Preparation method of acrylic copolymer / fluorinated organosilicon coating

Abstract

The invention relates to a preparation method of an acrylic copolymer / fluorinated organosilicon coating, which comprises the following steps: S1, dissolving a carboxyl-containing acrylate copolymer in a solvent to obtain an acrylate copolymer solution with the mass concentration of 30%; s2, dissolving fluorinated epoxy silicon resin in a solvent to obtain a fluorinated epoxy silicon resin solution with the mass concentration of 30%; and S3, in a stirring state, adding the fluorinated epoxy silicon resin solution prepared in the S2 into the acrylate copolymer solution prepared in the S1, adding a solvent to prepare a mixed solution with the mass concentration of 5-30%, coating the surface of a base material with the mixed solution, and performing drying and high-temperature crosslinking film forming to obtain the acrylic copolymer / fluorinated organic silicon coating. According to the invention, the compatibility of the epoxy silicon fluoride resin and the carboxyl-containing acrylate copolymer can be improved, the wear resistance and antifouling performance of the prepared coating can be improved, and meanwhile, the prepared coating has good light transmittance.

Description

Technical Field

[0001] The invention relates to the technical field of composite coatings, in particular to a method for preparing an acrylic copolymer / fluorinated organosilicon coating. Background Art

[0002] Wear-resistant and antifouling coatings are in widespread use for surface protection. The primary method for preparing organic polymer-based wear-resistant and antifouling coatings is to add wear-resistant and antifouling nanoparticles to an organic polymer matrix and then blend them. This method offers advantages such as simplicity and low cost. However, it also suffers from poor compatibility between the nanoparticles and the organic polymer matrix, as well as poor dispersion of the nanoparticles in the composite coating. This results in poor wear resistance and antifouling properties, as well as low light transmittance.

[0003] Chinese patent CN 111100524 A discloses an epoxy polymer with hydrophobic and oleophobic properties. The preparation method is as follows: in a 50°C water bath, episulfide resin and epoxy resin are mixed, stirred, and bubbles are removed. The mixture is cooled to room temperature, and a curing agent and fluorinated silicone are added, stirred, and poured into a silicone mold. The mixture is cured at room temperature for 12 hours, and then transferred to a 60°C oven for curing for 1 hour. The epoxy resin is selected from bisphenol A epoxy resin or bisphenol F epoxy resin; and the curing agent is selected from an anhydride curing agent, an aromatic amine curing agent, and an aliphatic amine curing agent. The epoxy polymer with hydrophobic and oleophobic properties of the present invention has a refractive index of 1.5 or above, close to that of glass, and a transmittance of 80% or above. The epoxy polymer can be applied as a coating on optical materials. When applied to the glass surface, the epoxy polymer can achieve both oil and water repellency, with a hydrophobic angle greater than 130°, which can maintain the light transmittance of the glass under special conditions and improve its reliability. However, the coating prepared from the epoxy polymer has low hardness, poor wear resistance, and a short service life. Summary of the Invention

[0004] Based on this, it is necessary to provide a method for preparing an acrylic copolymer / fluorinated silicone coating to address the problems of poor compatibility between nanoparticles and organic polymer substrates and poor dispersion of nanoparticles in composite coatings in existing organic polymer-based wear-resistant and antifouling coatings, which lead to poor wear resistance and antifouling properties of the prepared coatings and low light transmittance.

[0005] A method for preparing an acrylic copolymer / fluorinated organosilicon coating comprises the following steps:

[0006] S1, dissolving the carboxyl group-containing acrylate copolymer in a solvent to obtain an acrylate copolymer solution with a mass concentration of 30%;

[0007] S2, dissolving the fluorinated epoxy silicone resin in a solvent to obtain a fluorinated epoxy silicone resin solution with a mass concentration of 30%;

[0008] S3. Under stirring, add the fluorinated epoxy silicone resin solution prepared in S2 to the acrylate copolymer solution prepared in S1, add a solvent to prepare a mixed solution with a mass concentration of 5% to 30%, apply the mixed solution on the surface of the substrate, and after drying and high-temperature cross-linking to form a film, obtain an acrylic copolymer / fluorinated silicone coating.

[0009] As a preferred embodiment, the method for preparing the carboxyl-containing acrylate copolymer comprises the following steps:

[0010] 60% of the initiator, carbonyl-containing acrylic monomer, acrylate monomer, and solvent are added to a reactor, and reacted under nitrogen protection and a first temperature condition, and then 40% of the initiator is added, and reacted under nitrogen protection and a second temperature condition to obtain a carboxyl-containing acrylic ester copolymer.

[0011] As a preferred solution, the carboxyl-containing acrylic acid monomer is acrylic acid, methacrylic acid or a mixture of acrylic acid and methacrylic acid.

[0012] As a preferred solution, the acrylic ester monomer is prepared by mixing methyl methacrylate and a long-chain acrylic ester monomer in a mass ratio of 2:1.

[0013] As a preferred embodiment, the chemical structure of the long-chain acrylic ester monomer is as follows:

[0014]

[0015] Here, n is an integer from 1 to 17.

[0016] As a preferred embodiment, the initiator is azoisobutylcyanide, azoisoheptylcyanide or a mixture of azoisobutylcyanide and azoisoheptylcyanide.

[0017] As a preferred solution, the mass of the initiator is 0.5% to 3% of the total mass of the carbonyl-containing acrylic monomer and the acrylate monomer.

[0018] As a preferred embodiment, the solvent is acetone, butanone, isophorone, ethyl acetate, butyl acetate, lactic acid ester, toluene or a mixture thereof.

[0019] As a preferred solution, the first temperature is 60°C.

[0020] As a preferred solution, the second temperature is 70°C.

[0021] As a preferred embodiment, the chemical structure of the fluorinated epoxy silicone resin in S2 is as follows:

[0022]

[0023] Here, n is an integer from 3 to 15.

[0024] As a preferred embodiment, the content of epoxy groups in the fluorinated epoxy silicone resin is 0.3 to 2.0 mol / 100 g.

[0025] As a preferred solution, the content of fluorinated groups in the fluorinated epoxy silicone resin is 0.3 to 2.0 mol / 100 g.

[0026] As a preferred solution, the mass of the epoxy fluorinated silicone resin is 0.5% to 5% of the mass of the carboxyl-containing acrylate copolymer.

[0027] As a preferred embodiment, the preparation method of the epoxy fluorinated silicone resin comprises the following steps:

[0028] S21, dissolving allyl glycidyl ether, fluorinated acrylate, and a catalyst in a low-polarity solvent to obtain a solution A;

[0029] S22, dissolving the hydrogenated silicone resin in a low-polarity solvent to obtain a solution B;

[0030] S23. Under nitrogen protection and heat preservation, the solution B obtained in S22 is added dropwise to the solution A obtained in S21 to react and obtain a fluorinated epoxy silicone resin.

[0031] As a preferred embodiment, the molecular structure of the allyl glycidyl ether is as follows:

[0032]

[0033] As a preferred embodiment, the molecular structure of the fluorinated acrylate is as follows:

[0034]

[0035] Wherein, n is an integer from 3 to 15.

[0036] As a preferred embodiment, the molecular structure of the hydrogenated silicone resin is as follows:

[0037]

[0038] The hydrogen content of the hydrogen-containing silicone resin is 0.3% to 2.0%.

[0039] As a preferred embodiment, the catalyst is chloroplatinic acid, and the catalyst accounts for 0.002‰ to 0.015‰ of the total mass of the reaction system.

[0040] As a preferred embodiment, the low-polarity solvent is toluene, benzene, xylene, hexane, heptane, ethyl acetate, butyl acetate, heptyl acetate or a mixture thereof.

[0041] As a preferred embodiment, the molar amount of the allyl glycidyl ether is 10% to 99% of the molar amount of hydrogen in the hydrogen-containing silicone resin.

[0042] As a preferred solution, the molar amount of the fluorine-containing acrylate is 1% to 10% of the molar amount of hydrogen in the hydrogen-containing silicone resin.

[0043] As a preferred solution, the drying temperature in S3 is 60°C to 90°C.

[0044] As a preferred solution, the high-temperature cross-linking temperature in S3 is 120°C to 180°C.

[0045] The present invention improves the compatibility of the epoxy fluorinated silicone resin and the carboxyl-containing acrylate copolymer by reacting the epoxy groups in the epoxy fluorinated silicone resin with the carboxyl groups in the carboxyl-containing acrylate copolymer. At the same time, the low surface energy and low friction coefficient of the silicone resin and the fluorine-containing group are utilized to improve the wear resistance and antifouling properties of the prepared coating, and at the same time, the prepared coating has good light transmittance. BRIEF DESCRIPTION OF THE DRAWINGS

[0046] Figure 1 FIG1 is a synthetic reaction equation diagram of the carboxyl-containing acrylate copolymer of the present invention;

[0047] Figure 2 FIG1 is a synthetic reaction equation diagram of the fluorinated epoxy silicone resin of the present invention;

[0048] Figure 3 is the FTIR spectrum of the fluorinated epoxy silicone resin of the present invention;

[0049] Figure 4 The fluorinated epoxy silicone resin of the present invention 19 F NMR spectrum.

[0050] Figure 5 These are scanning electron microscope images of the acrylic copolymer / fluorinated silicone coating of the present invention (a is a scanning electron microscope image of the cross section of the acrylic copolymer / fluorinated silicone coating, and b is a scanning electron microscope image of the surface of the acrylic copolymer / fluorinated silicone coating). DETAILED DESCRIPTION

[0051] The endpoints of the ranges and any values ​​disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoints of each range, the endpoints of each range and individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered to be specifically disclosed herein.

[0052] The following is a detailed description of the specific embodiments of the present invention. It should be understood that the specific embodiments described herein are only used to illustrate and explain the present invention and are not intended to limit the present invention.

[0053] A method for preparing an acrylic copolymer / fluorinated organosilicon coating comprises the following steps:

[0054] S1, dissolving the carboxyl group-containing acrylate copolymer in a solvent to obtain an acrylate copolymer solution with a mass concentration of 30%;

[0055] S2, dissolving the fluorinated epoxy silicone resin in a solvent to obtain a fluorinated epoxy silicone resin solution with a mass concentration of 30%;

[0056] S3. Under stirring, add the fluorinated epoxy silicone resin solution prepared in S2 to the acrylate copolymer solution prepared in S1, add a solvent to prepare a mixed solution with a mass concentration of 5% to 30%, apply the mixed solution on the surface of the substrate, and after drying and high-temperature cross-linking to form a film, obtain an acrylic copolymer / fluorinated silicone coating.

[0057] like Figure 1 As shown, the preparation method of the carboxyl-containing acrylate copolymer comprises the following steps:

[0058] 60% of the initiator, carbonyl-containing acrylic monomer, acrylate monomer, and solvent are added to a reactor, and reacted under nitrogen protection and a first temperature condition, and then 40% of the initiator is added, and reacted under nitrogen protection and a second temperature condition to obtain a carboxyl-containing acrylic ester copolymer.

[0059] As a preferred solution, the carboxyl-containing acrylic acid monomer is acrylic acid, methacrylic acid or a mixture of acrylic acid and methacrylic acid.

[0060] As a preferred solution, the acrylic ester monomer is prepared by mixing methyl methacrylate and a long-chain acrylic ester monomer in a mass ratio of 2:1.

[0061] As a preferred embodiment, the chemical structure of the long-chain acrylic ester monomer is as follows:

[0062]

[0063] Here, n is an integer from 1 to 17.

[0064] As a preferred embodiment, the initiator is azoisobutylcyanide, azoisoheptylcyanide or a mixture of azoisobutylcyanide and azoisoheptylcyanide.

[0065] As a preferred solution, the mass of the initiator is 0.5% to 3% of the total mass of the carbonyl-containing acrylic monomer and the acrylate monomer.

[0066] As a preferred embodiment, the solvent is acetone, butanone, isophorone, ethyl acetate, butyl acetate, lactic acid ester, toluene or a mixture thereof.

[0067] As a preferred solution, the first temperature is 60°C.

[0068] As a preferred solution, the second temperature is 70°C.

[0069] As a preferred embodiment, the chemical structure of the fluorinated epoxy silicone resin in S2 is as follows:

[0070]

[0071] Here, n is an integer from 3 to 15.

[0072] As a preferred embodiment, the content of epoxy groups in the fluorinated epoxy silicone resin is 0.3 to 2.0 mol / 100 g.

[0073] As a preferred solution, the content of fluorinated groups in the fluorinated epoxy silicone resin is 0.3 to 2.0 mol / 100 g.

[0074] As a preferred solution, the mass of the epoxy fluorinated silicone resin is 0.5% to 5% of the mass of the carboxyl-containing acrylate copolymer.

[0075] like Figure 2 As shown, the preparation method of the epoxy fluorinated silicone resin comprises the following steps:

[0076] S21, dissolving allyl glycidyl ether, fluorinated acrylate, and a catalyst in a low-polarity solvent to obtain a solution A;

[0077] S22, dissolving the hydrogenated silicone resin in a low-polarity solvent to obtain a solution B;

[0078] S23. Under nitrogen protection and heat preservation, the solution B obtained in S22 is added dropwise to the solution A obtained in S21 to react and obtain a fluorinated epoxy silicone resin.

[0079] As a preferred embodiment, the molecular structure of the allyl glycidyl ether is as follows:

[0080]

[0081] As a preferred embodiment, the molecular structure of the fluorinated acrylate is as follows:

[0082]

[0083] Wherein, n is an integer from 3 to 15.

[0084] As a preferred embodiment, the molecular structure of the hydrogenated silicone resin is as follows:

[0085]

[0086] The hydrogen content of the hydrogen-containing silicone resin is 0.3% to 2.0%.

[0087] As a preferred embodiment, the catalyst is chloroplatinic acid, and the catalyst accounts for 0.002‰ to 0.015‰ of the total mass of the reaction system.

[0088] As a preferred embodiment, the low-polarity solvent is toluene, benzene, xylene, hexane, heptane, ethyl acetate, butyl acetate, heptyl acetate or a mixture thereof.

[0089] As a preferred embodiment, the molar amount of the allyl glycidyl ether is 10% to 99% of the molar amount of hydrogen in the hydrogen-containing silicone resin.

[0090] As a preferred solution, the molar amount of the fluorine-containing acrylate is 1% to 10% of the molar amount of hydrogen in the hydrogen-containing silicone resin.

[0091] As a preferred solution, the drying temperature in S3 is 60°C to 90°C.

[0092] As a preferred solution, the high-temperature cross-linking temperature in S3 is 120°C to 180°C.

[0093] The present invention improves the compatibility of the epoxy fluorinated silicone resin and the carboxyl-containing acrylate copolymer by reacting the epoxy groups in the epoxy fluorinated silicone resin with the carboxyl groups in the carboxyl-containing acrylate copolymer. At the same time, the low surface energy and low friction coefficient of the silicone resin and the fluorine-containing group are utilized to improve the wear resistance and antifouling properties of the prepared coating, and at the same time, the prepared coating has good light transmittance.

[0094] Example 1

[0095] Preparation of carboxyl-containing acrylate copolymers

[0096] 6.0 g of azoisobutyl cyanide, 100 g of methacrylic acid, 600 g of methyl methacrylate, 300 g of dodecafluoroheptyl methacrylate, and 1.5 kg of toluene were added to a reactor. After the addition, nitrogen was introduced to remove the air in the reactor. Then, under nitrogen protection, the reaction was carried out at a first temperature of 60° C. for 2 hours. Then, 4.0 g of azoisobutyl cyanide was added, and under nitrogen protection, the reaction was carried out at a second temperature of 70° C. for 1.5 hours to obtain a carboxyl-containing acrylate copolymer.

[0097] Example 2

[0098] Preparation of carboxyl-containing acrylate copolymers

[0099] 3.0 g of azoisoheptyl cyanide, 100 g of acrylic acid, 600 g of methyl methacrylate, 300 g of dodecafluoroheptyl methacrylate, and 1.5 kg of isophorone were added to a reactor. After the addition, nitrogen was introduced to remove the air in the reactor. Then, under nitrogen protection, the reaction was carried out at a first temperature of 60° C. for 2 hours. Then, 2.0 g of azoisoheptyl cyanide was added, and under nitrogen protection, the reaction was carried out at a second temperature of 70° C. for 1.5 hours to obtain a carboxyl-containing acrylate copolymer.

[0100] Example 3

[0101] Preparation of carboxyl-containing acrylate copolymers

[0102] 18.0 g of a mixture of azoisobutylcyanide and azoisoheptylcyanide (the mass ratio of azoisobutylcyanide to azoisoheptylcyanide is 1:1), 100 g of a mixture of acrylic acid and methacrylic acid (wherein the mass ratio of acrylic acid to methacrylic acid is 1:1), 600 g of methyl methacrylate, 300 g of dodecafluoroheptyl methacrylate, and 1.5 kg of ethyl acetate were added to a reactor. After the addition, nitrogen was introduced to remove the air in the reactor. Then, under nitrogen protection, the first temperature was 60° C., and the reaction was carried out for 2 hours. Then, 12.0 g of a mixture of azoisobutylcyanide and azoisoheptylcyanide (the mass ratio of azoisobutylcyanide to azoisoheptylcyanide is 1:1) was added, and under nitrogen protection, the second temperature was 70° C., and the reaction was carried out for 1.5 hours to obtain a carboxyl-containing acrylate copolymer.

[0103] Example 4

[0104] Preparation of fluorinated epoxy silicone resin

[0105] S1. Dissolve 114.14 g of allyl glycidyl ether (1.0 mol), 43.22 g of ethyl perfluorohexyl methacrylate (0.1 mol), and 2.5 mg of chloroplatinic acid in 300.0 g of toluene and add the solution to a reactor to obtain solution A.

[0106] S2. Dissolve 149.28 g (1.05 mol) of hydrogenated silicone resin (hydrogen content is 0.7 mol / 100 g) in 150 g of toluene to obtain solution B, and place solution B into a dropping funnel;

[0107] S3. Nitrogen is introduced into the reactor to evacuate the air, and the reaction temperature is raised to 85°C under nitrogen protection. Solution B in the dropping funnel is added to solution A in the reactor within 3 hours. After the addition is complete, the reaction is continued for 1 hour. After the reaction is completed, the temperature of the solution in the reactor is reduced to 30°C, and then filtered through an activated carbon column to remove chloroplatinic acid in the reaction solution. The unreacted small amount of alkenyl glycidyl ether, ethyl perfluorohexyl methacrylate and toluene are removed by vacuum distillation to obtain a fluorinated epoxy silicone resin.

[0108] Example 5

[0109] Preparation of fluorinated epoxy silicone resin

[0110] S1. Dissolve 11.985 g of allyl glycidyl ether (0.105 mol), 4.538 g of ethyl perfluorohexyl methacrylate (0.0105 mol), and 0.33 mg of chloroplatinic acid in 300.0 g of heptane, and add the solution to a reactor to obtain solution A.

[0111] S2. Dissolve 149.28 g (1.05 mol) of hydrogenated silicone resin (hydrogen content is 0.7 mol / 100 g) in 150 g of heptane to obtain solution B, and place solution B into a dropping funnel;

[0112] S3. Nitrogen was introduced into the reactor to evacuate the air, and the reaction temperature was raised to 85°C under nitrogen protection. Solution B in the dropping funnel was added to solution A in the reactor within 3 hours. After the addition was complete, the reaction was continued for 1 hour. After the reaction was completed, the temperature of the solution in the reactor was reduced to 30°C, and then filtered through an activated carbon column to remove chloroplatinic acid in the reaction solution. The unreacted small amount of alkenyl glycidyl ether, ethyl perfluorohexyl methacrylate and heptane were removed by distillation under reduced pressure to obtain a fluorinated epoxy silicone resin.

[0113] Example 6

[0114] Preparation of fluorinated epoxy silicone resin

[0115] S1. Dissolve 118.65 g of allyl glycidyl ether (1.0395 mol), 45.38 g of ethyl perfluorohexyl methacrylate (0.105 mol), and 4.7 mg of chloroplatinic acid in 300.0 g of heptyl acetate, and add the solution to a reactor to obtain solution A.

[0116] S2, 149.28g (1.05mol) of hydrogenated silicone resin (hydrogen content of 0.7mol / 100g) was dissolved in 150g of heptyl acetate to obtain solution B, and solution B was placed in a dropping funnel;

[0117] S3. Nitrogen is introduced into the reactor to evacuate the air, and the reaction temperature is raised to 85°C under nitrogen protection. Solution B in the dropping funnel is added to solution A in the reactor within 3 hours. After the addition is complete, the reaction is continued for 1 hour. After the reaction is completed, the temperature of the solution in the reactor is reduced to 30°C, and then filtered through an activated carbon column to remove chloroplatinic acid in the reaction solution. Then, unreacted small amounts of alkenyl glycidyl ether, ethyl perfluorohexyl methacrylate and heptyl acetate are removed by distillation under reduced pressure to obtain a fluorinated epoxy silicone resin.

[0118] Example 7

[0119] Preparation of acrylic copolymer / fluorinated silicone coating

[0120] S1, dissolving the carboxyl group-containing acrylate copolymer prepared in Example 1 in toluene to obtain an acrylate copolymer solution with a mass concentration of 30%;

[0121] S2, dissolving the fluorinated epoxy silicone resin prepared in Example 4 in toluene to obtain a fluorinated epoxy silicone resin solution with a mass concentration of 30%;

[0122] S3. Under stirring, add the fluorinated epoxy silicone resin solution prepared in S2 to the acrylate copolymer solution prepared in S1, wherein the mass of the epoxy fluorinated silicone resin is 0.5% of the mass of the carboxyl-containing acrylate copolymer, add toluene to prepare a mixed solution with a mass concentration of 5% to 30%, apply the mixed solution on the surface of the substrate, dry at 80°C for 0.5 hour, and crosslink at 120°C for 2 hours to obtain an acrylic copolymer / fluorinated silicone coating.

[0123] Example 8

[0124] Preparation of acrylic copolymer / fluorinated silicone coating

[0125] S1, dissolving the carboxyl group-containing acrylate copolymer prepared in Example 1 in toluene to obtain an acrylate copolymer solution with a mass concentration of 30%;

[0126] S2, dissolving the fluorinated epoxy silicone resin prepared in Example 4 in toluene to obtain a fluorinated epoxy silicone resin solution with a mass concentration of 30%;

[0127] S3. Under stirring, add the fluorinated epoxy silicone resin solution prepared in S2 to the acrylate copolymer solution prepared in S1, wherein the mass of the epoxy fluorinated silicone resin is 1.0% of the mass of the carboxyl-containing acrylate copolymer, add toluene to prepare a mixed solution with a mass concentration of 5% to 30%, apply the mixed solution on the surface of the substrate, dry at 80°C for 0.5 hour, and crosslink at 120°C for 2 hours to obtain an acrylic copolymer / fluorinated silicone coating.

[0128] Example 9

[0129] Preparation of acrylic copolymer / fluorinated silicone coating

[0130] S1, dissolving the carboxyl group-containing acrylate copolymer prepared in Example 1 in toluene to obtain an acrylate copolymer solution with a mass concentration of 30%;

[0131] S2, dissolving the fluorinated epoxy silicone resin prepared in Example 4 in toluene to obtain a fluorinated epoxy silicone resin solution with a mass concentration of 30%;

[0132] S3. Under stirring, add the fluorinated epoxy silicone resin solution prepared in S2 to the acrylate copolymer solution prepared in S1, wherein the mass of the epoxy fluorinated silicone resin is 2.0% of the mass of the carboxyl-containing acrylate copolymer, add toluene to prepare a mixed solution with a mass concentration of 5% to 30%, apply the mixed solution on the surface of the substrate, dry at 80°C for 0.5 hour, and crosslink at 120°C for 2 hours to obtain an acrylic copolymer / fluorinated silicone coating.

[0133] Example 10

[0134] Preparation of acrylic copolymer / fluorinated silicone coating

[0135] S1, dissolving the carboxyl group-containing acrylate copolymer prepared in Example 1 in toluene to obtain an acrylate copolymer solution with a mass concentration of 30%;

[0136] S2, dissolving the fluorinated epoxy silicone resin prepared in Example 4 in toluene to obtain a fluorinated epoxy silicone resin solution with a mass concentration of 30%;

[0137] S3. Under stirring, add the fluorinated epoxy silicone resin solution prepared in S2 to the acrylate copolymer solution prepared in S1, wherein the mass of the epoxy fluorinated silicone resin is 5.0% of the mass of the carboxyl-containing acrylate copolymer, add toluene to prepare a mixed solution with a mass concentration of 5% to 30%, apply the mixed solution on the surface of the substrate, dry at 80°C for 0.5 hour, and crosslink at 120°C for 2 hours to obtain an acrylic copolymer / fluorinated silicone coating.

[0138] Comparative Example

[0139] Preparation of acrylic copolymer coating

[0140] The carboxyl-containing acrylate copolymer prepared in Example 1 was dissolved in toluene to obtain an acrylate copolymer solution with a mass concentration of 5% to 30%. The acrylate copolymer solution was applied to the surface of the substrate, dried at 80°C for 0.5 hour, and cross-linked at 120°C for 2 hours to obtain an acrylic copolymer coating.

[0141] Test Example 1

[0142] Fourier transform infrared spectroscopy

[0143] The fluorinated epoxy silicone resin HMQ-AGE-G06B prepared in Example 4 was tested using a Fourier transform infrared spectrometer. The experimental results are as follows: Figure 2 shown.

[0144] Depend on Figure 3 It can be seen that 900cm -1 The peak at 2960 cm is attributed to the epoxy group. -1 The peaks at 1062 and 833 cm are due to the stretching vibrations of the -CH2- group in glycidyloxypropyl and ethyl perfluorohexyl methacrylate. -1 The peaks at 1251 cm-1 correspond to Si-O-Si and Si-C stretching vibrations, respectively. -1 The peak at is from the CF bond in ethyl perfluorohexyl methacrylate

[113] , 2138cm -1 The peaks at are attributed to the unreacted Si-H bonds in the hydrogenated silicone resin (HMQ), which indicates that the epoxy groups (AGE) and fluorine-containing groups (G06B) have been successfully grafted onto the hydrogenated silicone resin (HMQ).

[0145] Test Example 2

[0146] NMR fluorine spectrum test

[0147] The fluorinated epoxy silicone resin HMQ-AGE-G06B prepared in Example 4 was tested by nuclear magnetic resonance fluorine spectrum using a nuclear magnetic resonance instrument. The results are as follows: Figure 3 shown.

[0148] Depend on Figure 4 It can be seen that the signal at -64ppm corresponds to -CH2-C F2 -F in the environment a The signals centered at -108ppm and -123ppm correspond to F c and F dThe fluorine atom (-C F2 -C F2 -CF3). The signal at -80ppm corresponds to F b The fluorine atom (-CF2-C F3 The above characterizations indicate that the fluorinated epoxy silicone resin has been successfully synthesized.

[0149] Test Example 3

[0150] Scanning electron microscopy experiments of acrylic copolymer / fluorinated silicone coatings

[0151] The acrylic copolymer / fluorinated organosilicon coating prepared in Example 7 was tested using an electron scanning microscope. The experimental results are as follows: Figure 5 shown.

[0152] Test Example 4

[0153] Relationship between the amount of fluorinated epoxy silicone resin and the hardness, adhesion, wear resistance and water contact angle of the coating

[0154] 1) Testing the abrasion resistance of the acrylic copolymer / fluorinated silicone coatings prepared in Examples 7 to 10 and the acrylic copolymer coating prepared in the comparative example using ASTM D4060-10, and testing the number of cycles required to abrade the acrylic copolymer / fluorinated silicone coatings prepared in Examples 7 to 10 and the acrylic copolymer coating prepared in the comparative example; wherein, elastic CS-10 abrasive particles with a load of 1000 g were used during the testing;

[0155] 2) The acrylic copolymer / fluorinated silicone coatings prepared in Examples 7 to 10 and the acrylic copolymer coating prepared in the comparative example were tested for water contact angle using a water drop contact angle meter. The test data were recorded and organized. The results are shown in Table 1.

[0156] Table 1 Relationship between the amount of fluorinated epoxy silicone resin and the hardness, adhesion, wear resistance and water contact angle of the coating

[0157]

[0158] As shown in Table 1, the hardness, adhesion, and wear resistance of the coating prepared with the addition of fluorinated epoxy silicone resin are all improved compared to the coating prepared without the addition of fluorinated epoxy silicone resin. The hardness and wear resistance of the coating prepared with the addition of fluorinated epoxy silicone resin improve as the amount of fluorinated epoxy silicone resin added increases. The water contact angle increases with the amount of fluorinated epoxy silicone resin added. This demonstrates that during the coating preparation process, the epoxy groups in the fluorinated epoxy silicone resin react with the carboxyl groups in the carboxyl-containing acrylic copolymer resin, improving the compatibility between the fluorinated epoxy silicone resin and the carboxyl-containing acrylic copolymer resin. Simultaneously, the low surface energy and low friction coefficient of the hydrogenated silicone resin and the fluorinated groups are utilized to improve the hardness and wear resistance of the coating. The resulting coating exhibits excellent antifouling properties.

[0159] The technical features of the above-mentioned embodiments can be combined arbitrarily. In order to make the description concise, not all possible combinations of the technical features in the above-mentioned embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0160] The above-described embodiments merely illustrate several implementations of the present invention, and while their descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the patent. It should be noted that a person skilled in the art would be able to make numerous variations and improvements without departing from the spirit of the present invention, all of which fall within the scope of protection of the present invention. Therefore, the scope of protection of the patent for this invention shall be determined by the appended claims.

Claims

1. A method for preparing an acrylic copolymer / fluorinated organosilicon coating, characterized in that: The following steps are involved: S1, dissolving the carboxyl group-containing acrylate copolymer in a solvent to obtain an acrylate copolymer solution with a mass concentration of 30%; S2, dissolving the fluorinated epoxy silicone resin in a solvent to obtain a fluorinated epoxy silicone resin solution with a mass concentration of 30%; S3. Under stirring, add the fluorinated epoxy silicone resin solution prepared in S2 to the acrylate copolymer solution prepared in S1, add a solvent to prepare a mixed solution with a mass concentration of 5% to 30%, apply the mixed solution on the surface of the substrate, and after drying and high-temperature cross-linking to form a film, obtain an acrylic copolymer / fluorinated silicone coating.

2. The method for preparing the acrylic copolymer / fluorinated organosilicon coating according to claim 1, wherein: The preparation method of the carboxyl-containing acrylate copolymer comprises the following steps: 60% of the initiator, carbonyl-containing acrylic monomer, acrylate monomer, and solvent are added to a reactor, and reacted under nitrogen protection and a first temperature condition, and then 40% of the initiator is added, and reacted under nitrogen protection and a second temperature condition to obtain a carboxyl-containing acrylic ester copolymer.

3. The method for preparing the acrylic copolymer / fluorinated organosilicon coating according to claim 2, wherein: The carboxyl-containing acrylic acid monomer is acrylic acid, methacrylic acid or a mixture of acrylic acid and methacrylic acid.

4. The method for preparing the acrylic copolymer / fluorinated organosilicon coating according to claim 2, wherein: The acrylic acid ester monomer is prepared by mixing methyl methacrylate and a long-chain acrylic acid ester monomer in a mass ratio of 2:

1.

5. The method for preparing the acrylic copolymer / fluorinated organosilicon coating according to claim 4, wherein: The chemical structural formula of the long-chain acrylate monomer is as follows: Here, n is an integer from 1 to 17.

6. The method for preparing the acrylic copolymer / fluorinated organosilicon coating according to claim 2, wherein: The initiator is azoisobutylcyanide, azoisoheptylcyanide or a mixture of azoisobutylcyanide and azoisoheptylcyanide. The mass of the initiator is 0.5% to 3% of the total mass of the carbonyl-containing acrylic monomer and the acrylate monomer.

7. The method for preparing an acrylic copolymer / fluorinated organosilicon coating according to claim 1, wherein: The chemical structure of the fluorinated epoxy silicone resin in S2 is as follows: Here, n is an integer from 3 to 15.

8. The method for preparing the acrylic copolymer / fluorinated silicone coating according to claim 1, characterized in that: The content of epoxy groups in the fluorinated epoxy silicone resin is 0.3 to 2.0 mol / 100g.

9. The method for preparing the acrylic copolymer / fluorinated organosilicon coating according to claim 1, characterized in that: The content of fluorinated groups in the fluorinated epoxy silicone resin is 0.3 to 2.0 mol / 100g.

10. The method for preparing an acrylic copolymer / fluorinated organosilicon coating according to claim 1, wherein: The mass of the epoxy fluorinated silicone resin is 0.5% to 5% of the mass of the carboxyl-containing acrylate copolymer.

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