.06%, and the crosslinking density was 8.2×10 -4 mol / cm 3 , the average molecular weight between two adjacent crosslinking sites is 1350 g / mol, and the water contact angle is 96.1°.

[0133] Comparative Examples 1 - 3 prepared poly(dimethylsiloxane) terminated with acryloyloxyethyl oxypropyl at both ends

[0134] Using poly(dimethylsiloxane) terminated with hydroxyethyl oxypropyl at both ends (abbreviated as double - end hydroxy hydrocarbon - based silicone oil, the same below) to replace the intermediate A in Examples 5 - 7 for condensation reaction with acryloyl chloride, the chemical equation of the reaction is shown as follows. Poly(dimethylsiloxane) terminated with acryloyloxyethyl oxypropyl at both ends (abbreviated as component C1S) was prepared. The dosages of each material in Comparative Examples 1 - 3 are shown in Table 3.

[0135]

[0136] Table 3 Dosages of each component in Comparative Examples 1 - 3

[0137]

[0138] Comparative Examples 4 - 6

[0139] Respectively, use the component C1 prepared in Comparative Examples 1-3 with the same mass to replace the component C1 in Example 8, mix it with other components according to the method and dosage described in Example 8, and then carry out UV curing under the same conditions to prepare UV-cured film samples of Comparative Examples 4 to 6.

[0140] Perform performance tests on the UV-cured silicone film prepared in Comparative Example 4. Its water absorption rate is 5.7%, the crosslinking density is 39.3×10 -4 mol / cm 3 , the average molecular weight between two adjacent crosslinking sites is 172 g / mol, and the water contact angle is 72.8°.

[0141] Perform performance tests on the UV-cured silicone film prepared in Comparative Example 5. Its water absorption rate is 12.0%, the crosslinking density is 10.0×10 -4 mol / cm 3 , the average molecular weight between two adjacent crosslinking sites is 881 g / mol, and the water contact angle is 81.7°.

[0142] Perform performance tests on the UV-cured silicone film prepared in Comparative Example 6. Its water absorption rate is 3.3%, the crosslinking density is 6.3×10 -4 mol / cm 3 , the average molecular weight between two adjacent crosslinking sites is 1413 g / mol, and the water contact angle is 83.6°.

[0143] In Comparative Example 7, component C2 was not added, and only the polyorganosiloxane capped with acryloyloxyethyl oxypropyl at one end was added, and a silicone film could not be obtained by UV curing.

[0144] Weigh 10.0 g of α-trimethylsiloxy-ω-dimethyl(γ-acryloyloxyethyl oxypropyl) terminated polydimethylsiloxane (component C1) prepared in Example 2, add a mixture of 0.1 g of 2-hydroxy-2-methyl-1-phenyl-propanone and 0.1 g of 1-hydroxycyclohexyl phenyl ketone as a photoinitiator. After stirring each component evenly, weigh 1 g of the mixed sample according to the method described in Example 8 and pour it into a mold. After removing the bubbles, irradiate it in a UV curing machine for 30 s. After taking it out, it was found that the viscosity of the sample increased slightly, but a film could not be cured.

[0145] In Comparative Example 8, component C2 was not added, and only the polyorganosiloxane capped with acryloyloxy groups at both ends (C1S) was added, and a silicone film could not be obtained by UV curing.

[0146] Weigh 10.0 g of the double-ended propionyloxy-terminated polydimethylsiloxane (Component C1S) prepared in Comparative Example 5, add 0.1 g of a mixture composed of 2-hydroxy-2-methyl-1-phenylpropanone and 1-hydroxycyclohexyl phenyl ketone as a photoinitiator thereto. After stirring each component evenly, weigh 1 g of the mixed sample according to the method described in Example 8 and pour it into a mold. After removing air bubbles, irradiate it in a UV curing machine for 30 s. After taking it out, it is found that the viscosity of the sample increases, but a cured thin film material cannot be obtained.

[0147] The test data of the above examples and comparative examples show that a mixture composed of a polyorganosiloxane terminated with a single-ended acryloxyethyloxypropyl group (Component C1) and a linear polydimethylsiloxane with multiple acryloxy functional groups at both ends (Component C2) can be UV cured within 30 s under the action of a mixed photoinitiator composed of 2-hydroxy-2-methyl-1-phenylpropanone and 1-hydroxycyclohexyl phenyl ketone to obtain a polymer thin film with a water contact angle greater than 90° and exhibiting hydrophobicity; when using double-ended propionyloxy-terminated polydimethylsiloxane (Component C1S) with a similar molecular weight to replace the polyorganosiloxane terminated with a single-ended acryloxyethyloxypropyl group (Component C1) and keeping other components and curing conditions unchanged, the water contact angle of the prepared UV cured thin film is less than 90°, showing hydrophilicity.

Claims

1. A UV-cured silicone hydrophobic coating, characterized in that: Comprising raw material components: component C1, component C2 and component C3; Component C1 is a polydimethylsiloxane terminated with a single-end acryloxyethyloxypropyl functional group as shown in Formula I, and its usage is 100 parts by weight; Component C2 is a linear polydimethylsiloxane having a plurality of acryloyloxy functional groups at both ends and a chemical structure as shown in Formula II, and its mass is 5 to 50% of the mass of component C1; Component C3 is a photoinitiator, and its mass is 0.1-5% of the total mass of component C1 and component C2; Wherein n and m represent the degree of polymerization, n is a natural number ranging from 3 to 50, and m is a natural number ranging from 30 to 100.

2. The UV-curable silicone hydrophobic coating according to claim 1, characterized in that: The molecular weight of the component C1 is 370 to 2500 g / mol; the molecular weight of the component C2 is 2900 to 8500 g / mol.

3. The UV-curable silicone hydrophobic coating according to claim 1, characterized in that: The preparation process of the organic silicon hydrophobic coating comprises the steps of: mixing component C1, component C2 and component C3, removing gas in vacuum, and curing by ultraviolet light under the protection of inert gas to obtain the coating.

4. The UV-curable silicone hydrophobic coating according to claim 1, characterized in that: The component C3 is a mixture of one or more of 2-hydroxy-2-methyl-1-phenyl-propanone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2-(4-morpholinyl)-1-[4-(methylthio)phenyl]-1-propanone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylphosphonic acid ethyl ester, 2-dimethylamino-2-benzyl-1-[4-(4-morpholinyl)phenyl]-1-butanone, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-propanone and methyl benzoylformate.

5. The UV-curable silicone hydrophobic coating according to claim 1 or 4, characterized in that: The component C3 is a mixture of 2-hydroxy-2-methyl-1-phenyl-acetone and 1-hydroxycyclohexyl phenyl ketone, and the mass ratio of 2-hydroxy-2-methyl-1-phenyl-acetone to 1-hydroxycyclohexyl phenyl ketone is 1:10 to 10:

1.

6. The UV-curable silicone hydrophobic coating according to claim 1, characterized in that: The preparation of component C1 comprises the steps of: Step 1-1, using α-trimethylsilyl-ω-dimethylsiloxy-terminated polydimethylsiloxane and allyl hydroxyethyl ether as raw materials, a hydrosilylation reaction is carried out under the action of a Custer catalyst to obtain an intermediate A having the structure shown below; Step 1-2, using intermediate A and acryloyl chloride as raw materials, undergoing a condensation reaction in the presence of an acid-binding agent to obtain the component C1; And / or, the preparation of component C2 comprises the steps of: Step 2-1, using double-terminal hydrogen-containing silicone oil and trimethylolpropane allyl ether as raw materials, a hydrosilylation reaction is carried out under the action of a Custer catalyst to obtain an intermediate B having the structure shown below; Step 2-2, using the obtained intermediate B and acryloyl chloride as raw materials, a condensation reaction is carried out in the presence of an acid binding agent to obtain component C2.

7. The UV-curable silicone hydrophobic coating according to claim 6, characterized in that: Step 1-1 specifically comprises: after activating the Custer catalyst and allyl hydroxyethyl ether, adding α-trimethylsilyl-ω-dimethylsiloxy-terminated polydimethylsiloxane thereto for hydrosilylation reaction, adding an organic amine after the reaction is completed to deactivate the catalyst, and distilling and purifying the reaction mixture to obtain intermediate A; And / or, step 1-2 specifically comprises the steps of: under the protection of inert gas, mixing the intermediate A, the acid binding agent and the organic solution, adding acryloyl chloride dropwise thereto, continuing the condensation reaction after the addition is completed, and purifying the reactants after the reaction to obtain the component C1; And / or, step 2-1 specifically comprises the steps of: mixing and activating a Custer catalyst and trimethylolpropane allyl ether, adding double-terminal hydrogenated silicone oil dropwise thereto for hydrosilylation reaction, adding an organic amine after the reaction to deactivate the catalyst, and distilling and purifying the reaction mixture to obtain an intermediate B; And / or, step 2-2 specifically includes the steps of: under the protection of inert gas, mixing the intermediate B, the acid binding agent and the organic solution, adding acryloyl chloride dropwise thereto, continuing the condensation reaction after the addition is completed, and purifying the reactants to obtain the component C2.

8. The UV-curable silicone hydrophobic coating according to claim 7, characterized in that: In step 1-1, the molar ratio of the allyl hydroxyethyl ether to the α-trimethylsilyl-ω-dimethylsiloxy-terminated polydimethylsiloxane is 1.0 to 2.5:1; And / or, in step 2-1, the molar ratio of the trimethylolpropane allyl ether to the double-terminal hydrogen-containing silicone oil is 1.5 to 5.0:1; And / or, the ratio of the mass of the platinum element in the Custer catalyst in step 1-1 or step 2-1 to the total mass of the reaction raw materials is (3 to 300)×10 -6 :1; And / or, in step 1-1 or step 2-1, the activation temperature is 60 to 90° C., and the activation time is 0.25 to 5.0 h; And / or, the dropping time of the α-trimethylsilyl-ω-dimethylsiloxy-terminated polydimethylsiloxane in step 1-1 or the double-terminal hydrogenated silicone oil in step 2-1 is 0.5 to 6.0 hours, the continued reaction time after the dropping is completed is 1.0 to 10.0 hours, and the reaction temperature is 60 to 90° C.; And / or, in step 1-1 or step 2-1, the organic amine includes at least one of ethylenediamine, triethylamine, n-butylamine, triethanolamine, tetramethylammonium hydroxide, isopropylamine, and diisopropylamine, and the mass ratio of the organic amine to the platinum element in the Custer catalyst is 50 to 500:1; and / or, in step 1-2, the molar ratio of acryloyl chloride to intermediate A is 0.8 to 5.0:1; And / or, in step 2-2, the molar ratio of acryloyl chloride to intermediate B is 2.0-10.0:1; And / or, in step 1-2 or step 2-2, the molar ratio of intermediate A or intermediate B to the acid binding agent is 1:0.75-3.0; the mass ratio of the acid binding agent to the organic solvent is 1:5-50; the acid binding agent is selected from at least one of ethylenediamine, triethylamine, n-butylamine, triethanolamine, tetramethylammonium hydroxide, isopropylamine, and diisopropylamine; the organic solvent includes at least one of dichloromethane, ethyl acetate, acetone, chloroform, carbon tetrachloride, n-pentane, isopentane, n-hexane, and cyclohexane; And / or, in step 1-2 or step 2-2, when acryloyl chloride is added dropwise, the temperature of the reaction mixture is -20 to 15°C, the addition time is 5 to 180 min, and after the addition is completed, the temperature of the reaction mixture is 15 to 35°C, and the condensation reaction is continued for 3 to 12 h.

9. The method for preparing a UV-curable silicone hydrophobic coating according to any one of claims 1 to 8, characterized in that: The method comprises the following steps: mixing component C1, component C2 and component C3, removing gas in vacuum, and curing by ultraviolet light under the protection of inert gas to obtain the product.

10. The method for preparing a UV-curable silicone hydrophobic coating according to claim 9, characterized in that: During UV curing, the UV light source power is 50-200 mW, the electric power is 1-5 kW, and the curing time is 5-200 s.

11. Use of the UV-cured silicone hydrophobic coating according to any one of claims 1 to 8 in the preparation of antifouling materials, hydrophobic materials or anticorrosive materials.

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