Preparation method of polymer coating with bowknot-shaped core-shell nanometer container

Abstract

The invention provides a preparation method of a polymer coating with a bowknot-shaped core-shell nano container, which comprises the following steps: firstly preparing a Ce-MOF nano container through specific steps, and then carrying out functional modification by loading tannic acid and polyethyleneimine to obtain CTAP. And then, synthesizing a bornyl fluorine-containing acrylic polymer (PBAF), and combining the bornyl fluorine-containing acrylic polymer with the CTAP to form the nano container polymer coating with the bowknot-shaped core-shell structure. In the preparation process, the raw material ratio, the reaction conditions and the like are optimized in detail, and the purity, the structural stability and the functionalization effect of the product are ensured. The coating has excellent anti-fouling, anti-corrosion and self-repairing performance, and is suitable for various complex environments. Compared with a traditional coating material, the performance of the prepared coating is remarkably improved, and the anti-fouling and anti-corrosion application with higher requirements can be met.

Description

Technical Field

[0001] The present invention relates to the field of polymer coating materials, and particularly to a preparation method of a polymer coating with bow-shaped core-shell nanocontainers. Background Art

[0002] Tannic acid is a widely existing natural polyphenol, which has antibacterial, antioxidant, anti-inflammatory and antitumor activities. A tannic acid molecule contains 15 phenolic hydroxyl groups. Metal chelation is a remarkable feature of tannic acid, and it can act as a multidentate ligand to coordinate with metal ions. Therefore, the phenolic hydroxyl groups of tannic acid can form highly stable monodentate or multidentate complexes with iron ions (Fe 3+ / Fe 2+ ), and tannic acid can provide active corrosion protection for carbon steel as an environmentally friendly corrosion inhibitor.

[0003] With the rapid development of nanotechnology, nanomaterials with special structures and functions have shown great application potential in multiple fields, especially in materials science, biomedicine, environmental protection, etc. Among them, core-shell nanocontainers, as a unique nanostructure, have attracted much attention because they can encapsulate and protect various functional substances while providing controllable release characteristics. Such materials have broad application prospects in the fields of drug delivery, catalytic reactions, sensors, and antifouling and anticorrosion coatings.

[0004] However, there are often some problems in the preparation process of core-shell nanocontainers in the prior art, such as cumbersome preparation steps, low product purity, poor structural stability, and difficult functionalization modification. Especially when preparing core-shell nanocontainers with complex structures (such as bow-shaped), these problems are particularly prominent. In addition, although the polymer coatings in the prior art can provide antifouling and anticorrosion functions to a certain extent, their performance is often limited by factors such as coating uniformity, adhesion, and durability.

[0005] In the field of antifouling and anticorrosion coatings, although traditional coating materials can resist the erosion and pollution of the external environment to a certain extent, their limitations gradually emerge in the face of increasingly complex use environments and higher performance requirements. For example, traditional coatings may not be able to maintain their antifouling and anticorrosion performance for a long time, or are prone to failure under extreme conditions (such as high temperature, high humidity, strong corrosion, etc.). Therefore, it is particularly important to develop a new type of antifouling and anticorrosion coating material with excellent performance. Summary of the Invention

[0006] In view of this, the present invention proposes a preparation method of a polymer coating with bow-shaped core-shell nanocontainers.

[0007] The technical solution of the present invention is realized as follows: A preparation method of a polymer coating with a bow-shaped core-shell nanocontainer: The method comprises the following steps:

[0008] S1. Preparation of Ce-MOF nanocontainers: Take 1,3,5-benzenetricarboxylic acid and dissolve it in a mixed solution of deionized water and ethanol to obtain solution A. Use a cerium nitrate solution with a pH adjusted to 3-4 as solution B. Add solution B to solution A to obtain Ce-MOF nanocontainers;

[0009] S2. Preparation of CTA: Add the above-mentioned Ce-MOF nanocontainers to a tannic acid phosphate buffer solution, stir, centrifuge, wash, and collect the Ce-MOF loaded with tannic acid, which is CTA;

[0010] S3. Preparation of CTAP: Add a polyethyleneimine solution to a tannic acid phosphate buffer solution and stir. Then add CTA to the above solution and continue to stir. Centrifuge, wash, and dry. The final product obtained is CTAP;

[0011] S4. Preparation of PBAF: Add xylene and propylene glycol methyl ether to a bottle and heat. Then take methyl methacrylate, ethyl acrylate, isobornyl methacrylate, hexafluorobutyl methacrylate, a chain transfer agent, and azobisisobutyronitrile, mix them and add them to the above bottle. After stirring, a transparent mixed solution is obtained. Then dissolve benzoyl peroxide in the above mixed solution and react to obtain a colorless and transparent isobornyl fluorinated acrylic polymer (PBAF);

[0012] S5. Preparation of CTAP-PBAF: Disperse the CTAP prepared in S3 into N,N-dimethylformamide and add the isobornyl fluorinated acrylic polymer prepared in S4. After stirring evenly, cure at room temperature to obtain an isobornyl fluorinated acrylic polymer coating with a bow-shaped core-shell nanocontainer;

[0013] S6. Disperse CTAP into dimethylformamide and add it to the isobornyl fluorinated acrylic polymer coating. After stirring evenly, cure at room temperature to obtain a polymer coating with a bow-shaped core-shell nanocontainer.

[0014] Preferably, the preparation method of the polymer coating with a bow-shaped core-shell nanocontainer: The method comprises the following steps:

[0015] S1. Preparation of Ce-MOF nanocontainers: Dissolve 0.3 - 0.8 mmol of 1,3,5-benzenetricarboxylic acid in a mixed solution of 30 - 50 mL of deionized water and ethanol to obtain solution A. Then, adjust the pH of the cerium nitrate solution to 3 - 4 with a 0.03 - 0.08 mol / L nitric acid solution to obtain solution B. Take 0.5 - 1.5 mL of solution B and slowly and evenly drip it into solution A. After stirring at room temperature for 5 - 15 min, centrifuge for 8 - 12 min, wash 2 - 4 times with deionized water and ethanol respectively, and dry at 50 - 80 °C for 20 - 30 h to obtain Ce-MOF nanocontainers;

[0016] S2. Preparation of CTA: Add 0.05 - 0.15 g of the above Ce-MOF nanocontainers to a tannic acid phosphate buffer solution (TPBS, pH≈8.0) with a concentration of 18 - 22 g / L, stir in a vacuum state for 8 - 12 min, then centrifuge at 3500 - 4500 rpm for 5 - 15 min, wash 2 - 4 times with deionized water, and collect the Ce-MOF loaded with tannic acid (TA), which is CTA;

[0017] S3. Preparation of CTAP: Add a 6 - 7 g / L polyethyleneimine solution to 8 - 12 mL of tannic acid phosphate buffer solution (TPBS-PEI) and stir for 3 - 8 min. Then, add 0.05 - 0.15 g of the above-prepared CTA to the above solution and continue to stir for 3 - 8 min. After that, centrifuge at 3500 - 4500 rpm for 5 - 15 min, wash 3 times with deionized water, and dry at 50 - 80 °C for 20 - 30 h. The final product obtained is named CTAP;

[0018] S4. Preparation of PBAF: Add xylene and propylene glycol methyl ether to a four-necked flask equipped with a thermometer and a spherical condenser, heat the temperature to 90 - 100 °C. Subsequently, weigh 4 - 5 g of methyl methacrylate (MMA), 3 - 5 g of ethyl acrylate (EA), 1 - 3 g of isobornyl methacrylate (IBOMA), 2 - 8 g of hexafluorobutyl methacrylate (HFBMA), 8 - 10 g of chain transfer agent (MSD), and 1 - 3 g of azobisisobutyronitrile (AIBN). After mixing, add them to the above xylene and propylene glycol methyl ether, and stir with a magnetic stirrer for 2 - 4 min to obtain a transparent mixed solution. Transfer the mixed solution to a constant pressure dropping funnel and drop it into the four-necked flask drop by drop. The dropping time is 2 - 6 h. During this period, maintain a nitrogen atmosphere in the flask. After the dropping is completed, weigh benzoyl peroxide (BPO) and dissolve it in the above mixed solution, and drop it into the four-necked flask within 30 min. Keep the reaction for 90 - 100 min to obtain a colorless and transparent borneol-based fluorinated acrylic polymer (PBAF);

[0019] S5. Preparation of CTAP-PBAF: Disperse CTAP with a resin mass fraction of 0.3 - 0.8 wt% into N,N-dimethylformamide (DMF), add 0.5 - 1.5 g of norbornene-based fluorinated acrylic polymer (PBAF), stir evenly, and cure at room temperature for 4 - 5 h for standby to obtain a norbornene-based fluorinated acrylic polymer coating with a bow-shaped core-shell nanocontainer.

[0020] Preferably, in S1, the volume ratio of deionized water to ethanol is 1:1.

[0021] Preferably, in S1, the pH of the cerium nitrate solution is adjusted to 3 - 4 with a 0.03 - 0.08 mol / L nitric acid solution to obtain solution B.

[0022] Preferably, in S1, S2, and S3, the centrifugation speed is 3500 - 4500 rpm and the centrifugation time is 5 - 15 min.

[0023] Preferably, in S4, the volume ratio of xylene to propylene glycol methyl ether is 0.3 - 0.8:1.

[0024] Preferably, in S4, the mass-volume ratio of benzoyl peroxide to the mixed solution is 3 - 8:100 g / mL.

[0025] Preferably, in S4, the weight-average molecular weight of the norbornene-based fluorinated acrylic polymer is 3.10 - 3.75×10 4 g / mol, and the molecular weight distribution (PDI) is between 1.63 and 1.90.

[0026] The polymer coating with a bow-shaped core-shell nanocontainer prepared by the above preparation method.

[0027] Preferably, a polymer coating with a bow-shaped core-shell nanocontainer is applied to anti-fouling and anti-corrosion coatings.

[0028] Compared with the prior art, the beneficial effects of the present invention are:

[0029] The present invention constructs a pH-responsive self-healing norbornene-based fluorinated acrylic polymer coating (CTAP-PBAF) with a bow-shaped core-shell nanocontainer. The coating is composed of tannic acid as an environmentally friendly corrosion inhibitor, Ce-MOF as a nanocontainer, and polyethyleneimine (PEI) as a shell. Among them, the polyethyleneimine shell is coated by a Schiff base reaction with a quinonylated tannic acid corrosion inhibitor. The pH response of the synthesized CTAP depends on the instability of the Schiff base reaction in a relatively strong acidic environment, enabling the tannic acid corrosion inhibitor to be rapidly released from CTAP. The CTAP-PBAF coating has good corrosion resistance, self-healing performance, and anti-fouling performance. Description of the Drawings

[0030] Figure 1 It is a schematic diagram of the preparation process of CTAP nanocontainers;

[0031] Figure 2 It is a schematic diagram of the synthesis of borneol-based fluorinated acrylic polymer;

[0032] Figure 3 It is the SEM diagram of the structural characterization of Ce-MOF, CTA, and CTAP;

[0033] Figure 4 It is the TEM and corresponding mappings diagrams of CTAP;

[0034] Figure 5 It is the infrared spectra diagrams of acrylic polymer, borneol-based acrylic polymer, and borneol-based fluorinated acrylic polymer;

[0035] Figure 6 It is the Nyquist and Bode diagrams of (a-c) EP, (d-f) Ce-MOF-EP, (g-i) CTA-EP, and (j-l) CTAP-PBAF after being immersed in 3.5 wt.% NaCl solution for different times;

[0036] Figure 7 It is the Nyquist and Bode diagrams of (a-c) S-Ce-MOF-PBAF and (d-f) S-CTAP-PBAF after being immersed in 3.5 wt.% NaCl solution for different times. Detailed implementation manners

[0037] In order to better understand the technical content of the present invention, specific embodiments are provided below to further illustrate the present invention.

[0038] The experimental methods used in the embodiments of the present invention are all conventional methods unless otherwise specified.

[0039] The materials, reagents, etc. used in the embodiments of the present invention can be obtained from commercial channels unless otherwise specified.

[0040] Example 1 - Preparation of Ce-MOF nanocontainers:

[0041] Dissolve 0.5 mmol of 1,3,5-benzenetricarboxylic acid in a mixed solution of 40 mL of deionized water and ethanol to obtain solution A. Then, adjust the pH of the cerium nitrate solution to 3.5 with 0.05 mol / L nitric acid solution to obtain solution B. Take 1 mL of solution B and slowly drip it into solution A at a constant speed. Immediately, a large amount of white powder is produced. After stirring at room temperature for 10 min, centrifuge the suspension for 10 min, wash it three times with deionized water and ethanol respectively, and dry it at 60 °C for 24 h to obtain Ce-MOF nanocontainers. The preparation process of CTAP nanocontainers is as Figure 1 shown.

[0042] Example 2 - Preparation of CTA:

[0043] Add 0.1 g of the above Ce-MOF nanocontainers to 20 g / L tannic acid phosphate buffer solution (TPBS, pH≈8.0), stir under vacuum for 10 min, then centrifuge at 4000 rpm for 10 min, wash three times with deionized water, and collect the Ce-MOF loaded with tannic acid (TA), which is CTA.

[0044] Example 3 - Preparation of CTAP:

[0045] Add 6.6 g / L polyethyleneimine solution to 10 mL of tannic acid phosphate buffer solution (TPBS-PEI) and stir for 5 min. Then, add 0.05 - 0.15 g of the above-prepared CTA to the above solution and continue to stir for 5 min. After that, centrifuge the suspension at 4000 rpm for 10 min, wash three times with deionized water, and dry the sample at 60 °C for 24 h. The final product obtained is named CTAP.

[0046] Example 4 - Preparation of PBAF:

[0047] Add xylene and propylene glycol methyl ether with a volume ratio of 0.5:1 to a four-necked flask equipped with a thermometer and a spherical condenser, heat the temperature to 95 °C. Subsequently, weigh 5 g of methyl methacrylate (MMA), 4 g of ethyl acrylate (EA), 2 g of isobornyl methacrylate (IBOMA), 6 g of hexafluorobutyl methacrylate (HFBMA), 9 g of chain transfer agent (MSD), and 2 g of azobisisobutyronitrile (AIBN). After mixing, add them to the above xylene and propylene glycol methyl ether, and stir with a magnetic stirrer for 3 min to obtain a transparent mixed solution. Transfer the mixed solution to a constant pressure dropping funnel and drop it into the four-necked flask drop by drop. The dropping time is 4 h. During this period, maintain a nitrogen atmosphere in the flask. After the dropping is completed, weigh 5 g of benzoyl peroxide (BPO) and dissolve it in 100 mL of the above mixed solution, and drop it into the four-necked flask within 30 min. Keep the reaction for 90 min to obtain a colorless and transparent borneol-based fluorinated acrylic polymer (PBAF), whose weight average molecular weight is 3.10 - 3.75×104 g / mol, with a molecular weight distribution (PDI) ranging from 1.63 to 1.90. The synthesis of the bornyl fluorinated acrylic polymer is as Figure 2 shown.

[0048] Example 5 - Preparation of CTAP - PBAF:

[0049] Disperse Ce - MOF with a resin mass fraction of 0.5 wt% into N,N - dimethylformamide (DMF), add 1 g of bornyl fluorinated acrylic polymer, stir evenly, and cure at room temperature for 5 h for later use to obtain a bornyl fluorinated acrylic polymer coating with bow - tie - shaped core - shell nanocontainers.

[0050] I. Structure Characterization of Ce - MOF

[0051] The surface morphologies and structures of Ce - MOF, CTA, and CTAP were observed by SEM and TEM / EDS ( Figure 3 ). It can be seen from Figure 3 a - d that the bow - tie - shaped Ce - MOF is composed of nanorods bundled together. Their lengths are 4 - 6 μm, and the diameter of the middle knot is 1 - 2 μm. Then, the surfaces of these Ce - MOF are relatively flat and smooth.

[0052] For CTA, they are still bow - tie - shaped, but their surfaces become relatively rough. Compared with Ce - MOF, the size slightly increases, and the O content increases ( Figure 3 k), which is related to the loading of TA on Ce - MOF ( Figure 3 e - h).

[0053] For CTAP, its size is significantly larger than that of CTA ( Figure 3 f, i), and the N content (3.13 wt%) is significantly higher than that of Ce - MOF (0.63 wt%) and CTA (1.63 wt%). This is attributed to the coating of the PEI shell. It can be clearly seen from Figure 4 that C, O, N, and Ce are the main elements of CTAP, and the outermost shell can also be clearly seen. Zeta potential further shows ( Figure 4 ) that the positively charged PEI can be adsorbed onto the negatively charged TA surface through electrostatic interaction.

[0054] II. Molecular Structure Analysis of PBAF Polymer

[0055] Figure 5 are the Fourier transform infrared spectra of acrylic polymer (PAC), bornyl acrylic polymer (PBA), and bornyl fluorinated acrylic polymer (PBAF). In all polymers, at 1630 cm -1No peaks appear at this position, indicating that the reaction is complete and there is no residual monomer. At 2800 cm -1 ~3000 cm -1 The peaks appearing in the region are the stretching vibration absorption peaks of -C-H on methyl and methylene groups. At 1740 cm -1 The peak corresponds to the stretching vibration absorption peak of the carbonyl group in different polymers. For PBA 3 F polymer, the newly emerged peak at 1286 cm -1 is the stretching vibration absorption peak of -C-F 3 , while the new peaks at 1096 cm -1 and 1135 cm -1 are the stretching vibration absorption peaks of -C-F 2 .

[0056] III. Long-term corrosion resistance of CTAP-PBAF

[0057] Figure 6 . are the Nyquist and Bode plots of EP, Ce-MOF-EP, CTA-EP, and CTAP-PBAF after immersion in 3.5 wt.% NaCl solution for different times

[0058] Generally, a high value of the low-frequency impedance modulus (|Z| 0.01Hz ) indicates excellent protective ability of the coating. For EP, |Z| 0.01Hz decreases significantly with time. After immersion for 35 d, it drops from the initial 1.79×10 10 Ω·cm 2 to 1.16×10 6 Ω·cm 2 ( Figure 6 .b), because micropores and defects are inevitably generated in the EP coating during the preparation process due to the volatilization of organic solvents, making it easy for the electrolyte to reach the coating / metal interface and causing EP inactivation. For Ce-MOF-EP, its |Z| 0.01Hz drops from 1.88×10 10 Ω·cm 2 to 1.22×10 9 Ω·cm 2 after immersion for 28 d, and gradually rises to 2.07×10 9 Ω·cm 2 ( Figure 6 .e), which can be attributed to the self-healing ability of Ce-MOF to some extent. In addition, Ce-MOF as a filler can better improve the passive barrier performance of EP. For CTA-EP, its |Z| 0.01Hz drops from 2.17×10 9 Ω·cm2 Dropped to 4.28×10 9 Ω·cm 2 , and gradually increased to 3.35×10 9 Ω·cm 2 . This is related to the gradual release of TA. However, for CTAP-EP, |Z| 0.01Hz From 3.21×10 10 Ω·cm 2 at the beginning of immersion dropped to 4.60×10 9 Ω·cm 2 after 21d, and then increased to 5.53×10 9 Ω·cm 2 ( Figure 6 .h). This is because once corrosion occurs, TA can be released from CTAP and adsorbed on the steel surface. Therefore, CTAP-PBAF shows excellent long-term corrosion resistance. Figure 6 .j clearly shows that after 35d, |Z| 0.01Hz is significantly greater than that of other coatings, indicating that CTAP-PBAF can effectively extend the service life of carbon steel. The above results show that CTAP-PBAF can provide dual passive and active corrosion protection capabilities for carbon steel.

[0059] IV. Self-healing performance of CTAP-PBAF

[0060] Figure 7 . are the Nyquist and Bode plots of Ce-MOF-PBAF and CTAP-PBAF scratch coatings with a length of about 6 mm after immersion in 3.5 wt.% NaCl solution for different times. These two scratch coatings are named S-Ce-MOF-PBAF and S-CTAP-PBAF respectively. Generally speaking, a larger impedance arc radius usually means that the coating has excellent corrosion resistance. For S-Ce-MOF-PBAF and S-CTAP-PBAF, in the initial stage of immersion (3 - 7 h), the impedance arc radius first decreases in the first 3 h of immersion, gradually rises to 5 h, and then drops to 7 h. In the later stage of immersion (9 - 11 h), the impedance arc radius of S-CTAP-PBAF slightly increases, while that of S-Ce-MOF-PBAF gradually decreases. At the same time, the impedance arc radius of S-CTAP-PBAF is significantly higher than that of S-Ce-MOF-PBAF. These results are attributed to the fact that tannic acid can be released from CTAP according to the pH change caused by local corrosion. At the same time, Figure 7 .a is the variation of |Z| 0.01Hz of S-Ce-MOF-PBAF and S-CTAP-PBAF with immersion time. For S-CTAP-PBAF, its |Z|0.01Hz is significantly higher than that of S-Ce-MOF-PBAF. The |Z| of S-CTAP-PBAF 0.01Hz shows a process of decreasing first and then increasing four times. The results show that the TA corrosion inhibitor can be gradually released from CTAP, adsorbed onto the microdefects on the surface of carbon steel, and hinder the continuous downward penetration of the corrosive electrolyte, thereby showing good self-healing performance.

[0061] The above are only the preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention shall be included within the protection scope of the present invention.

Claims

1. A method for preparing a polymer coating having a bow-tie-shaped core-shell nanocontainer, characterized in that: The following steps are involved: S1. Preparation of Ce-MOF nanocontainer: 1,3,5-trimesic acid was dissolved in a mixed solution of deionized water and ethanol to obtain solution A, cerium nitrate solution with pH adjusted to 3-4 was used as solution B, solution B was added to solution A to obtain Ce-MOF nanocontainer; S2. Preparation of CTA: adding the Ce-MOF nanocontainer to a tannic acid phosphate buffer solution, stirring, centrifuging, washing and collecting the Ce-MOF loaded with tannic acid, namely CTA; S3, preparation of CTAP: adding polyethyleneimine solution to tannic acid phosphate buffer solution and stirring, then adding CTA to the above solution and continuing stirring, centrifuging, washing, and drying to obtain the final product of CTAP; S4, preparation of PBAF: xylene and propylene glycol methyl ether are added to a bottle and heated, and then methyl methacrylate, ethyl acrylate, isobornyl methacrylate, hexafluorobutyl methacrylate, chain transfer agent and azobisisobutyronitrile are mixed and added to the above bottle, and a transparent mixed solution is obtained after stirring, and dibenzoyl peroxide is dissolved in the above mixed solution for reaction, so as to obtain a colorless and transparent bornyl fluorinated acrylic polymer (PBAF); S5. Preparation of CTAP-PBAF: Disperse the CTAP prepared in S3 into N,N-dimethylformamide and add the borneol-based fluorinated acrylic polymer prepared in S4. After stirring evenly, cure at room temperature to obtain a borneol-based fluorinated acrylic polymer coating with a bow-knot-shaped core-shell nanocontainer.

2. The method for preparing a polymer coating having a bow-tie-shaped core-shell nanocontainer according to claim 1, characterized in that: The following steps are involved: S1. Preparation of Ce-MOF nanocontainer: 0.3-0.8 mmol 1,3,5-trimesic acid was dissolved in a mixed solution of 30-50 mL deionized water and ethanol to obtain solution A. The pH of cerium nitrate solution was adjusted to 3-4 as solution B. 0.5-1.5 mL solution B was slowly added dropwise to solution A at a uniform speed. After stirring at room temperature for 5-15 min, the solution was centrifuged for 8-12 min, washed with deionized water and ethanol for 2-4 times respectively, and dried at 50-80°C for 20-30 h to obtain a Ce-MOF nanocontainer. S2. Preparation of CTA: 0.05-0.15 g of the above Ce-MOF nanocontainer was added to 18-22 g / L tannic acid phosphate buffer solution, stirred for 8-12 min under vacuum, centrifuged, washed with deionized water 2-4 times and Ce-MOF loaded with tannic acid (TA) was collected, i.e., CTA; S3. Preparation of CTAP: Add 6-7 g / L polyethyleneimine solution to 8-12 mL tannic acid phosphate buffer solution and stir for 3-8 min, then add 0.05-0.15 g of the CTA prepared above to the solution and continue stirring for 3-8 min, centrifuge, wash with deionized water 2-4 times, and dry at 50-80° C. for 20-30 h. The final product is named CTAP; S4, preparation of PBAF: add xylene and propylene glycol methyl ether into a bottle, heat the temperature to 90-100°C, then weigh 4-5g methyl methacrylate, 3-5g ethyl acrylate, 1-3g isobornyl methacrylate, 2-8g hexafluorobutyl methacrylate, 8-10g chain transfer agent and 1-3g azobisisobutyronitrile, mix and add the above xylene and propylene glycol methyl ether, stir for 2-4min to obtain a transparent mixed solution, drip the mixed solution into the flask drop by drop, the dripping time is 2-6h, during which time the nitrogen atmosphere in the flask is maintained, after the dripping is completed, weigh dibenzoyl peroxide and dissolve it in the above mixed solution, drip it into the flask within 30min, keep the reaction for 90-100min, and obtain a colorless and transparent bornyl fluorine-containing acrylic polymer (PBAF); S5. Preparation of CTAP-PBAF: Disperse CTAP containing a resin mass fraction of 0.3-0.8 wt% in N,N-dimethylformamide and add 0.5-1.5 g of borneol-based fluorinated acrylic polymer. Stir evenly and cure at room temperature for 4-5 hours to obtain a borneol-based fluorinated acrylic polymer coating with a bow-knot-shaped core-shell nanocontainer.

3. The method for preparing a polymer coating having a bow-tie-shaped core-shell nanocontainer according to claim 2, characterized in that: The volume ratio of deionized water to ethanol in S1 is 1:

1.

4. The method for preparing a polymer coating having a bow-tie-shaped core-shell nanocontainer according to claim 2, characterized in that: In the S1, the pH of the cerium nitrate solution is adjusted to 3-4 using a 0.03-0.08 mol / L nitric acid solution, which is used as solution B.

5. The method for preparing a polymer coating having a bow-tie-shaped core-shell nanocontainer according to claim 2, characterized in that: The centrifugal speed in S1, S2 and S3 is 3500-4500 rpm, and the centrifugal time is 5-15 min.

6. The method for preparing a polymer coating having a bow-tie-shaped core-shell nanocontainer according to claim 2, characterized in that: The volume ratio of xylene to propylene glycol methyl ether in S4 is 0.3-0.8:

1.

7. The method for preparing a polymer coating having a bow-tie-shaped core-shell nanocontainer according to claim 2, characterized in that: The mass volume ratio of dibenzoyl peroxide to the mixed solution in S4 is 3-8:100 g / mL.

8. The method for preparing a polymer coating having a bow-tie-shaped core-shell nanocontainer according to claim 2, characterized in that: The weight average molecular weight of the bornyl fluorinated acrylic polymer in S4 is 3.10-3.75×10 4 g / mol, and the molecular weight distribution (PDI) is between 1.63 and 1.

90. 9 . A polymer coating having a bow-tie-shaped core-shell nanocontainer prepared by the preparation method according to any one of claims 1 to 8 .

10. A polymer coating with bow-knot-shaped core-shell nanocontainers is used in anti-fouling and anti-corrosion coatings.

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