Artemisinin modification-based polymer composite anti-marine fouling coating and preparation method thereof

Abstract

The invention discloses a polymer composite material based on artemisinin modification, which is characterized in that the polymer composite material comprises organic silicon polyurethane modified by an artemisinin compound and organic silicon polyurea, and the mass ratio of the organic silicon polyurethane modified by the artemisinin compound to the organic silicon polyurea is (2-1): (1-2). The coating is high in hardness, good in mechanical performance, low in elastic modulus, good in stain removal effect and good in adhesion performance, can be stably attached to a substrate and is not prone to falling off, meanwhile, has an excellent antibacterial effect, is not prone to being hydrolyzed by water in seawater or air in the using process on the premise that all the conditions are met, is good in water resistance and can be widely applied to the field of water treatment. Therefore, the long-term stability of the composite coating is ensured, the comprehensive performance of the coating can be comprehensively improved, and the marine antifouling coating serving as an environment-friendly marine antifouling coating has a good application prospect.

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. For example, the mechanical properties of the coating are very excellent, which may lead to a decrease in the antifouling performance, so that the fouling organisms are difficult to be easily removed by water shear force, and it is difficult to achieve both. Therefore, researchers have begun to prepare composite coatings by compounding two single coatings to make up for the defects of single coatings in some aspects (such as mechanical properties, adhesion properties, antibacterial properties and antifouling properties). Although the comprehensive performance of the polymer coating after compounding is improved to a certain extent, 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 of the current composite antifouling coating material, such as mechanical properties, antifouling effect and adhesion performance, needs to be improved.

[0006] The above purpose of the present application is achieved by the following technical scheme: A polymer composite material based on artemisinin modification, 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).

[0007] 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.

[0008] 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.

[0009] In an alternative embodiment, the molecular weight of the polytetramethylene glycol is 2900.

[0010] In an alternative embodiment, the mass ratio of the polydimethylsiloxane to the polytetramethylene glycol is 1:1.

[0011] In an alternative embodiment, the method for preparing the silicone polyurethane polymer comprises the following steps: (I) Preparation of a polyurethane prepolymer 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 nitrogen is introduced for 3-5 min the second time, the switch of the constant-pressure funnel is adjusted, and the solution is added dropwise at a rate of 3-4 drops / s at 80°C under nitrogen protection. After the dropwise addition is completed, the solution is stirred for 2-4 h to obtain a polyurethane prepolymer solution. (II) Preparation of a silicone polyurethane polymer 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 step (I) are repeated. After the dropwise addition is completed, the solution is stirred for 2-4 h, and is then freeze-dried to obtain a silicone polyurethane polymer.

[0012] In an alternative embodiment, the artemisinin is one of artesunate, dihydroartemisinin, or artemether.

[0013] In an alternative embodiment, the organic silicone polyurea comprises polydimethylsiloxane PDMS, isophorone diisocyanate IPDI and hexamethylenediamine HMDA, and the polydimethylsiloxane PDMS: isophorone diisocyanate IPDI: hexamethylenediamine HMDA = 4 mol: 6 mol: 2 mol, or the polydimethylsiloxane PDMS: isophorone diisocyanate IPDI: hexamethylenediamine HMDA = 4 mol: 7 mol: 3 mol.

[0014] The second aspect of the present application is to provide a preparation method of the artemisinin-modified polymer composite, mixing the artemisinin-modified organic silicone polyurethane solution and the organic silicone polyurea solution at 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.

[0015] The third aspect of the present application is to provide the application of the artemisinin-modified polymer composite in marine antifouling coating.

[0016] Compared with the prior art, the technical scheme of the present application has the following advantages: The composite material obtained by compounding the artemisinin-modified organic silicone polyurethane polymer and the organic silicone-modified polyurea polymer has high hardness, good mechanical properties, low elastic modulus, good fouling removal effect, good adhesion, and can be stably attached to the substrate without falling off, and also has excellent antibacterial effect, and under the premise of meeting these conditions, 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

[0017] Figure 1 The elastic modulus (A), water contact angle (B), surface free energy (C), and water absorption rate (D) of the organic silicone polyurethane polymer PDMS-PTMG-2900 of Example 1 of the present application as a single coating layer; Figure 2 The removal strength (A) and biofilm removal rate (B) of the organic silicone polyurethane polymer PDMS-PTMG-2900 of Example 1 of the present application as a single coating layer on simulated barnacles; Figure 3 The infrared spectrum of the composite coating PDMS-PUa-PDMS-PTMG-(①-⑥) of the present application; Figure 4The stress-strain curve (A) and elastic modulus (B) of the composite coating PDMS-PUa-PDMS-PTMG-(①-⑥) of the application; Figure 5 The water contact angle (A) and surface free energy (B) of the composite coating PDMS-PUa-PDMS-PTMG-(①-⑥) of the application; Figure 6 The water absorption rate of the composite coating PDMS-PUa-PDMS-PTMG-(①-⑥) of the application; Figure 7 The distribution of Si and O elements on the surface of the composite coating PDMS-PUa-PDMS-PTMG-(①-⑥) of the application; Figure 8 The field emission scanning electron microscope (FESEM) picture of the composite coating PDMS-PUa-PDMS-PTMG-(①-⑥) of the application; Figure 9 The removal intensity of the composite coating PDMS-PUa-PDMS-PTMG-(①-⑥) of the application on simulated barnacles; Figure 10 The effect diagram of the composite coating PDMS-PUa-PDMS-PTMG-(①, ③, ⑤) of the application on E. coli (A) and Staphylococcus aureus (B); Figure 11 The bacteriostatic efficiency of the composite coating PDMS-PUa-PDMS-PTMG-(①, ③, ⑤) of the application on E. coli and Staphylococcus aureus; Figure 12 The removal rate of the composite coating PDMS-PUa-PDMS-PTMG-(①-⑥) of the application on biofilm. DETAILED DESCRIPTION

[0018] 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.

[0019] 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 Yinn Chemical Technology Co., Ltd.) and isopropyl alcohol (IPA) (Shanghai Yinn Chemical Technology Co., Ltd.), dimethylbenzene (Shanghai Maikelin Biotechnology Co., Ltd.), γ-aminopropyl triethoxysilane (KH-550) are chromatographically pure; deionized water is laboratory self-made.

[0020] 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, and 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.

[0021] Example 1 A polymer composite based on artemisinin modification, comprising the following steps: I. Preparation of silicone polyurethane polymer (I) Preparation of polyurethane prepolymer HT-PDMS (α, ω-hydroxypropyl-terminated polydimethylsiloxane) was 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 double-necked flask with a magnetic stirrer for stirring. After uniform stirring, a first mixed solution was obtained. To the first mixed solution, 1.54 g (6.76 mmol) of IPDI (isophorone diisocyanate) and 0.05 g (0.08 mmol) of DBTDL (dibutyltin dilaurate) were added, and after uniform mixing and stirring, a second mixed solution was obtained. The second mixed solution was added to a constant pressure funnel, and then vacuum was drawn and nitrogen was passed through, repeated twice. After 3 min of nitrogen passing through for the second time, the opening of the constant pressure funnel was slowly adjusted so that the solution was added at a rate of 3-4 drops / s under the protection of nitrogen at 80 °C. The addition time was about 20 min. After the addition was completed, the reaction was stirred for another 2 h to obtain a polyurethane prepolymer solution.

[0022] (II) Preparation of silicone-modified polyurethane polymer 1 g (4.52 mmol) of KH-550 (γ-aminopropyltriethoxysilane) was dissolved in the polyurethane prepolymer solution, and after uniform mixing, a third mixed solution was obtained. The third mixed solution was added to a constant pressure funnel, and then added at a rate of 3-4 drops / s under the protection of nitrogen at 80 °C. The addition time was about 30 min. After the addition was completed, the reaction was stirred for another 3 h, and then freeze-dried to obtain a silicone polyurethane polymer. The obtained product was named PDMS-PTMG-2900.

[0023] II. Preparation of artemisinin-modified silicone-based polyurethane polymer The silicone polyurethane polymer was dissolved in a xylene solvent to prepare a 20 wt% solution, and then 0.028 g / mL of dihydroartemisinin solution was added to the silicone polyurethane polymer solution at a mass ratio of 5 (silicone polyurethane polymer): 1 (dihydroartemisinin). The two were mixed uniformly using a high-speed disperser at a speed of 70 rpm for 6 min. After freeze-drying, a solid artemisinin silicone polyurethane polymer was obtained. The obtained product was named PDMS-PTMG-2900-A.

[0024] III. Preparation of silicone polyurea Firstly, the PDMS was placed in a vacuum drying oven for dehydration treatment at 110 °C for 2 h. Then, 4 g (0.004 mol) of the treated PDMS was weighed and dissolved in 10 ml of a 1:1 mixed solution of THF (tetrahydrofuran) and IPA (isopropyl alcohol) to obtain solution A; 1.34 g (0.006 mol) of IPDI (isophorone diisocyanate) was dissolved in 20 ml 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. Solution A was added dropwise to solution B at room temperature under a nitrogen atmosphere for 30 min, and the reaction was continued for 1 h after the dropwise addition was completed. Then, 0.23 g (0.002 mol) 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 1 h, and the reaction was continued for 3 h after the dropwise addition was completed, to obtain a transparent and uniform polymer solution. After freeze-drying, a solid-state silicone polyurea polymer was obtained, which was named PDMS-PUa-4:6:2 (4:6:2 = 4 mol:6 mol:2 mol = polydimethylsiloxane PDMS: isophorone diisocyanate IPDI: hexanediamine HMDA).

[0025] IV. Preparation of artemisinin-modified polymer composite 1 g of artemisinin silicone polyurethane polymer was weighed and dissolved in xylene, and 1 g of silicone polyurea polymer was dissolved in isopropyl alcohol. Then, the two completely dissolved solutions were poured into beakers, respectively, and mixed uniformly with a high-speed disperser at a speed of 80 rpm for 5 min. The mixed solution was artemisinin-modified polymer composite, which was named PDMS-PUa-PDMS-PTMG-① (in PDMS-PUa, polydimethylsiloxane PDMS: isophorone diisocyanate IPDI: hexanediamine HMDA = 4 mol:6 mol:2 mol).

[0026] Example 2 The preparation of the silicone polyurethane polymer, artemisinin-modified silicone-based polyurethane polymer, and artemisinin-modified polymer composite of this example was the same as that of Example 1, except that in the preparation of the silicone polyurea, polydimethylsiloxane PDMS: isophorone diisocyanate IPDI: hexanediamine HMDA = 4 mol:6 mol:2 mol. The preparation steps of the silicone polyurea were as follows: APT-PDMS (a, w-amino propyl terminated polydimethylsiloxane) was first dehydrated at 110 °C for 2 h in a vacuum oven. Then 4 g (0.004 mol) of the treated APT-PDMS was dissolved in 10 ml of THF (tetrahydrofuran) and IPA (isopropyl alcohol) 1:1 mixed solution to obtain solution A; 1.56 g (0.007 mol) of IPDI (isophorone diisocyanate) was dissolved in 20 ml 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. Solution A was added dropwise into solution B at room temperature under nitrogen for 30 min, and then reacted for 1 h after the dropwise addition was completed. Then 0.35 g (0.003 mol) of HMDA (1,6-hexanediamine) was dissolved in a 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 1 h, and then reacted for 3 h after the dropwise addition was completed, to obtain a transparent and uniform polymer solution. After freeze-drying, a solid-state silicone polyurea polymer was obtained, which was named PDMS-PUa-4:7:3. The artemisinin-modified polymer composite prepared by the silicone polyurea was named PDMS-PUa-PDMS-PTMG-② (in PDMS-PUa, polydimethylsiloxane PDMS: isophorone diisocyanate IPDI: hexanediamine HMDA = 4 mol:7 mol:3 mol).

[0027] Comparative Example 1 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 = 4 mol:6 mol:2 mol).

[0028] Comparative Example 2 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 = 4 mol:7 mol:3 mol).

[0029] Comparative Example 3 This comparative example is different 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: 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 APT-PDMS (α, ω-aminopropyl terminated polydimethylsiloxane) is placed in a vacuum drying box at 110°C for 2 hours before use.

[0030] First, 1.34 g (6 mmol) of IPDI (isophorone diisocyanate) is added to a 250 ml two-necked flask containing 20 ml of solvent and a magnetic stirrer. 4 g (4 mmol) of APT-PDMS is dissolved in 10 ml of solvent, then added to a constant pressure funnel, vacuumed and purged with nitrogen, repeated twice, and after the second time purging with nitrogen for 3 minutes, the oil bath temperature is maintained at 25°C and the solution is added at a speed of 3-4 s / drop under magnetic stirring, which takes about half an hour, and after the addition is completed, it is reacted for one hour.

[0031] Then 0.03 g (0.171 mmol) of 7-amino-4-methylcoumarin is dissolved in 10 ml of solvent, added to a constant pressure funnel, and slowly adjusted to the opening of the constant pressure funnel under the catalysis of DBTDL (dibutyltin dilaurate), 80°C and nitrogen protection, which takes about 0.5 h, and finally 0.23 g (2 mmol) of HMDA (1,6-hexanediamine) is dissolved in 10 ml of mixed solvent, added to a constant pressure funnel, re-vacuumed and purged with nitrogen, and the solution is added at a speed of 5-6 s / drop by slowly adjusting the opening of the constant pressure funnel, which takes about one hour, and 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, then the product is washed with deionized water, and after the washing is completed, it is placed in a vacuum drying oven at 60°C, and the drying time is about 45-48 h. The obtained product is the 7-amino-4-methylcoumarin grafted silicone polyurea, named PDMS-PUa-4:6:2-AMC (in PDMS-PUa, polydimethylsiloxane PDMS: isophorone diisocyanate IPDI: hexanediamine HMDA = 4 mol:6 mol:2 mol).

[0032] 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.

[0033] Comparative Example 4 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: 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 2 h before use.

[0034] First, 1.70 g (7.65 mmol) of IPDI (isophorone diisocyanate) is added to a 250 ml two-necked flask containing 20 ml of solvent and a magnetic stirrer. 4 g (4 mmol) of APT-PDMS is dissolved in 10 ml of solvent, then added to a constant pressure funnel, and vacuumed and purged with nitrogen twice. After 3 min 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 3-4 s / drop under magnetic stirring. The process takes about half an hour, and after the addition is completed, it is reacted for one hour.

[0035] 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. Under the catalysis of DBTDL (dibutyl tin dilaurate), at 80 °C and under the protection of nitrogen, the switch of the constant pressure funnel was slowly adjusted, and 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 vacuum was re-pumped and the nitrogen was re-purged, and the switch of the constant pressure funnel was slowly adjusted 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 was completed, the reaction was continued for three hours. After the reaction was completed, the reaction product needed to be purified. The excess solvent in the product was removed by a rotary evaporator, and then the product was washed with deionized water. After the washing was completed, it was placed in a vacuum drying oven at 60 °C, and 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).

[0036] The polymer composite obtained by mixing the artemisinin-modified silicone polyurethane polymer and the silicone polyurea polymer grafted with 7-amino-4-methylcoumarin was named PDMS-PUa-PDMS-PTMG-⑥.

[0037] It should be noted that grafting 7-amino-4-methylcoumarin onto the silicone polyurea polymer is a process of modifying the silicone polyurea polymer, which is consistent with the artemisinin-modified silicone-based polyurethane polymer, and both are modified polymers.

[0038] Application Example 1 Fourier infrared spectroscopy characterization The polymers prepared in Examples 1 and 2 and Comparative Examples 1-4 were used as the 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 .

[0039] 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 peak at 2840 cm -1-2968 cm -1 The peak at 1692 cm is attributed to the stretching vibration of -CH, while the peak at 1692 cm -1 The peak at 2260 cm is attributed to the stretching vibration of the C=O group. -1 The peak at 1000-1100 cm -1 There are two peaks at 795 cm, which are the characteristic absorption peaks of Si-O-Si. -1 The peak at 1252 cm is attributed to the stretching vibration of Si-C groups, while the peak at 1252 cm -1 The peak at is the bending vibration absorption peak of the Si-C group, which proves that the polymer synthesis is successful.

[0040] Application Example 2 Elastic Modulus Test When the composite polymer acts on the antifouling coating, due to the incompatibility of the chain segment and hard segment of PDMS, microphase separation will occur, which may affect its mechanical properties. The composite material prepared in this study is composed of two different polymers, which may affect its own mechanical properties. Therefore, the mechanical properties of the composite coating were studied through tensile tests. The polymer composite materials in Examples 1 and 2 and Comparative Examples 1-4 were dissolved and naturally formed into films, and then placed in an oven for drying. The films were punched into dumbbell-shaped test samples and tested using a universal material testing machine. The tensile rate was 10 mm / min, 5 repetitions were set for each sample, and the experimental results were averaged. The results are as follows Figure 4 shown. Figure 4 Figure A is the stress-strain curve of PDMS-PUa-PDMS-PTMG-(①~⑥). Figure 4 Figure B is the elastic modulus data of PDMS-PUa-PDMS-PTMG-(①~⑥).

[0041] from Figure 4 As shown in Figure B, PDMS-PUa-PDMS-PTMG-⑤ and ⑥ have higher elastic moduli, while ① has the lowest elastic modulus. The comparison between these six elastic moduli is: ②>①, ④>③, ⑥>⑤. This is also because the hard segments of PDMS-PUa contained increase, and the hard segments produced by microphase separation act as the second phase, which will enhance the mechanical properties of the coating, thereby improving the elastic modulus of the modified coating. However, the overall elastic modulus of the composite coating does not exceed 0.25 MPa, maintaining a low elastic modulus. 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.

[0042] Application Example 3 Hydrophobicity Test 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 occupies a great factor in the evaluation of the fouling release performance thereof.

[0043] PDMS-PUa-PDMS-PTMG-(①-⑥) were respectively dissolved in xylene solvent, poured into a polytetrafluoroethylene dish, and naturally dried into a film at room temperature. Before testing, they were first placed in a 50 ℃ oven and baked for 24 h. A contact angle tester (JC2000CS, Shanghai Zhongchen Co., Ltd.) was used to test the static contact angle of the coating surface. The test used the solid drop method, and the surrounding environment was stabilized at about 25 ℃. The water contact angle test used 3 μL as the quantitative, and the diiodomethane contact angle test used 2 μL as the quantitative. Each sample was tested at 5 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.

[0044]

[0045] The results are shown in Figure 5 and Table 1. Figure 5 In the figures, A is the water contact angle of the polymer coating; and B is the surface free energy of the polymer coating.

[0046] As can be seen from A of Figure 5 and Table 1, the water contact angle of PDMS-PUa-PDMS-PTMG-(①-⑥) is in the range of 98°-104°. This is 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 on 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. As can be seen from the above, ① is the largest, ③ is the second, and ⑥ is the smallest. From the comparison, ①>②, ③>④, and ⑤>⑥. This is because the proportion of the hard segment increases, and the proportion of the polydimethylsiloxane soft segment decreases, which weakens the hydrophobicity.

[0047] Table 1 Contact angle and surface free energy of PDMS-PUa-PDMS-PTMG-(①-⑥) polymer coating

[0048] According to the contents of Table 1 above, the contact angles of water and diiodomethane were respectively measured, and the surface free energy of the composite coating was calculated according to the Owens and Wendt method. As can be seen from B of Figure 5 , the surface free energy of the PDMS-PUa-PDMS-PTMG-(①-⑥) coating is in the range of 20-22 mJ / m -2Within the scope, it also shows that the polymer coating surface 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 The degree of interaction between the coating and marine fouling organisms is relatively low, and the fouling organisms attached to the coating surface can be easily stripped by water shear force, and it is not easy to maintain stable adhesion during navigation.

[0049] Application Example 4 Water resistance test 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, and to evaluate the damage resistance and service life of the composite coating for long-term application in marine environment.

[0050] PDMS-PUa-PDMS-PTMG- (① ~ ⑥) polymer as the sample to be tested, respectively dissolved in isopropyl alcohol solvent, poured into a polytetrafluoroethylene dish, dried at room temperature to form a film, and then placed in a 50°C oven for 24h, the dried film was cut into a 3cm x 1cm strip, and the original mass was m0. Then put it into a small glass bottle containing deionized water, and after 24h, weigh the mass after water absorption as m1. Each sample sets 5 replicates, and the average value is calculated. The water absorption rate W is calculated as follows:

[0051] The results are shown in Figure 6 From Figure 6 , the water absorption rates of the six coatings are: ⑥> ⑤> ④> ③> ②> ①, among which, the water absorption rates of ① and ② are significantly different from the other four coatings, which also shows that PDMS-PUa-4:6:2 / 4:7:3 and PDMS-PTMG-2900-A can be better combined, and the structure has fewer voids, making it difficult for water molecules to enter, thus the water absorption rate is low, and the water resistance is good; The water absorption rates of ⑤ and ⑥ are larger, which may be because the AMC (7-amino-4-methyl coumarin) grafted PDMS-PUa-4:6:2 / 4:7:3 and PDMS-PTMG-2900-A cannot be completely aggregated together during the fusion process, and there are voids in the molecular structure, so water molecules can enter the coating, and the water absorption rate becomes larger. Although the overall water absorption rate does not exceed 3.5%, it still has good water resistance, but the difference is still significant compared to ① and ②, and the service life of ① and ② is much longer than that of ③, ④, ⑤ and ⑥.

[0052] Application Example 5 Mechanical property test For the composite antifouling coating, whether it can form good adhesion with the substrate is an important indicator, and in the research, the compatibility between the two different polymers is also considered, whether the combination of the two will affect some mechanical properties needs to be explored.

[0053] To investigate the mechanical durability of PDMS-PUa-PDMS-PTMG-(①-⑥), the mechanical properties of the polymer coating were evaluated by measuring the adhesion of the coating, the hardness of the coating, the flexibility of the coating, and the impact resistance of the coating. The following tests use PDMS-PUa-PDMS-PTMG-(①-⑥) polymer as the sample to be tested.

[0054] a) Coating adhesion test: Dissolve the sample to be tested in isopropyl alcohol solvent, then evenly coat on the iron sheet, and test the coating adhesion according to GB / T 1720-2020. Use the paint film adhesion tester to test by drawing a circle. The test result range is 1-7 levels.

[0055] b) Coating hardness test Dissolve the sample to be tested in isopropyl alcohol solvent, then evenly coat on the iron sheet, and test the coating hardness according to GB / T6739-2006 "Pigment and varnish, pencil method for testing paint film hardness". Use the coating pencil hardness scratch hardness tester to test the hardness. The test result range is 6B-6H.

[0056] c) Coating flexibility test Dissolve the sample to be tested in isopropyl alcohol solvent, then evenly coat on the iron sheet, and test the coating flexibility according to GB / T1731-2020. Use the paint film impact tester to test the flexibility. The test result range is 1-7 levels.

[0057] d) Coating impact resistance test Dissolve the sample to be tested in isopropyl alcohol solvent, then evenly coat on the iron sheet, and test the coating impact resistance according to GB / T20624.2-2006. Use the paint film impact tester to test the impact resistance. The test result is evaluated by the impact height of the weight hammer from 0-50 cm.

[0058] The mechanical properties (adhesion, hardness, flexibility, impact resistance) of different samples to be tested are shown in Table 2.

[0059] Table 2 Mechanical properties of PDMS-PUa-PDMS-PTMG-(①-⑥) composite coating

[0060] From the above table, the adhesion of the composite coating is all at 2-3 level, while the hardness, flexibility and impact resistance are consistent, indicating that the adhesion of the composite coating is good.

[0061] Example 6 Energy dispersive X-ray spectroscopy (EDS) analysis All samples were placed in an oven to keep them dry before being sent for testing. Energy dispersive X-ray spectroscopy was used to scan the surface of the coating to obtain the elemental content and distribution of Si, O and N in the coating. By performing EDS analysis on the polymer composite coatings of PDMS-PUa-PDMS-PTMG-① ~ ⑥, the surface chemical composition of the coating can be obtained, and the results are shown in Figure 7 .

[0062] From Figure 7 the elemental distribution of Si and O in PDMS-PUa-PDMS-PTMG-① ~ ⑥ can be observed. It can be seen that the distribution of Si and O in PDMS-PUa-PDMS-PTMG-① and ② is very dense and uniform, which also proves that PDMS-PUa and PDMS-PTMG-2900 modified with dihydroartemisinin have good compatibility, and the two substances can be well compounded together. However, the distribution of Si and O in PDMS-PUa-PDMS-PTMG-③, ④, ⑤ and ⑥ is very dense but not uniform, which may be due to the poor compatibility of PDMS-PUa and PDMS-PTMG-2900. The PDMS-PUa grafted with 7-amino-4-methyl coumarin cannot have good compatibility with PDMS-PTMG-2000-A, so there are phenomena such as clumping after mixing, resulting in uneven distribution of Si and O elements.

[0063] Example 7 Field emission scanning electron microscope (FESEM) analysis As an antifouling coating, surface roughness also affects the adhesion of marine fouling organisms on its surface. Generally, the greater the surface roughness, the easier it is for fouling organisms to adhere to the surface, and the surface roughness also affects the change of the surface contact angle. PDMS-PUa-PDMS-PTMG-① ~ ⑥ were used as test samples, dissolved in isopropyl alcohol solvent, and then uniformly coated on iron pieces. The thin films obtained after natural curing were first placed in an oven to keep them dry before testing. Field emission scanning electron microscope (FESEM, Thermo Apreo2C) was used to observe the morphology of the coating surface during testing, with magnifications of 1000 and 250000. The results are shown in Figure 8 . Figure 8In the middle, A figure represents PDMS-PUa-PDMS-PTMG-①, B figure represents PDMS-PUa-PDMS-PTMG-②, C figure represents PDMS-PUa-PDMS-PTMG-③, D figure represents PDMS-PUa-PDMS-PTMG-④, E figure represents PDMS-PUa-PDMS-PTMG-⑤, F figure represents PDMS-PUa-PDMS-PTMG-⑥.

[0064] From Figure 8 It can be seen from the figures that PDMS-PUa-PDMS-PTMG-① and ② have only a little protrusion and white spots, and the white spots are aggregated hard segments. Overall, they have good flatness and smoothness, which corresponds to the EDS element distribution map, indicating that the PDMS-PUa-PDMS-PTMG-① and ② composite coatings can be well fused and not excluded. PDMS-PUa-PDMS-PTMG-③, ④, ⑤ and ⑥ have more protrusions and lumps, which corresponds to the EDS element distribution map, indicating that the grafted PDMS-PUa of AMC cannot be well compatible with PDMS-PTMG-2900-A and PDMS-PTMG-2900 cannot be well compatible with PDMS-PUa. After being mixed and cured into a film, they will be unevenly distributed, and the flatness and smoothness are poor.

[0065] Application Example 8 Simulation barnacle removal effect test A simulation barnacle experiment is carried out in the laboratory to replace the real barnacle for testing. The removal strength of the simulation barnacle on the coating surface is measured to evaluate the anti-adhesion of the coating to marine macrofouling organisms. The smaller the removal strength is, the better the coating prevents the adhesion of fouling organisms. The simulation barnacle removal experiment is tested according to ASTM D5618 (2011).

[0066] PDMS-PUa-PDMS-PTMG-①-⑥ are used as test samples. The test samples are 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 are set on the epoxy resin plate, and the positions are kept as uniform as possible. Then, the adhesives are used for bonding. Then, it is placed at room temperature for natural curing for 3 days. During the test, the force gauge is used to hook the cylinder, and the shear force required to remove the cylinder is measured by pulling at a uniform speed and parallel to the coating. Five repetitions are set for each sample, and the average value is taken. The results are shown in Figure 9 .

[0067] From Figure 9It 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).

[0068] Application Example 9 Antibacterial effect test PDMS-PUa-PDMS-PTMG-①, ③ and ⑤ were selected as test samples, dissolved in xylene and mixed solvent of xylene, and then naturally formed into films and placed in an oven to keep dry. 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 experiment were sterilized in an autoclave at 121 ℃ for 15 min before use. Then the coating samples (0.1 g each) were placed in a 24-well plate, and 2 ml of bacterial suspension (diluted with 2 ml 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 5 h. Then the suspension was diluted 500 times with PBS, and 100 μL was uniformly coated on the LB plate, and then 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:

[0069] 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 antibacterial effect diagram of PDMS-PUa-PDMS-PTMG-① against Escherichia coli; C is the antibacterial effect diagram of PDMS-PUa-PDMS-PTMG-③ against Escherichia coli; D is the antibacterial effect diagram of PDMS-PUa-PDMS-PTMG-⑤ against Escherichia coli. 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 The antibacterial rate of PDMS-PUa-PDMS-PTMG composite coating on E. coli and Staphylococcus aureus.

[0070] From Figure 10 and Figure 11 It can be seen that, compared with the blank control group, the antibacterial rate of PDMS-PUa-PDMS-PTMG-① on E. coli is 100%, but the antibacterial rate of PDMS-PUa-PDMS-PTMG-③ and ⑤ on E. 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.

[0071] The above results show that: the composite coating obtained by mixing PDMS-PTMG-2900-A and PDMS-PUa-4:6:2 and 4:7:3 has a certain inhibitory effect on E. 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 E. coli, and the inhibitory rate on Staphylococcus aureus also decreases slightly, which may be due to the poor compatibility of PDMS-PTMG-2900 (PDMS-PTMG-2900-A) and modified PDMS-PUa after mixing, the bactericide is wrapped and cannot release the efficacy, and the two have certain incompatibility in the bactericidal process, resulting in reduced bactericidal effect.

[0072] Application Example 10 Diatom biofilm removal rate test Diatoms can form biofilms on the surface of substrates, and biofilms are the main factors that attract large-scale biological fouling to settle and grow on the surface of substrates. Triangular brown algae (representative marine fouling diatoms) were selected to determine the removal rate of diatom biofilms formed by the coating.

[0073] PDMS-PUa-PDMS-PTMG-①~⑥ were used as test samples. The test samples were first dissolved in a mixed solvent of xylene and xylene, and evenly coated on a 24-well plate. Three biological replicates were performed for each sample, and the plates were allowed to dry thoroughly. 1 ml of algae solution with an OD of 0.1 was then taken and added to a 24-well plate. The plates were cultured in a light incubator (25°C, 150 r / min, 2500 lux) for 72 h. The culture medium was removed, the wells were washed three times with PBS buffer solution, and dried at 37°C. Subsequently, 1 ml of 0.1% crystal violet solution was added and incubated at room temperature for 15 min. The crystal violet solution was then discarded, and the wells were washed three times with PBS buffer solution and dried at 37°C. Subsequently, 1 ml of 30% acetic acid was added to dissolve the crystal violet, incubated for 15 min, and transferred to a new 96-well plate. The absorbance was then read at 550 nm on a microplate reader. The biofilm removal rate was measured using the OD value of the blank group (OD c ) and OD value of coating group (OD p ) and the OD value of the control group (OD c ) is expressed as a percentage of the average value, and the calculation formula is as follows.

[0074]

[0075] The results are as follows Figure 12 As shown, from Figure 12 It can be seen that the diatom biofilm removal rate of the PDMS-PUa-PDMS-PTMG composite coating is between 78% and 85%, indicating that the diatom biofilm is removed in large quantities. The coating has a certain effect of inhibiting the attachment of diatoms to the surface. The composite coating has a good desorption performance on the fouling formed by triangular algae. PDMS-PUa-PDMS-PTMG-⑤ shows the highest biofilm removal rate of 84.84%, showing good anti-diatom performance. The fouling desorption performance is improved, thus having good anti-fouling performance. The difference between PDMS-PUa-PDMS-PTMG-① and ⑤ is not much, close to 80%.

[0076] Based on the performance of the above-mentioned multiple indicators, PDMS-PUa-PDMS-PTMG-③, ④, ⑤ and ⑥ are slightly better than PDMS-PUa-PDMS-PTMG-① and ② in some properties. However, in terms of comprehensive performance, the effects of PDMS-PUa-PDMS-PTMG-① and ② coatings are better than PDMS-PUa-PDMS-PTMG-③, ④, ⑤ and ⑥. While having excellent adhesion, mechanical properties and water resistance, they also show good antibacterial and anti-diatom properties, and have dual physical and chemical properties. This shows that when modifying the composite coating, the effect of modifying only a single polymer is better than modifying both polymers at the same time.

[0077] From the above, 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 the water absorption rate, PDMS-PUa-PDMS-PTMG-③ and ④ are nearly one time different from PDMS-PTMG-2900, indicating that the water absorption rate of the composite coating after compounding is significantly improved, and the water resistance is not good, but the water absorption rate 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 the removal intensity of simulated barnacles, the removal intensity of the single coating is between 0.25 MPa-0.30 MPa, but the removal intensity of the composite coating PDMS-PUa-PDMS-PTMG-③ and ④ is more than 0.30 MPa, and the removal intensity of the modified composite coating PDMS-PUa-PDMS-PTMG-① and ② is reduced to 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 the biological membrane removal rate, the difference between the single coating PDMS-PTMG-2900 and the composite coating PDMS-PUa-PDMS-PTMG-③ and ④ and the modified composite coating PDMS-PUa-PDMS-PTMG-① and ② is more significant, about 65%, and the difference between the composite coating PDMS-PUa-PDMS-PTMG-③ and ④ and the modified composite coating 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 biological membrane 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 biological membrane, but also has good water resistance, and the remaining indicators are also good, and the overall comprehensive performance is greatly improved.

[0078] 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 based on artemisinin modification, characterized by, The polymer composite material includes organosilicon polyurethane modified with an artemisinin compound and organosilicon polyurea, and the mass ratio of the organosilicon polyurethane modified with an artemisinin compound to the organosilicon polyurea is (2-1):(1-2).

2. The artemisinin-modified polymer composite according to claim 1, characterized in that, The artemisinin-modified organosilicon polyurethane is obtained by mixing an organosilicon polyurethane polymer solution and an artemisinin compound solution and freeze-drying them, wherein the volume ratio of the organosilicon polyurethane polymer solution to the artemisinin compound solution is 5:0.5-2, and the concentration of the artemisinin compound is 0.01-0.04 g / mL.

3. The artemisinin-modified polymer composite according to claim 1, wherein In the organosilicon polyurethane modified with artemisinin compounds, the organosilicon polyurethane is an organosilicon polyurethane polymer synthesized by using dihydroxy-terminated polydimethylsiloxane and polytetrahydrofuran as soft segments and γ-aminopropyltriethoxysilane as a capping agent.

4. The artemisinin-modified polymer composite according to claim 3, wherein The molecular weight of the polytetrahydrofuran is 2900.

5. The artemisinin-modified polymer composite according to claim 3, wherein The mass ratio of the polydimethylsiloxane to polytetrahydrofuran is 1:

1.

6. The artemisinin-modified polymer composite according to claim 3, wherein The preparation method of the organosilicon polyurethane polymer comprises the following steps: (1) Preparation of polyurethane prepolymer Dissolve dihydroxy-terminated polydimethylsiloxane HT-PDMS and polytetrahydrofuran PTMG in xylene solvent and stir magnetically to mix thoroughly to obtain a first mixed solution. Add isophorone diisocyanate IPDI and dibutyltin dilaurate DBTDL to the first mixed solution to obtain a second mixed solution. Add the second mixed solution dropwise to a constant pressure funnel and evacuate and purge with nitrogen twice. After the second nitrogen purging for 3 to 5 minutes, adjust the switch of the constant pressure funnel and add the solution dropwise at a rate of 3 to 4 drops / s under nitrogen protection at 80°C for 20 to 40 minutes. After the addition is complete, stir and react for 2 to 4 hours to obtain a polyurethane prepolymer solution. (2) Preparation of silicone polyurethane polymer γ-Aminopropyltriethoxysilane is added to the polyurethane prepolymer solution to obtain a third mixed solution. The third mixed solution is added to the constant pressure funnel, and the steps in step (1) are repeated. After the addition is completed, the mixture is stirred for reaction for 2 to 4 hours, and then freeze-dried to obtain a silicone polyurethane polymer.

7. The artemisinin-modified polymer composite according to claim 1 or 2, wherein The artemisinin compound is one of artesunate, dihydroartemisinin or artemether.

8. The artemisinin-modified polymer composite according to claim 1, wherein The silicone polyurea includes polydimethylsiloxane (PDMS), isophorone diisocyanate (IPDI) and hexamethylenediamine (HMDA), wherein the polydimethylsiloxane (PDMS): isophorone diisocyanate (IPDI): hexamethylenediamine (HMDA) is in the ratio of 4 mol: 6 mol: 2 mol, or the polydimethylsiloxane (PDMS): isophorone diisocyanate (IPDI): hexamethylenediamine (HMDA) is in the ratio of 4 mol: 7 mol: 3 mol.

9. A method for preparing the artemisinin-modified polymer composite according to claim 1, characterized by, The organosilicon polyurethane solution modified with an artemisinin compound and the organosilicon polyurea solution are mixed in a mass ratio of 1:1, and then the mixture is rotated and stirred at a speed of 60 to 80 rpm for 5 to 8 minutes. The resulting solution is an artemisinin-modified polymer composite material.

10. Use of a polymer composite based on artemisinin modification according to any one of claims 1 to 8 in marine antifouling coatings.

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