Polymer composite anti-marine fouling coating based on artemisinin modification and preparation method thereof

Abstract

The application discloses a polymer composite based on artemisinin modification, which is characterized in that the polymer composite comprises artemisinin compound modified organic silicon polyurethane and artemisinin compound modified organic silicon polyurea, and the mass ratio of the artemisinin compound modified organic silicon polyurethane and the artemisinin compound modified organic silicon polyurea is (2-1):(1-2). The application has the advantages of high hardness, good mechanical property, low elastic modulus, good stain removal effect, good adhesion, stable adhesion on a substrate and difficulty in falling off, excellent antibacterial effect, difficulty in hydrolysis in seawater or air moisture in use, good water resistance and long-term stability of the composite coating, so that the comprehensive performance of the coating is improved, and the application prospect of the environment-friendly marine antifouling coating is good.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of marine antifouling, and particularly relates to a polymer composite marine antifouling coating based on artemisinin modification and a preparation method. BACKGROUND

[0002] Marine biofouling refers to the adverse accumulation of microorganisms, algae and animals on the surface of structures immersed in seawater, which not only increases the sailing resistance of ships, speeds up metal corrosion, increases operating costs, etc., but also increases the emission of greenhouse gases, and marine biofouling has become a key problem restricting the development of the marine industry.

[0003] At present, coating an antifouling coating on the surface of a ship and marine equipment is the most effective measure to deal with the above problems. However, it is a big problem to prepare an antifouling coating with excellent performance in all aspects. Tributyltin (TBT) is the most successful material for preventing biofouling of artificial marine infrastructure, although it has excellent antifouling performance, but the very serious environmental problems caused by the accumulation of TBT and the widespread damage to shellfish have attracted widespread attention from countries around the world. Therefore, environmentally friendly coatings that are non-toxic to the environment are gradually being replaced.

[0004] Most of the currently used are environmentally friendly single coatings, and the environmentally friendly single coatings have defects in some performances, such as the mechanical performance of the coating is very excellent, which may lead to a decrease in the fouling detachment performance, so that the fouling organisms are difficult to be easily removed by water shear force, and both are difficult to achieve; therefore, researchers begin to prepare a composite coating by compounding two single coatings to make up for the defects of the single coating in some aspects (such as mechanical performance, adhesion performance, antibacterial performance and antifouling performance, etc.), although the comprehensive performance of the polymer coating after compounding is improved to a certain extent, but it has not yet reached the ideal state. SUMMARY

[0005] Therefore, the purpose of the present application is to provide a polymer composite marine antifouling coating based on artemisinin modification and a preparation method, so as to solve the technical problem that the comprehensive performance such as mechanical performance, antifouling effect and adhesion performance of the current composite antifouling coating material needs to be improved.

[0006] The above purpose of the present application is achieved by the following technical scheme:

[0007] A polymer composite material based on artemisinin modification, the polymer composite material comprising artemisinin compound modified silicone polyurethane and silicone polyurea, and the mass ratio of the artemisinin compound modified silicone polyurethane and silicone polyurea is (2-1):(1-2).

[0008] In an alternative embodiment, the artemisinin-modified silicone polyurethane is obtained by mixing a silicone polyurethane polymer solution and an artemisinin solution, and then freeze-drying, wherein the volume ratio of the silicone polyurethane polymer solution to the artemisinin solution is 5:0.5-2, and the concentration of the artemisinin is 0.01-0.04 g / mL.

[0009] In an alternative embodiment, in the artemisinin-modified silicone polyurethane, the silicone polyurethane is a silicone polyurethane polymer synthesized by using a dihydroxyl-terminated polydimethylsiloxane and polytetramethylene glycol as soft segments, and using γ-aminopropyl triethoxysilane as a blocking agent.

[0010] In an alternative embodiment, the molecular weight of the polytetramethylene glycol is 2900.

[0011] In an alternative embodiment, the mass ratio of the polydimethylsiloxane to the polytetramethylene glycol is 1:1.

[0012] In an alternative embodiment, the method for preparing the silicone polyurethane polymer comprises the following steps:

[0013] (I) Preparation of a polyurethane prepolymer

[0014] The dihydroxyl-terminated polydimethylsiloxane HT-PDMS and the polytetramethylene glycol PTMG are dissolved in a xylene solvent, and are fully mixed by magnetic stirring to obtain a first mixed solution. Isophorone diisocyanate IPDI and dibutyltin dilaurate DBTDL are added to the first mixed solution to obtain a second mixed solution. The second mixed solution is added to a constant-pressure funnel for dropwise addition. Vacuum is applied and nitrogen is introduced, and the process is repeated twice. After the second time of nitrogen introduction for 3-5 min, the switch of the constant-pressure funnel is adjusted, and the solution is added dropwise at a speed of 3-4 drops / s under the protection of nitrogen at 80°C. The dropwise addition is performed for 20-40 min. After the dropwise addition is completed, the solution is stirred for 2-4 h to obtain a polyurethane prepolymer solution.

[0015] (II) Preparation of a silicone polyurethane polymer

[0016] The γ-aminopropyl triethoxysilane is added to the polyurethane prepolymer solution to obtain a third mixed solution. The third mixed solution is added to a constant-pressure funnel, and the steps in (I) are repeated. After the dropwise addition is completed, the solution is stirred for 2-4 h, and is freeze-dried to obtain a silicone polyurethane polymer.

[0017] In an alternative embodiment, the artemisinin is one of artesunate, dihydroartemisinin, or artemether.

[0018] In an alternative embodiment, the organic silicon polyurea comprises polydimethylsiloxane PDMS, isophorone diisocyanate IPDI and hexamethylene diamine HMDA, and the polydimethylsiloxane PDMS: isophorone diisocyanate IPDI: hexamethylene diamine HMDA = 4 mol: 6 mol: 2 mol, or the polydimethylsiloxane PDMS: isophorone diisocyanate IPDI: hexamethylene diamine HMDA = 4 mol: 7 mol: 3 mol.

[0019] The second aspect of the present application is to provide a preparation method of the artemisinin-modified polymer composite, mixing the artemisinin-modified organic silicon polyurethane solution and the organic silicon polyurea solution in a mass ratio of 1:1, and then rotating and stirring the mixed solution at a rotating speed of 60-80 rpm for 5-8 min, and the obtained solution is the artemisinin-modified polymer composite.

[0020] The third aspect of the present application is to provide the application of the artemisinin-modified polymer composite in the marine antifouling coating.

[0021] Compared with the prior art, the technical scheme of the present application has the following advantages:

[0022] The composite material obtained by compounding the artemisinin-modified organic silicon polyurethane polymer and the organic silicon-modified polyurea polymer has high hardness, good mechanical properties, low elastic modulus, good fouling removal effect, good adhesion, and can be firmly attached to the substrate without falling off, and also has excellent antibacterial effect, and under the premise of meeting these conditions, it is not easy to be hydrolyzed by seawater or moisture in the air, and has good water resistance, thereby ensuring the long-term stability of the composite coating, thereby comprehensively improving the comprehensive performance of the coating, and having good application prospect as an environmentally friendly marine antifouling coating. BRIEF DESCRIPTION OF DRAWINGS

[0023] Figure 1 The elastic modulus (A), water contact angle (B), surface free energy (C) and water absorption rate (D) of the organic silicon polyurethane polymer PDMS-PTMG-2900 of the present application embodiment 1 as a single coating layer;

[0024] Figure 2 The removal strength of the artificial barnacle (A) and the biofilm removal rate (B) of the organic silicon polyurethane polymer PDMS-PTMG-2900 of the present application embodiment 1 as a single coating layer;

[0025] Figure 3 The infrared spectrum of the composite coating PDMS-PUa-PDMS-PTMG-(①-⑥) of the present application;

[0026] Figure 4 Stress-strain curve (A) and elastic modulus (B) of the composite coating PDMS-PUa-PDMS-PTMG-(①-⑥) of the application;

[0027] Figure 5 Water contact angle (A) and surface free energy (B) of the composite coating PDMS-PUa-PDMS-PTMG-(①-⑥) of the application;

[0028] Figure 6 Water absorption of the composite coating PDMS-PUa-PDMS-PTMG-(①-⑥) of the application;

[0029] Figure 7 Distribution of Si and O elements on the surface of the composite coating PDMS-PUa-PDMS-PTMG-(①-⑥) of the application;

[0030] Figure 8 Field emission scanning electron microscope (FESEM) picture of the composite coating PDMS-PUa-PDMS-PTMG-(①-⑥) of the application;

[0031] Figure 9 Removal intensity of the composite coating PDMS-PUa-PDMS-PTMG-(①-⑥) of the application on simulated barnacles;

[0032] Figure 10 Effect picture of the composite coating PDMS-PUa-PDMS-PTMG-(①, ③, ⑤) of the application against E. coli (A) and Staphylococcus aureus (B);

[0033] Figure 11 Bacteriostatic efficiency of the composite coating PDMS-PUa-PDMS-PTMG-(①, ③, ⑤) of the application on E. coli and Staphylococcus aureus.

[0034] Figure 12 Removal rate of the composite coating PDMS-PUa-PDMS-PTMG-(①-⑥) of the application on biofilm. DETAILED DESCRIPTION

[0035] In order to enable persons skilled in the art to better understand the present application, the technical solutions in the embodiments of the present application will be described clearly and completely below with reference to the drawings in the embodiments of the present application. Obviously, the described embodiments are only some of the embodiments of the present application, but not all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by persons skilled in the art without creative labor fall within the scope of protection of the present application.

[0036] In the following experiments, the materials used are: α, ω-hydroxypropyl-terminated polydimethylsiloxane (HT-PDMS) (Mw = 2000) (Shanghai Maikelin Biotechnology Co., Ltd.), isophorone diisocyanate (IPDI) (Shanghai Aladdin Reagent Co., Ltd.), 7-amino-4-methyl coumarin (AMC) (Shanghai Maikelin Biotechnology Co., Ltd.), polytetrahydrofuran (PTMG) (Mw = 2900) (Shanghai Maikelin Biotechnology Co., Ltd.), dibutyltin dilaurate (DBTDL) (Shanghai Maikelin Biotechnology Co., Ltd.) are chemically pure; α, ω-aminopropyl-terminated polydimethylsiloxane (APT-PDMS) (Shanghai Maikelin Biotechnology Co., Ltd.), 1, 6-hexanediamine (HMDA) (Shanghai Aladdin Reagent Co., Ltd.), anhydrous ethanol are analytically pure; tetrahydrofuran (THF) (Shanghai Yinan Chemical Technology Co., Ltd.) and isopropyl alcohol (IPA) (Shanghai Yinan Chemical Technology Co., Ltd.), dimethylbenzene (Shanghai Maikelin Biotechnology Co., Ltd.), γ-aminopropyl triethoxysilane (KH-550) are chromatographically pure; deionized water is laboratory self-made.

[0037] It should be noted that the composite coating prepared by the application is obtained on the basis of a single coating. The self-made silicone polyurethane polymer (PDMS-PTMG-2900) is used as a single coating. Based on this, the performance indicators of the composite coating obtained by compounding with other single coatings, compounding after modification with other single coatings, and compounding after modification with another single coating also modified are studied. Figure 1 and Figure 2 The experimental data of the hydrophobicity (reflected by the contact angle and free energy), water resistance, removal strength of simulated barnacles, and removal rate of biofilm of the silicone polyurethane polymer (PDMS-PTMG-2900) as a single coating are provided for reference and comparison.

[0038] Example 1

[0039] A polymer composite based on artemisinin modification, comprising the following steps:

[0040] I. Preparation of silicone polyurethane polymer

[0041] (I) Preparation of polyurethane prepolymer

[0042] HT-PDMS (α, ω-hydroxypropyl terminated polydimethylsiloxane) was first placed in a vacuum drying oven at 60 °C for 2 h before use. Then 7.50 g (3.75 mmol) of HT-PDMS and 7.50 g (3.75 mmol) of PTMG (polytetramethylene glycol) with a soft segment molecular weight of 2900 were weighed and dissolved in 30 ml of xylene solvent, and then added to a 250 ml two-necked flask with a magnetic stirrer for stirring. After stirring uniformly, a first mixed solution was obtained. Then 1.54 g (6.76 mmol) of IPDI (isophorone diisocyanate) and 0.05 g (0.08 mmol) of DBTDL (dibutyltin dilaurate) were added to the first mixed solution, and after stirring uniformly, a second mixed solution was obtained. The second mixed solution was then added to a constant pressure funnel, and vacuum was applied and then nitrogen was introduced twice. After 3 min of nitrogen introduction for the second time, the opening of the constant pressure funnel was slowly adjusted, and the solution was added dropwise at a rate of 3-4 drops / s under the protection of nitrogen at 80 °C. The dropwise addition time was about 20 min. After the dropwise addition was completed, the solution was stirred for 2 h to obtain a polyurethane prepolymer solution.

[0043] (II) Preparation of silicone-modified polyurethane polymer

[0044] 1 g (4.52 mmol) of KH-550 (γ-aminopropyl triethoxysilane) was dissolved in the polyurethane prepolymer solution, and after uniform mixing, a third mixed solution was obtained. The third mixed solution was then added to a constant pressure funnel, and dropwise addition was carried out at a rate of 3-4 drops / s under the protection of nitrogen at 80 °C. The dropwise addition time was about 30 min. After the dropwise addition was completed, the solution was stirred for 3 h, and then freeze-drying was carried out to obtain a silicone polyurethane polymer. The obtained product was named PDMS-PTMG-2900.

[0045] II. Preparation of artemisinin-modified silicone-based polyurethane polymer

[0046] The silicone polyurethane polymer was dissolved in a xylene solvent to prepare a 20 wt% solution. Then, according to a mass ratio of 5 (silicone polyurethane polymer): 1 (dihydroartemisinin), a dihydroartemisinin solution with a concentration of 0.028 g / mL was added to the silicone polyurethane polymer solution. A high-speed disperser was used to mix the two uniformly at a speed of 70 rpm for 6 min. Then, after freeze-drying, a solid artemisinin silicone polyurethane polymer was obtained. The obtained product was named PDMS-PTMG-2900-A.

[0047] III. Preparation of silicone polyurea

[0048] Firstly, the PDMS was placed in a vacuum drying oven for dehydration treatment at 110°C for 2h. Then, 4g (0.004mol) of the treated PDMS was weighed and dissolved in 10ml of a 1:1 mixed solution of THF (tetrahydrofuran) and IPA (isopropyl alcohol) to obtain solution A; 1.34g (0.006mol) of IPDI (isophorone diisocyanate) was dissolved in 20ml of a 1:1 mixed solution of THF (tetrahydrofuran) and IPA (isopropyl alcohol) to obtain solution B. Solution B was added to a flask equipped with a constant pressure funnel, a stirrer, a reflux condenser and a nitrogen inlet device, and solution A was added dropwise into solution B at room temperature under a nitrogen atmosphere for 30min, and the reaction was continued for 1h after the dropwise addition was completed. Then, 0.23g (0.002mol) of HMDA (1,6-hexanediamine) was dissolved in a 1:1 mixed solution of THF (tetrahydrofuran) and IPA (isopropyl alcohol) to obtain solution C. Solution C was also added to the flask at room temperature under a nitrogen atmosphere for 1h, and the reaction was continued for 3h after the dropwise addition was completed, to obtain a transparent and uniform polymer solution, which was then freeze-dried to obtain a solid silicone polyurea polymer. This polymer was named PDMS-PUa-4:6:2 (4:6:2 = 4mol:6mol:2mol = polydimethylsiloxane PDMS: isophorone diisocyanate IPDI: hexanediamine HMDA).

[0049] IV. Preparation of artemisinin-modified polymer composite

[0050] 1g of the artemisinin-modified silicone polyurethane polymer was dissolved in xylene, and 1g of the silicone polyurea polymer was dissolved in isopropyl alcohol, and then the two completely dissolved solutions were poured into beakers and mixed uniformly using a high-speed disperser at a speed of 80rpm for 5min. The mixed solution was the artemisinin-modified polymer composite, which was named PDMS-PUa-PDMS-PTMG-① (in PDMS-PUa, polydimethylsiloxane PDMS: isophorone diisocyanate IPDI: hexanediamine HMDA = 4mol:6mol:2mol).

[0051] Example 2

[0052] The preparation of the silicone polyurethane polymer, the artemisinin-modified silicone-based polyurethane polymer and the artemisinin-modified polymer composite of this example was the same as in Example 1, except that in the preparation of the silicone polyurea, polydimethylsiloxane PDMS: isophorone diisocyanate IPDI: hexanediamine HMDA = 4mol:6mol:2mol. The preparation steps of the silicone polyurea were as follows:

[0053] APT-PDMS (α, ω-amino propyl terminated polydimethylsiloxane) was first dehydrated at 110°C for 2h in a vacuum oven. Then 4g (0.004mol) of the treated APT-PDMS was weighed and dissolved in 10ml of THF (tetrahydrofuran) and IPA (isopropyl alcohol) 1:1 mixed solution to obtain solution A; 1.56g (0.007mol) of IPDI (isophorone diisocyanate) was dissolved in 20ml of THF (tetrahydrofuran) and IPA (isopropyl alcohol) 1:1 mixed solution to obtain solution B. Solution B was added into a flask equipped with a constant pressure funnel, a stirrer, a reflux condenser and a nitrogen inlet device, and solution A was added dropwise into solution B at room temperature under nitrogen for 30min, and reacted for 1h after the dropwise addition was completed. Then 0.35g (0.003mol) of HMDA (1,6-hexanediamine) was dissolved in THF (tetrahydrofuran) and IPA (isopropyl alcohol) 1:1 mixed solution to obtain solution C. Solution C was also added into the flask at room temperature under nitrogen for 1h, and reacted for 3h after the dropwise addition was completed, to obtain a transparent and uniform polymer solution, which was then freeze-dried to obtain a solid silicone polyurea polymer, which was named PDMS-PUa-4:7:3. The artemisinin-modified polymer composite obtained by the silicone polyurea was named PDMS-PUa-PDMS-PTMG-② (in PDMS-PUa, polydimethylsiloxane PDMS: isophorone diisocyanate IPDI: hexanediamine HMDA = 4mol:7mol:3mol).

[0054] Comparative Example 1

[0055] This comparative example is different from Example 1 in that there is no step "two", and the silicone polyurethane polymer without artemisinin modification is directly mixed with the silicone polyurea polymer, and the rest of the process is the same as Example 1. The obtained polymer composite is named PDMS-PUa-PDMS-PTMG-③ (in PDMS-PUa, polydimethylsiloxane PDMS: isophorone diisocyanate IPDI: hexanediamine HMDA = 4mol:6mol:2mol).

[0056] Comparative Example 2

[0057] This comparative example is different from Example 2 in that there is no step "two", and the silicone polyurethane polymer without artemisinin modification is directly mixed with the silicone polyurea polymer, and the rest of the process is the same as Example 2. The obtained polymer composite is named PDMS-PUa-PDMS-PTMG-④ (in PDMS-PUa, polydimethylsiloxane PDMS: isophorone diisocyanate IPDI: hexanediamine HMDA = 4mol:7mol:3mol).

[0058] Comparative Example 3

[0059] The comparative example differs from Example 1 in that the artemisinin-modified silicone polyurethane polymer is mixed with the 7-amino-4-methylcoumarin-grafted silicone polyurea polymer, and the rest of the process is the same as Example 1. The preparation steps of the 7-amino-4-methylcoumarin-grafted silicone polyurea are as follows:

[0060] The solvent required for the reaction is prepared by mixing chromatographic grade THF (tetrahydrofuran) and IPA (isopropyl alcohol) at a volume ratio of 1:1, and APT-PDMS (α, ω-aminopropyl-terminated polydimethylsiloxane) is placed in a vacuum drying oven at 110°C for 2h before use.

[0061] First, 1.34g (6mmol) of IPDI (isophorone diisocyanate) is added to a 250ml two-necked flask containing 20ml of solvent and a magnetic stirrer. 4g (4mmol) of APT-PDMS is dissolved in 10ml of solvent, then added to the constant pressure funnel, and vacuumed and purged with nitrogen twice. After 3min of the second nitrogen purging, the oil bath temperature is maintained at 25°C and the solution is added dropwise at a speed of 3-4s / drop under magnetic stirring for about half an hour. After the addition is completed, it is reacted for one hour.

[0062] Then 0.03g (0.171mmol) of 7-amino-4-methylcoumarin is dissolved in 10ml of solvent, added to the constant pressure funnel, and slowly adjusted to the opening of the constant pressure funnel under the catalysis of DBTDL (dibutyltin dilaurate) at 80°C and nitrogen protection. This process takes about 0.5h. Finally, 0.23g (2mmol) of HMDA (1,6-hexanediamine) is dissolved in 10ml of mixed solvent and added to the constant pressure funnel. Vacuum and nitrogen are re-purged, and the solution is added dropwise at a speed of 5-6s / drop by slowly adjusting the opening of the constant pressure funnel. This process takes about one hour. After the addition is completed, it is reacted for three hours. After the reaction is completed, the reaction product needs to be purified. The excess solvent in the product is removed by a rotary evaporator, and then the product is washed with deionized water. After the washing is completed, it is placed in a vacuum drying oven at 60°C, and the drying time is about 45-48h. The obtained product is the 7-amino-4-methylcoumarin-grafted silicone polyurea, which is named PDMS-PUa-4:6:2-AMC (in PDMS-PUa, polydimethylsiloxane PDMS: isophorone diisocyanate IPDI: hexanediamine HMDA = 4mol: 6mol: 2mol).

[0063] The polymer composite obtained by mixing the artemisinin-modified silicone polyurethane polymer with the 7-amino-4-methylcoumarin-grafted silicone polyurea polymer is named PDMS-PUa-PDMS-PTMG-⑤.

[0064] Comparative Example 4

[0065] This comparative example differs from Example 1 in that the artemisinin-modified silicone polyurethane polymer is mixed with the 7-amino-4-methylcoumarin-grafted silicone polyurea polymer, and the rest of the process is the same as in Example 1. The preparation steps of the 7-amino-4-methylcoumarin-grafted silicone polyurea are as follows:

[0066] The solvent required for the reaction is prepared by mixing chromatographic grade THF (tetrahydrofuran) and IPA (isopropanol) at a volume ratio of 1:1, and the APT-PDMS (α,ω-aminopropyl-terminated polydimethylsiloxane) is placed in a vacuum drying oven at 110°C for 2h before use.

[0067] First, 1.70g (7.65mmol) of IPDI (isophorone diisocyanate) is added to a 250ml two-necked flask containing 20ml of solvent and a magnetic stirrer. 4g (4mmol) of APT-PDMS is dissolved in 10ml of solvent, then added to a constant pressure funnel, and vacuumed and purged with nitrogen twice. After 3min of nitrogen purging in the second time, the oil bath temperature is maintained at 25°C and the solution is added dropwise at a speed of 3-4s / drop under magnetic stirring, which takes about half an hour. After the addition is completed, it is reacted for one hour.

[0068] Then 0.03 g (0.171 mmol) of 7-amino-4-methylcoumarin was dissolved in 10 ml of solvent, and added into the constant pressure funnel. The constant pressure funnel was slowly adjusted under the catalysis of DBTDL (dibutyl tin dilaurate) at 80°C and nitrogen protection. The process lasted about 0.5 h. Finally, 0.35 g (3.01 mmol) of HMDA (1,6-hexanediamine) was dissolved in 10 ml of mixed solvent and added into the constant pressure funnel. The constant pressure funnel was slowly adjusted again after vacuum and nitrogen, so that the solution could be added dropwise at a speed of 5-6 s / drop. The process lasted about one hour. After the dropwise addition, the reaction was continued for three hours. After the reaction was completed, the product needed to be purified. The product containing excess solvent was removed by a rotary evaporator. Then the product was washed with deionized water. After the washing was completed, it was placed in a vacuum drying oven at 60°C. The drying time was about 45-48 h. The obtained product was a silicone polyurea grafted with 7-amino-4-methylcoumarin, which was named PDMS-PUa-4:7:3-AMC (in PDMS-PUa, polydimethylsiloxane PDMS: isophorone diisocyanate IPDI: hexanediamine HMDA = 4 mol: 7 mol: 3 mol).

[0069] The polymer composite obtained by mixing the silicone polyurethane polymer modified by artemisinin and the silicone polyurea polymer grafted with 7-amino-4-methylcoumarin was named PDMS-PUa-PDMS-PTMG-⑥.

[0070] It should be noted that the grafting of 7-amino-4-methylcoumarin onto the silicone polyurea polymer is a modification process of the silicone polyurea polymer, which is consistent with the silicone-based polyurethane polymer modified by dihydroartemisinin. Both are modified polymers.

[0071] Application Example 1 Fourier infrared spectroscopy characterization

[0072] The polymers prepared in Examples 1 and 2 and Comparative Examples 1-4 were used as test samples. At room temperature, the potassium bromide was pressed into a sheet using the instrument. Then the test samples were dissolved in a mixed solvent of isopropyl alcohol and xylene to prepare a 20 wt% test solution. The test solution was added dropwise on the potassium bromide, and the infrared lamp was used for irradiation. After the solvent was volatilized, the test was performed. The instrument parameters were set as follows: the resolution was 4 cm -1 , and the scanning times were 64. The results are shown in Figure 3 .

[0073] As can be seen from Figure 3 , the peak at 3335 cm -1 is attributed to the stretching vibration of the N-H group in -NH-CO-O, and the peaks at 2840 cm -1 -2968 cm-1 The peak at 1692 cm⁻¹ is attributed to the stretching vibration of -CH, while the peak at 1692 cm⁻¹ is attributed to the stretching vibration of -CH. -1 The peak at that position is attributed to the stretching vibration of the C=O group. The absorption peak representing isocyanate is at 2260 cm⁻¹. -1 The peak at 1000-1100cm disappears completely. -1 Two peaks appear at 795 cm⁻¹, which are characteristic absorption peaks of Si-O-Si. -1 The peak at 1252 cm⁻¹ is attributed to the stretching vibration of the Si-C groups, while the peak at 1252 cm⁻¹ is attributed to the stretching vibration of the Si-C groups. -1 The peak at that point is the absorption peak of the bending vibration of the Si-C group, which proves that the polymer synthesis was successful.

[0074] Application Example 2: Elastic Modulus Test

[0075] When composite polymers are applied to antifouling coatings, the incompatibility of PDMS chain segments and hard segments can lead to microphase separation, potentially affecting its mechanical properties. The composite material prepared in this study consists of two different polymers, which may also affect its mechanical properties. Therefore, tensile tests were conducted to investigate the mechanical properties of the composite coating. The polymer composite materials from Examples 1 and 2, and Comparative Examples 1-4, were dissolved and allowed to form films naturally, then dried in an oven. The formed films were then pressed into dumbbell-shaped test samples and tested using a universal testing machine at a tensile rate of 10 mm / min. Five replicates were set for each sample, and the average value was taken. The results are as follows: Figure 4 As shown. Figure 4 Figure A in the diagram shows the stress-strain curves of PDMS-PUa-PDMS-PTMG-(①~⑥). Figure 4 Figure B in the diagram shows the elastic modulus data of PDMS-PUa-PDMS-PTMG-(①~⑥).

[0076] from Figure 4 As shown in Figure B, PDMS-PUa-PDMS-PTMG-⑤ and ⑥ have higher elastic moduli, while ① has the lowest. The comparison of these six elastic moduli is: ② > ①, ④ > ③, ⑥ > ⑤. This is because the increased presence of hard segments in the PDMS-PUa content, with the hard segments produced by microphase separation acting as a second phase, enhances the mechanical properties of the coating, thus increasing the elastic modulus of the modified coating. However, the overall elastic modulus of the composite coating does not exceed 0.25 MPa, maintaining a relatively low level. It is generally believed that in low surface energy antifouling coatings, the lower the elastic modulus, the better the fouling desorption performance. Therefore, among these six coatings, ① has the lowest elastic modulus and the best fouling desorption performance.

[0077] Application Example 3: Hydrophobicity Test

[0078] The water contact angle of the coating can reflect the wettability of the coating to a great extent, and the surface free energy of the composite coating plays a great role in the evaluation of the fouling release performance of the composite coating.

[0079] The PDMS-PUa-PDMS-PTMG-(①~⑥) was respectively dissolved in xylene solvent, poured into a polytetrafluoroethylene dish, and naturally dried into a film at room temperature. Before testing, it was placed in a 50°C oven and baked for 24h. The static contact angle of the coating surface was tested by a contact angle tester (JC2000CS, Shanghai Zhongchen Co., Ltd.). The test used the solid drop method, and the surrounding environment was stable at about 25°C. The water contact angle test used 3μL as the quantitative, and the diiodomethane contact angle test used 2μL as the quantitative. Each sample was tested 5 times at different points, and the average value was taken as the final contact angle data. The surface free energy of the polymer was calculated according to the following formula by the water contact angle and the diiodomethane contact angle.

[0080] γ s = γ s d + γ s p

[0081] γ L (1 + COSθ) = 2(γ s d γ L d ) 1 / 2 + 2(γ s P γ L P ) 1 / 2

[0082] For waterγ L P = 51.0 mN / m, γ L d = 21.8 mN / m

[0083] For diiodomethane, γ L P = 2.3 mN / m, γ L d = 48.5 mN / m

[0084] The results are shown in Figure 5 and Table 1, respectively. Figure 5 In the figures, A is the water contact angle of the polymer coating; B is the surface free energy of the polymer coating.

[0085] From Figure 5As can be seen from the A figure and Table 1 of the present application, the water contact angles of PDMS-PUa-PDMS-PTMG-(①-⑥) are all in the range of 98°-104°, because the main body of the composite coating is polydimethylsiloxane, when the composite coating is naturally cured into a film, the polymer chain segment has a certain mobility due to its flexibility, PDMS is easy to gather to the surface of the coating, and PDMS is hydrophobic, so the water contact angle of the composite coating is greater than 90°, and has a certain hydrophobicity. From the inside, ① is the largest, ③ is the second, close to ①, and ⑥ is the smallest. From mutual comparison: ①>②, ③>④, ⑤>⑥, because the proportion of hard segment increases, the proportion of polydimethylsiloxane soft segment decreases, and the hydrophobicity decreases.

[0086] Table 1 Contact angle and surface free energy of PDMS-PUa-PDMS-PTMG-(①-⑥) polymer coating

[0087]

[0088] In combination with the content of Table 1 above, by measuring the contact angles of water and diiodomethane respectively, the surface free energy of the composite coating is calculated according to the Owens and Wendt method, and the surface free energy of the composite coating is calculated according to the Owens and Wendt method. Figure 5 As can be seen from the B figure of the present application, the surface free energy of PDMS-PUa-PDMS-PTMG-(①-⑥) coating is all in the range of 20-22 mJ / m -2 , which also shows that the surface of the polymer coating has the property of low surface free energy, and has good fouling release performance, because the coating with a surface free energy of 20-30 mJ / m -2 has a relatively low degree of interaction with marine fouling organisms, and if the fouling organisms are attached to the coating surface, they will be easily stripped by water shear force and will not be easily stable attached during sailing.

[0089] Application Example 4 Water resistance detection

[0090] When the composite coating is applied as an antifouling coating in the ocean, the influence of the external environment (the ability of water permeation, immersion and a series of physical and chemical damage) needs to be considered, and the combination of two different polymers may also have an impact on itself, so the water absorption of the coating is measured to evaluate the water resistance of the composite coating, to evaluate the damage resistance and service life of the composite coating for long-term application in marine environment.

[0091] PDMS-PUa-PDMS-PTMG-(①~⑥) polymers were used as test samples, dissolved in isopropanol solvent, poured into polytetrafluoroethylene petri dishes, and allowed to dry naturally at room temperature to form films. Before testing, the films were dried in a 50℃ oven for 24 hours. The dried films were cut into strips of 3cm×1cm, and their initial mass was recorded as m0. These strips were then placed in small glass bottles containing deionized water and left to dry for 24 hours. The mass after water absorption was recorded as m1. Five replicates were set for each sample, and the average value was used to calculate the water absorption rate W. The calculation formula is as follows:

[0092]

[0093] The results are as follows Figure 6 As shown, from Figure 6 As can be seen from the data, the water absorption rates of these six coatings are: ⑥ > ⑤ > ④ > ③ > ② > ①. Among them, the water absorption rates of ① and ② are significantly different from the other four coatings. This also indicates that PDMS-PUa-4:6:2 / 4:7:3 and PDMS-PTMG-2900-A can adhere well, with fewer voids in the structure, making it difficult for water molecules to enter, thus resulting in lower water absorption rates and better water resistance. On the other hand, ⑤ and ⑥ have higher water absorption rates, possibly because the AMC (7-amino-4-methylcoumarin) grafted PDMS-PUa-4:6:2 / 4:7:3 and PDMS-PTMG-2900-A cannot be completely aggregated together during the fusion process, resulting in voids in the molecular structure. This allows water molecules to enter the coating, increasing the water absorption rate. Although the overall water absorption rate does not exceed 3.5%, it still has good water resistance. However, the difference is still significant compared to ① and ②. The service life of ① and ② is much longer than that of ③, ④, ⑤ and ⑥.

[0094] Application Example 5: Mechanical Property Testing

[0095] For composite antifouling coatings, whether they can form good adhesion to the substrate is an important indicator. In addition, when different polymers are fused together in the study, the compatibility between the two should be considered, and it is necessary to explore whether the combination of the two will affect some mechanical properties.

[0096] The mechanical durability of PDMS-PUa-PDMS-PTMG-(①~⑥) was investigated, primarily by measuring four indicators: coating adhesion, coating hardness, coating flexibility, and coating impact resistance. The following tests used PDMS-PUa-PDMS-PTMG-(①~⑥) polymers as the test samples.

[0097] a) Coating adhesion test:

[0098] The sample to be tested is dissolved in isopropyl alcohol solvent, then uniformly coated on the iron sheet, and the coating adhesion test is tested according to GB / T 1720-2020. The paint film adhesion tester is used, and the test is tested by drawing a circle. The test result range is 1-7 levels.

[0099] b) Coating hardness test

[0100] The sample to be tested is dissolved in isopropyl alcohol solvent, then uniformly coated on the iron sheet, and the coating hardness test is tested according to GB / T 6739-2006 “Pigment and varnish Paint film hardness by pencil method”. The coating hardness test is tested by using the coating film pencil hardness scratch hardness tester. The test result range is 6B-6H.

[0101] c) Coating flexibility test

[0102] The sample to be tested is dissolved in isopropyl alcohol solvent, then uniformly coated on the iron sheet, and the coating flexibility test is tested according to GB / T 1731-2020. The paint film impact tester is used for flexibility test, and the test result range is 1-7 levels.

[0103] d) Coating impact resistance test

[0104] The sample to be tested is dissolved in isopropyl alcohol solvent, then uniformly coated on the iron sheet, and the coating impact resistance test is tested according to GB / T 20624.2-2006. The paint film impact tester is used for impact resistance test, and the test result is evaluated by the impact resistance of the weight hammer from 0-50 cm.

[0105] The mechanical properties (adhesion, hardness, flexibility, impact resistance) of different samples to be tested are shown in Table 2.

[0106] Table 2 Mechanical properties of PDMS-PUa-PDMS-PTMG-(①-⑥) composite coating

[0107] Composite coating Adhesion / level Hardness / level Flexibility / mm Impact resistance / cm PDMS-PUa-PDMS-PTMG-① 2 6H 0.5 50 PDMS-PUa-PDMS-PTMG-② 2 6H 0.5 50 PDMS-PUa-PDMS-PTMG-③ 3 6H 0.5 50 PDMS-PUa-PDMS-PTMG-④ 2 6H 0.5 50 PDMS-PUa-PDMS-PTMG-⑤ 3 6H 0.5 50 PDMS-PUa-PDMS-PTMG-⑥ 2 6H 0.5 50

[0108] As can be seen from the above table, the adhesion of the composite coating is 2-3 levels, and the hardness, flexibility and impact resistance are consistent, indicating that the adhesion of these composite coatings is good.

[0109] Example 6 Energy dispersive X-ray spectroscopy (EDS) analysis

[0110] All samples are placed in the oven before inspection to keep them dry. The energy dispersive X-ray spectroscopy of the coating surface is scanned by using a scanning electron microscope, and the Si, O, N elements in the coating are scanned to obtain the element content and distribution on the surface of the coating. By EDS characterization of PDMS-PUa-PDMS-PTMG-①-⑥ polymer composite coating, the surface chemical composition of the coating can be obtained, and the results are as follows Figure 7As shown.

[0111] from Figure 7 The elemental distribution of Si and O in PDMS-PUa-PDMS-PTMG-① to ⑥ can be observed. It can be seen that Si and O are densely and uniformly distributed in PDMS-PUa-PDMS-PTMG-① and ②, proving that PDMS-PUa and dihydroartemisinin-modified PDMS-PTMG-2900 have good compatibility and can be well combined. However, although Si and O are densely distributed in PDMS-PUa-PDMS-PTMG-③, ④, ⑤, and ⑥, they are not uniform. This may be because PDMS-PUa and PDMS-PTMG-2900 do not have good compatibility, and 7-amino-4-methylcoumarin-grafted PDMS-PUa does not have good compatibility with PDMS-PTMG-2000-A. Therefore, clumping occurs after mixing, resulting in uneven distribution of Si and O elements.

[0112] Application Example 7: Field Emission Scanning Electron Microscopy (FESEM) Analysis

[0113] As an antifouling coating, surface roughness also affects the adhesion of marine fouling organisms to its surface. Generally, it is believed that the greater the surface roughness, the easier it is for fouling organisms to adhere to the surface, and surface roughness also affects the change in surface contact angle. PDMS-PUa-PDMS-PTMG-①~⑥ were used as test samples, dissolved in isopropanol solvent, and then uniformly coated onto iron sheets. After natural curing, the resulting films were placed in an oven to dry before testing. During testing, the morphology of the coating surface was observed using a field emission scanning electron microscope (FESEM, Thermo Fisher Apreo 2C) at magnifications of 1000 and 250000. The results are as follows: Figure 8 As shown, in Figure 8 In the diagram, Figure A represents PDMS-PUa-PDMS-PTMG-①, Figure B represents PDMS-PUa-PDMS-PTMG-②, Figure C represents PDMS-PUa-PDMS-PTMG-③, Figure D represents PDMS-PUa-PDMS-PTMG-④, Figure E represents PDMS-PUa-PDMS-PTMG-⑤, and Figure F represents PDMS-PUa-PDMS-PTMG-⑥.

[0114] from Figure 8As can be seen, PDMS-PUa-PDMS-PTMG-①, ② only a little convex and white spots, white spots for the aggregation of hard segment, overall good flatness and smoothness, which corresponds to the EDS element distribution map, shows that PDMS-PUa-PDMS-PTMG-①, ② composite coating can be better fusion and not rejection. While PDMS-PUa-PDMS-PTMG-③, ④, ⑤, ⑥ have more convex and clumps, corresponding to the EDS element distribution map, shows that the PDMS-PUa grafted by AMC cannot be compatible with PDMS-PTMG-2900-A and PDMS-PTMG-2900, and PDMS-PUa has good compatibility, the mixture will be unevenly distributed after curing into a film, flatness and smoothness are poor.

[0115] Application Example 8 Simulation barnacle removal effect test

[0116] In the laboratory, simulation barnacle experiments were carried out instead of real barnacles to test the removal strength of simulation barnacles on the coating surface to evaluate the anti-adhesion of the coating to marine macrofouling organisms. The smaller the removal strength, the better the anti-fouling adhesion of the coating. The simulation barnacle removal experiment was tested according to ASTM D5618 (2011).

[0117] PDMS-PUa-PDMS-PTMG-①~⑥ were used as test samples. The test samples were dissolved in xylene and a mixture of xylene solvents, then evenly coated on the surface of the epoxy resin plate. Then 5 aluminum cylinders (simulation barnacles) with a diameter of 10 mm and a height of 10 mm were set on the epoxy resin plate, and the position was kept as uniform as possible, and then bonded with adhesive. Then it was placed at room temperature for natural curing for 3 days. During the test, the force gauge was hooked to the cylinder, and the cylinder was pulled at a uniform speed and parallel to the coating. The shear force required to remove the cylinder was measured. Each sample was set with 5 replicates, and the average value was taken. The results are shown in Figure 9

[0118] From Figure 9 ​It can be seen that the removal strength in the range of 0.25 MPa-0.40 MPa is removed, because the content of hard segment has no effect on it, it can be seen that the removal strength of ① and ② is the lowest, below 0.30 MPa, ③ and ⑤ respectively reached 0.35 MPa and above, ④ and ⑥ respectively only have a small difference between ③ and ⑤, the removal strength of ⑤ is slightly larger, which may be because the fusion degree of AMC grafted PDMS-PUa and PDMS-PTMG-2900-A is not good, resulting in some fine protrusions on the surface of the composite coating, which will cause uneven stress when pulling the tension machine, thereby making the removal strength larger. The above shows that the fouling release performance of PDMS-PUa-PDMS-PTMG-① and ② is better than that of PDMS-PUa-PDMS-PTMG-(③, ④, ⑤, ⑥).

[0119] Application Example 9 Anti-bacterial effect test

[0120] PDMS-PUa-PDMS-PTMG-①, ③ and ⑤ were selected as samples to be tested, and were dissolved in xylene and a mixture of xylene solvents to form a film naturally, and then were placed in an oven to keep dry. The plate counting method was used to study the antibacterial performance of the coating, and Escherichia coli (representing gram-negative bacteria) and Staphylococcus aureus (representing gram-positive bacteria) were used, and all the equipment and samples used for antibacterial experiments were sterilized in a high-pressure sterilization pot at 121℃ for 15min before use. Then the coating samples (0.1g each) were placed in a 24-well plate, and 2ml of bacterial suspension (diluted with 2ml PBS buffer) was injected, in which the concentration of Escherichia coli was about 1×10 7 CFU / mL, and the concentration of Staphylococcus aureus was about 1×10 8 CFU / mL, and incubated in a constant temperature incubator at a constant temperature of 37℃ for 5h. Then the suspension was diluted 500 times with PBS, and 100μL was uniformly coated on the LB plate, and then was placed in a 37℃ incubator and incubated overnight. The number of colonies of the blank control group was recorded as Ab, and the number of colonies of the sample group was recorded as Ac, and the calculation formula was as follows:

[0121]

[0122] The results are shown in Figure 10 and Figure 11 . Figure 10 Figure (A) of the above is the number of colonies of Escherichia coli on the LB agar plate, A is the blank control group; B is the anti-Escherichia coli effect diagram of PDMS-PUa-PDMS-PTMG-①; C is the anti-Escherichia coli effect diagram of PDMS-PUa-PDMS-PTMG-③; D is the anti-Escherichia coli effect diagram of PDMS-PUa-PDMS-PTMG-⑤. Figure 10Figure B is the number of colonies of Staphylococcus aureus on LB agar plate, A is the blank control group; B is PDMS-PUa-PDMS-PTMG-① antibacterial effect of Staphylococcus aureus; C is PDMS-PUa-PDMS-PTMG-③ antibacterial effect of Staphylococcus aureus; D is PDMS-PUa-PDMS-PTMG-⑤ antibacterial effect of Staphylococcus aureus. Figure 9 Figure B is the number of colonies of Staphylococcus aureus on LB agar plate, A is the blank control group; B is PDMS-PUa-PDMS-PTMG-① antibacterial effect of Staphylococcus aureus; C is PDMS-PUa-PDMS-PTMG-③ antibacterial effect of Staphylococcus aureus; D is PDMS-PUa-PDMS-PTMG-⑤ antibacterial effect of Staphylococcus aureus.

[0123] From Figure 10 and Figure 11 It can be seen from and compared with the blank control group, the antibacterial rate of PDMS-PUa-PDMS-PTMG-① on Escherichia coli is 100%, but the antibacterial rate of PDMS-PUa-PDMS-PTMG-③ and ⑤ on Escherichia coli can only reach 24.39% and 12.84%. The antibacterial rate of PDMS-PUa-PDMS-PTMG-① on Staphylococcus aureus is as high as 99.87%, and the antibacterial rates of PDMS-PUa-PDMS-PTMG-③ and ⑤ on Staphylococcus aureus are 96.57% and 96.53% respectively.

[0124] The above results show that: PDMS-PTMG-2900-A and PDMS-PUa-4:6:2 and 4:7:3 mixed composite coating has a certain inhibitory effect on Escherichia coli and Staphylococcus aureus, and the coating has excellent antibacterial effect. The composite coating PDMS-PUa-PDMS-PTMG-③ and ⑤ has only a slight inhibitory effect on Escherichia coli, and the inhibition rate on Staphylococcus aureus also decreases slightly. It may be that after mixing PDMS-PTMG-2900 (PDMS-PTMG-2900-A) and modified PDMS-PUa, the compatibility of the two is poor, the bactericide is wrapped up and cannot release the efficacy, and the two have certain incompatibility in the bactericidal process, resulting in reduced bactericidal effect.

[0125] Application Example 10 Diatom biofilm removal rate test

[0126] Diatoms can form biofilms on the surface of substrates, and biofilms are the main factor for attracting large-scale biological fouling to settle and grow on the surface of substrates. Triangular brown algae (representative marine fouling diatoms) are selected to determine the removal rate of diatom biofilms formed by the coating.

[0127] PDMS-PUa-PDMS-PTMG-①~⑥ were used as test samples. The samples were first dissolved in a mixture of xylene and methyl methacrylate, and then evenly spread into 24-well plates. Three biological replicates were performed for each sample. The plates were allowed to dry completely. Then, 1 ml of an algae solution with an OD of 0.1 was added to each 24-well plate and incubated in a light incubator (25℃, 150 rpm, 2500 lux) for 72 h. The culture medium was removed, and the wells were washed three times with PBS buffer. The plates were then air-dried at 37℃. Next, 1 ml of 0.1% crystal violet solution was added, and the plates were incubated at room temperature for 15 min. The crystal violet solution was then discarded, and the wells were washed three times with PBS buffer and air-dried at 37℃. Finally, 1 ml of 30% acetic acid was added to dissolve the crystal violet, and the plates were incubated for 15 min before being transferred to a new 96-well plate. The absorbance was then read at 550 nm using a microplate reader. The biofilm removal rate was expressed as the OD value of the blank group (OD). c ) and coating group OD value (OD p The difference between the OD values ​​of the control group and the OD values ​​of the control group (OD) c The average percentage of ) is expressed by the following formula.

[0128]

[0129] The results are as follows Figure 12 As shown, from Figure 12 As can be seen, the diatom biofilm removal rate of the PDMS-PUa-PDMS-PTMG composite coating is between 78% and 85%, indicating that a large amount of diatom biofilm is removed. The coating has a certain ability to inhibit diatom adhesion to the surface. The composite coating has good desorption performance against fouling caused by *Phaeodactylum tricornutum*. PDMS-PUa-PDMS-PTMG-⑤ shows the highest biofilm removal rate of 84.84%, demonstrating good anti-diatom performance and improved fouling desorption performance, thus possessing good antifouling performance. The difference between PDMS-PUa-PDMS-PTMG-① and ⑤ is not significant, close to 80%.

[0130] Considering the performance of the above-mentioned indicators, PDMS-PUa-PDMS-PTMG-③, ④, ⑤, and ⑥ are slightly better than PDMS-PUa-PDMS-PTMG-① and ② in some aspects. However, in terms of overall performance, the coatings of PDMS-PUa-PDMS-PTMG-① and ② are better than those of PDMS-PUa-PDMS-PTMG-③, ④, ⑤, and ⑥. They exhibit excellent adhesion, mechanical properties, and water resistance, as well as good antibacterial and anti-diatom properties, demonstrating both physical and chemical properties. This indicates that when modifying composite coatings, modifying only a single polymer is more effective than modifying two polymers simultaneously.

[0131] In summary, from Figure 1 、 Figure 2 、 Figure 4 、 Figure 5 、 Figure 6 、 Figure 9 and Figure 12 , it can be seen that the elastic modulus, water contact angle and free energy of the organic silicone polyurethane polymer PDMS-PTMG-2900 are not much different from those of the composite coatings PDMS-PUa-PDMS-PTMG-③ and ④, PDMS-PUa-PDMS-PTMG-① and ②; in terms of water absorption, PDMS-PUa-PDMS-PTMG-③ and ④ are nearly one time different from PDMS-PTMG-2900, indicating that the water absorption of the composite coating after compounding is significantly improved, and the water resistance is not good, but the water absorption of the modified composite coating PDMS-PUa-PDMS-PTMG-① and ② is further reduced, and is also lower than that of the single coating, and has more excellent water resistance; in terms of the removal strength of simulated barnacles, the removal strength of the single coating is between 0.25 MPa-0.30 MPa, but the removal strength of the composite coating PDMS-PUa-PDMS-PTMG-③ and ④ is all more than 0.30 MPa, and the removal strength of the modified composite coating PDMS-PUa-PDMS-PTMG-① and ② is reduced to between 0.25 MPa-0.30 MPa, and overall, the difference between the single coating and the composite coating and the modified composite coating is not more than 0.1 MPa, and the difference is small; in terms of the biofilm removal rate, the difference between the single coating PDMS-PTMG-2900 and the composite coatings PDMS-PUa-PDMS-PTMG-③ and ④ and the modified composite coatings PDMS-PUa-PDMS-PTMG-① and ② is more significant, about 65%, and the difference between the composite coatings PDMS-PUa-PDMS-PTMG-③ and ④ and the modified composite coatings PDMS-PUa-PDMS-PTMG-① and ② is small, about 80%. Therefore, compared with the single coating, the removal rate of the composite coating to the biofilm is greatly improved, and except for the poor water resistance, the remaining performance indicators are not much different from those of the single coating, but the modified composite coating can not only improve the removal rate of the biofilm, but also has good water resistance, and the remaining indicators are also better, and the overall comprehensive performance is greatly improved.

[0132] Although the present application has been described by the above preferred embodiments, it is not intended to limit the scope of protection of the present application, and any person skilled in the art can make various changes and modifications to the above embodiments without departing from the spirit and scope of the present application.

Claims

1. A polymer composite material based on artemisinin modification, characterized in that, The polymer composite material comprises organosilicon polyurea and dihydroartemisinin-modified organosilicon polyurethane, wherein the mass ratio of organosilicon polyurea to dihydroartemisinin-modified organosilicon polyurethane is (1-2):(2-1). The mass ratio of dihydroartemisinin to organosilicon polyurethane is 1:

5. Organosilicon polyurethane is prepared by first obtaining a polyurethane prepolymer through α,ω-hydroxypropyl-terminated polydimethylsiloxane HT-PDMS, polytetrahydrofuran PTMG, and isophorone diisocyanate IPDI, and then by γ-aminopropyltriethoxysilane-terminated prepolymer. The organosilicon polyurea is composed of α,ω-aminopropyl-terminated polydimethylsiloxane APT-PDMS, isophorone diisocyanate IPDI, and hexamethylenediamine HMDA, wherein the ratio of α,ω-aminopropyl-terminated polydimethylsiloxane APT-PDMS:isophorone diisocyanate IPDI:hexamethylenediamine HMDA is 4 mol:6 mol:2 mol, or the ratio of α,ω-aminopropyl-terminated polydimethylsiloxane APT-PDMS:isophorone diisocyanate IPDI:hexamethylenediamine HMDA is 4 mol:7 mol:3 mol.

2. The artemisinin-modified polymer composite material according to claim 1, characterized in that, The molecular weight of the polytetrahydrofuran is Mw = 2900.

3. The artemisinin-modified polymer composite material according to claim 1, characterized in that, The mass ratio of the α,ω-hydroxypropyl-terminated polydimethylsiloxane to polytetrahydrofuran is 1:

1.

4. The artemisinin-modified polymer composite material according to claim 1, characterized in that, The preparation method of the organosilicon polyurethane includes the following steps: (I) Preparation of polyurethane prepolymer α,ω-hydroxypropyl-terminated polydimethylsiloxane HT-PDMS and polytetrahydrofuran PTMG were dissolved in xylene solvent and magnetically stirred to mix thoroughly, resulting in a first mixed solution. Isophorone diisocyanate IPDI and dibutyltin dilaurate DBTDL were added to the first mixed solution to obtain a second mixed solution. The second mixed solution was added to a constant pressure funnel, and a vacuum was drawn and nitrogen gas was purged. This process was repeated twice. After purging nitrogen gas for 3-5 minutes the second time, the switch of the constant pressure funnel was adjusted so that the solution was added dropwise at a rate of 3-4 drops / s under nitrogen protection at 80°C for 20-40 minutes. After the addition was completed, the reaction was stirred for 2-4 hours to obtain a polyurethane prepolymer solution. (II) Preparation of Organosilicon Polyurethane γ-aminopropyltriethoxysilane was added to the polyurethane prepolymer solution to obtain a third mixed solution. The third mixed solution was added to a constant pressure funnel and added dropwise at a rate of 3-4 drops / s under nitrogen protection at 80°C for 30 min. After the addition was completed, the mixture was stirred for 2-4 h and then freeze-dried to obtain organosilicon polyurethane.

5. A method for preparing a polymer composite material based on artemisinin modification according to claim 1, characterized in that, The organosilicon polyurea solution and the organosilicon polyurethane solution modified with dihydroartemisinin were mixed at a mass ratio of 1:

1. The mixture was then stirred at a speed of 60-80 rpm for 5-8 minutes. The resulting solution is the polymer composite material based on artemisinin modification.

6. The application of the artemisinin-modified polymer composite material according to any one of claims 1-4 in marine antifouling coatings.

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