Thiophene polyoxime urethanes, methods of making and using the same

Abstract

The application discloses thiophene polyoxime urethane and a preparation method and application thereof. The thiophene polyoxime urethane has any one of the following structures: wherein n is 10-20, and m is 16364-37821. The thiophene polyoxime urethane has excellent broad-spectrum antibacterial performance, good mechanical properties, water resistance and thermal stability, stable antifouling effect in a water environment, high durability, can effectively avoid the problems of easy migration, easy loss and large environmental burden of the existing antifouling agent, and has simple preparation process, clear synthesis route and strong parameter adjustability. The thiophene polyoxime urethane can be compounded with various matrix resins to prepare antifouling products, has high safety to human bodies and environment, and has wide application prospects in the fields of antifouling coatings and the like.

Description

Technical Field

[0001] This application belongs to the field of antifouling technology, specifically relating to thiophene polyoxime ester, its preparation method and application. Background Technology

[0002] Polyurethane, due to its excellent mechanical properties, corrosion resistance, and good biocompatibility, has been widely used in antifouling coatings, biomedical materials, and marine engineering. However, the functional units introduced into existing polyurethane-based antifouling systems often lack intrinsic antibacterial activity or function solely through physical barrier mechanisms. Under continuous microbial invasion, biofilm accumulation can still occur. Furthermore, some antifouling materials rely on the migration or release of small-molecule antifouling agents to achieve bactericidal effects, which can easily lead to the loss of antifouling components, limited service life, and potential environmental safety hazards. Therefore, how to introduce antifouling functional structures with intrinsic antibacterial capabilities and long-term stable function while maintaining the original comprehensive properties of polyurethane materials, and construct polyurethane materials that combine long-lasting antibiofilm and highly efficient antibacterial properties, has become a pressing technical problem to be solved in this field. Summary of the Invention

[0003] The main purpose of this application is to provide thiophene polyoxime ester, its preparation method and application, in order to overcome the shortcomings of the prior art.

[0004] To achieve the aforementioned objectives, this application employs the following technical solution.

[0005] The first aspect of this application provides a thiophene polyoxime urethane having the structure shown in Formula I, Formula II or Formula III:

[0006]

[0007] Formula I

[0008]

[0009] Formula II

[0010]

[0011] Formula III

[0012] Where n is 10~20 and m is any integer in the range of 16364~37821.

[0013] The second aspect of this application provides a method for preparing the thiophene polyoxime urethane, comprising: reacting a mixed reaction system containing at least a polyisocyanate, a polyol, a thiophene-based antifouling agent and an organic solvent to obtain the thiophene polyoxime urethane;

[0014] The thiophene-based antifouling agent can be selected from 2,5-thiophene dioxime, 2,2-bithiophene-5,5-dioxime, or thiophene[3,2-b]thiophene-2,5-dioxime, with the following structural formulas:

[0015] , , .

[0016] In one embodiment, the molar ratio of polyisocyanate, polyol and thiophene-based antifouling agent is 100:0.01~99.99:0.01~9.99, preferably 100:12.5~25:75~87.5.

[0017] In one embodiment, the reaction temperature is 60~80°C.

[0018] In one embodiment, the reaction time is 2 to 7 hours.

[0019] In one embodiment, the reaction is preferably carried out in a protective atmosphere, such as a nitrogen atmosphere or an inert atmosphere.

[0020] Furthermore, the polyisocyanate includes, but is not limited to, one or more of isophorone diisocyanate, hexamethylene diisocyanate, L-lysine diisocyanate, and 4,4-diisocyanate dicyclohexylmethane.

[0021] Furthermore, the polyol includes, but is not limited to, one or more combinations of polytetrahydrofuran diol, polycaprolactone diol, and ethylene glycol.

[0022] Furthermore, the organic solvent includes, but is not limited to, one or more combinations of N,N-dimethylacetamide, N,N-dimethylformamide, and tetrahydrofuran.

[0023] For example, a mixed reaction system comprising polyisocyanate, polyol, 2,5-thiophene dioxime and organic solvent can be reacted to prepare thiophene polyoxime urethane. The molar ratio of polyisocyanate, polyol and 2,5-thiophene dioxime can be controlled to be 100:0.01~99.99:0.01~9.99, preferably 100:12.5~25:75~87.5; and the reaction temperature is controlled to be 60~80°C and the reaction time to be 2~7 hours.

[0024] For example, a mixed reaction system comprising polyisocyanate, polyol, 2,2-bithiophene-5,5-dioxime and organic solvent can be reacted to prepare thiophene polyoxime urethane. The molar ratio of polyisocyanate, polyol and 2,2-bithiophene-5,5-dioxime can be controlled to be 100:0.01~99.99:0.01~9.99, preferably 100:12.5~25:75~87.5; and the reaction temperature is controlled to be 60~80°C and the reaction time to be 2~7 hours.

[0025] For example, a mixed reaction system comprising polyisocyanate, polyol, thieno[3,2-b]thiophene-2,5-dioxime, and organic solvent can be reacted to prepare thiophene polyoxime urethane. The molar ratio of polyisocyanate, polyol, and thieno[3,2-b]thiophene-2,5-dioxime can be set to 100:0.01~99.99:0.01~9.99, preferably 100:12.5~25:75~87.5; and the reaction temperature is set to 60~80°C, and the reaction time is set to 2~7 h.

[0026] In some more specific implementation schemes, polytetrahydrofuran diol can be stirred for about 1 hour, isophorone diisocyanate can be dissolved in N,N-dimethylacetamide and added and stirred for about 3 hours, and finally 2,5-thiophene dioxime, 2,2-bithiophene-5,5-dioxime, or thiophene[3,2-b]thiophene-2,5-dioxime can be dissolved in N,N-dimethylacetamide and added and stirred for about 3 hours; after the reaction is completed, the organic solvent in the reaction system is dried under vacuum to obtain thiophene polyoxime urethane.

[0027] The third aspect of this application provides a method for preparing an antifouling material, comprising: mixing at least a polyisocyanate, a polyol, a thiophene-based antifouling agent and an organic solvent, followed by a curing treatment to obtain the antifouling material;

[0028] The thiophene-based antifouling agent has any of the following structures:

[0029] , , ;

[0030] The curing temperature is 100~150℃.

[0031] In one embodiment, the molar ratio of polyisocyanate, polyol and thiophene-based antifouling agent is 100:0.01~99.99:0.01~9.99, preferably 100:12.5~25:75~87.5.

[0032] Furthermore, the polyisocyanate includes, but is not limited to, one or more of isophorone diisocyanate, hexamethylene diisocyanate, L-lysine diisocyanate, and 4,4-diisocyanate dicyclohexylmethane.

[0033] Furthermore, the polyol includes, but is not limited to, one or more combinations of polytetrahydrofuran diol, polycaprolactone diol, and ethylene glycol.

[0034] Furthermore, the organic solvent includes, but is not limited to, one or more combinations of N,N-dimethylacetamide, N,N-dimethylformamide, and tetrahydrofuran.

[0035] In one embodiment, the curing process takes 12 to 24 hours.

[0036] The thiophene-based antifouling agent described in this application can be prepared by the following method: subjecting a mixed reaction system containing at least 2,5-thiophene dicarboxaldehyde, 2,2-bithiophene-5,5-dicarboxaldehyde or thiophene[3,2-b]thiophene-2,5-dicarboxaldehyde, hydroxylamine hydrochloride, and sodium acetate to an oxime reaction to obtain the thiophene-based antifouling agent.

[0037] The preferred molar ratio of 2,5-thiophene dicarboxaldehyde, 2,2-bithiophene-5,5-dicarboxaldehyde or thiophene[3,2-b]thiophene-2,5-dicarboxaldehyde, hydroxylamine hydrochloride, and sodium acetate is 1:3~4:3~4.

[0038] The preferred temperature for the oxime reaction is 20-60°C.

[0039] The preferred time for the oxime reaction is 2 to 4 hours.

[0040] Furthermore, 2,5-thiophene dicarboxaldehyde, 2,2-bithiophene-5,5-dicarboxaldehyde or thiophene[3,2-b]thiophene-2,5-dicarboxaldehyde, hydroxylamine hydrochloride, and sodium acetate can be dissolved in water to form the mixed reaction system, and the mixed reaction system can be subjected to the oxime reaction. After the reaction is completed, the water is removed to obtain the thiophene-based antifouling agent.

[0041] More specifically, 2,5-thiophene dicarboxaldehyde, 2,2-bithiophene-5,5-dicarboxaldehyde, or thiophene[3,2-b]thiophene-2,5-dicarboxaldehyde can be placed in deionized water and stirred. Then, hydroxylamine hydrochloride and sodium acetate dissolved in deionized water are added and stirred to carry out an oxime reaction. The reaction temperature is 20~60℃ and the time is 2~6h. After the reaction is completed, the mixture is filtered and washed 3 or more times, and then freeze-dried to remove the solvent to obtain a thiophene-based antifouling agent.

[0042] The preparation process of the thiophene-based antifouling agent is clear, simple to operate, and has mild reaction conditions. The raw materials are widely available and the yield is high. The entire preparation process is safe, environmentally friendly, and cost-controllable, making it suitable for large-scale preparation.

[0043] The fourth aspect of this application provides the use of the thiophene polyoxime ester in the preparation of products with antifouling properties.

[0044] In one embodiment, the product with anti-fouling function is an anti-fouling material, which can take the form of a film, sheet, block, or other forms.

[0045] In one embodiment, the product with antifouling function may include a composite material of the thiophene polyoxime ester with other organic and / or inorganic materials.

[0046] In one embodiment, the product with anti-fouling function includes an anti-fouling coating.

[0047] In one embodiment, the product with anti-fouling function may also be a composite coating structure including the anti-fouling coating and other functional layers. The other functional layers may include, but are not limited to, a primer layer and / or an intermediate bonding layer.

[0048] For example, a method for preparing a coating with antifouling function may include the following steps:

[0049] The coating is prepared by mixing polyisocyanate, polyol, thiophene-based antifouling agent and organic solvent, applying the mixture to the substrate surface, and then curing and crosslinking it at high temperature.

[0050] The preferred molar ratio of polyisocyanate, polyol and thiophene-based antifouling agent is 100:0.01~99.99:0.01~9.99; more preferably 100:12.5~25:75~87.5.

[0051] The curing temperature is preferably 100~150℃, and the curing time is preferably 12~24h.

[0052] The thiophene-based antifouling agent, polyisocyanate, polyol, and organic solvent mentioned herein are the same as those described above and will not be repeated here.

[0053] Compared with the prior art, this application has at least the following beneficial effects:

[0054] (1) In this application, a thiophene oxime compound with an oxime structure as the core (i.e., the aforementioned thiophene antifouling agent) is used as an antifouling functional unit and is introduced into the polyurethane main chain through covalent means. The resulting thiophene polyoxime urethane has high thermal stability during preparation and use, is not easy to decompose or migrate, and can maintain good mechanical properties while having long-lasting and stable intrinsic antibacterial properties.

[0055] (2) The thiophene polyoxime ester or the coating material formed therefrom of this application has excellent contact antibacterial properties, exhibits broad-spectrum inhibition and killing effects on a variety of common bacteria, and has good overall mechanical properties. It is safe and reliable to use, has no obvious odor, and has low harm and pollution to the human body and the environment.

[0056] (3) The preparation process of the thiophene polyoxime ester or its coating material of this application is simple and controllable, the parameters are highly adjustable, the process stability is high, and it is easy to realize continuous and large-scale production, which is very suitable for industrial applications.

[0057] (4) The thiophene polyoxime urethane product of this application achieves long-term stable antibacterial effect through the material surface contact mechanism. Its antibacterial performance does not depend on the migration or release of antifouling components. The effective action time is basically consistent with the service life of the material, and it has good durability. Attached Figure Description

[0058] Figure 1 This is the 1H NMR spectrum of 2,5-thiophene dioxime in the embodiments of this application;

[0059] Figure 2 This is the 1H NMR spectrum of 2,2-bithiophene-5,5-dioxime in the embodiments of this application;

[0060] Figure 3 This is the 1H NMR spectrum of thiopheno[3,2-b]thiophene-2,5-dioxime in the embodiments of this application;

[0061] Figure 4 These are the 1H NMR spectra of products 4, 5, and 6 in the embodiments of this application;

[0062] Figure 5 These are the Fourier transform infrared spectra of products 4, 5, and 6 in the embodiments of this application. Detailed Implementation

[0063] To address the aforementioned deficiencies of existing technologies, this application introduces antifouling active thiophene oxime compounds (such as 2,5-thiophene dioxime, 2,2-bithiophene-5,5-dioxime, or thiophene[3,2-b]thiophene-2,5-dioxime, etc.) into the polyurethane backbone, thereby fixing the antifouling functional groups in the internal structure of the polymer material through covalent bonds, thus endowing the formed thiophene polyoxime urethane with durable and stable antifouling properties. Simultaneously, the thiophene polyoxime urethane also possesses excellent broad-spectrum antibacterial properties, as well as good mechanical properties, water resistance, and thermal stability. Especially in aquatic environments, it exhibits stable antifouling effects and high durability, effectively overcoming the shortcomings of existing antifouling agents such as easy migration, easy runoff, and high environmental burden. It can be compounded with various matrix resins to prepare antifouling products that are safe, reliable, odorless, and have low harm and pollution levels to human health and the environment, showing broad application prospects in the field of antifouling coatings. Furthermore, the preparation process of the thiophene polyoxime ester is simple, the synthesis route is clear, and the parameters are highly adjustable, making it suitable for large-scale production.

[0064] The technical solution of this application will be clearly and completely described below with reference to several embodiments. Obviously, the described embodiments are only some embodiments of this application, not all embodiments. Based on the embodiments of this application, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this application.

[0065] Unless otherwise specified, the experimental materials used in the examples below can be purchased from conventional biochemical reagent companies.

[0066] Example 1: Synthesis of Thiophene-based Antifouling Agent

[0067] 25 mmol / L of 2,5-thiophene dioxaldehyde was placed in 500 mL of deionized water and stirred. Then, 100 mmol / L of hydroxylamine hydrochloride and 100 mmol / L of sodium acetate were dissolved in 500 mL of deionized water and added to the solution, stirring for about 4 hours. The oxime reaction was controlled at a temperature of about 40°C and a time of about 3 hours. After the reaction was completed, the product was washed three times with deionized water and then freeze-dried to remove the solvent. The obtained solid was the target product, 2,5-thiophene dioxime (TDOX). Its 1H NMR spectrum (solvent: deuterated DMSO) is shown below. Figure 1 As shown.

[0068] 25 mmol / L of 2,2-bithiophene-5,5-dicarboxaldehyde was placed in 500 mL of deionized water and stirred. Then, 100 mmol / L of hydroxylamine hydrochloride and 100 mmol / L of sodium acetate were dissolved in 500 mL of deionized water and added to the solution, stirring for about 4 hours. The oxime reaction was controlled at a temperature of about 40°C and a time of about 3 hours. After the reaction was completed, the product was filtered and washed three times with deionized water, and then freeze-dried to remove the solvent. The obtained solid was the target product 2,2-bithiophene-5,5-dioxime (BTPDOX). Its 1H NMR spectrum (solvent: deuterated DMSO) is shown below. Figure 2 As shown.

[0069] 25 mmol / L of thieno[3,2-b]thiophene-2,5-dicarboxaldehyde was placed in 500 mL of deionized water and stirred. Then, 100 mmol / L of hydroxylamine hydrochloride and 100 mmol / L of sodium acetate were dissolved in 500 mL of deionized water and added to the solution, stirring for about 4 hours. The oxime reaction was controlled at a temperature of about 40°C and a time of about 3 hours. After the reaction was completed, the product was filtered and washed three times with deionized water, and then freeze-dried to remove the solvent. The obtained solid was the target product, thieno[3,2-b]thiophene-2,5-dioxime (TTDOX), and its 1H NMR spectrum is shown below. Figure 3 As shown.

[0070] Example 2 Synthesis of thiophene polyoxime ester

[0071] Polytetrahydrofuran diol was stirred for about 1 hour. Isophorone diisocyanate was dissolved in 30 mL of N,N-dimethylacetamide and added to the mixture, stirring for about 3 hours. Finally, 2,5-thiophene dioxime, 2,2-bithiophene-5,5-dioxime, or thiophene[3,2-b]thiophene-2,5-dioxime were dissolved in 30 mL of N,N-dimethylacetamide and added to the mixture, stirring for about 3 hours. After the reaction was completed, the organic solvent in the reaction system was removed by vacuum drying to obtain various thiophene polyoxime urethane products, named products 1 to 9. The amounts of polyisocyanate, polyol, and thiophene-based antifouling agent and the corresponding reaction conditions for each product are shown in Table 1, with the unit of amount being mmol / L. The 1H NMR spectrum (solvent: deuterated trifluoroacetic acid) and Fourier transform infrared spectrum of products 4, 5, and 6, i.e., the polyoxime urethanes with structures shown in formulas 1, 2, and 3, are shown in Table 1. Figure 4 , Figure 5 As shown. The molecular weights of products 4, 5, and 6 are 26284, 28293, and 27394, respectively.

[0072] Table 1. Types and amounts of raw materials used for thiophene polyoxime ester products 1-9 in Example 2.

[0073] Comparative Example 1

[0074] The synthesis method of the thiophene polyoxime urethane provided in this comparative example is basically the same as that of product 1, except that 2,3-dioxime-thiophene is used instead of 2,5-thiophene dioxime. The product obtained in this comparative example is named product 10.

[0075] Comparative Example 2

[0076] The synthesis method of the furan polyoxime urethane provided in this comparative example is basically the same as that of Product 1, except that 2,5-thiophene dioxime is replaced with 2,5-furandicarboxaldehyde oxime. The product obtained in this comparative example is named Product 11.

[0077] Comparative Example 3

[0078] The method for synthesizing polyurethane provided in this comparative example is basically the same as the method for synthesizing product 1, except that 2,5-thiophene dioxime is omitted. The product obtained in this comparative example is named product 12.

[0079] The antibacterial properties of products 1 to 12 were tested according to the method of GB / T 21866-2008, and the mechanical properties, thermal stability, glass transition temperature, odor, etc. of products 1 to 12 were tested according to the method of literature 1 (ACS Nano, 2025, 19 (37), 33346-33360). The results are shown in Table 2.

[0080] According to the neutral salt spray test (NSS) method in GB / T 10125-2021 "Civilization test of artificial atmosphere - Salt spray test", thiophene polyoxime ester products 1 to 12 were sprayed onto carbon steel plates (Q235) and the film thickness was controlled at 80±2μm. Salt spray tests were conducted on these coatings, and the results are shown in Table 2.

[0081] According to reference 2 (Chem. Eng. J., 2026, 531, 173640), thiophene polyoxime ester products 1 to 12 were sprayed onto carbon steel plates (Q235) to prepare multiple antifouling test plates. The multiple antifouling test plates were subjected to static hanging tests in the Meishan sea area of ​​Ningbo (East China Sea), and the antifouling effect was observed after 90 days.

[0082] Table 2 Performance test results of thiophene polyoxime ester products 1-12 in Example 2 ;

[0083] Note: The data shown in the table above are the average values ​​after testing multiple samples.

[0084] Example 3

[0085] The polyol was stirred for about 1 hour in a nitrogen atmosphere. The polyisocyanate was dissolved in an organic solvent and added, then stirred for about 3 hours. Finally, the thiophene-based antifouling agent was dissolved in an organic solvent and added, then stirred for about 3 hours. The resulting mixture was then uniformly coated onto the surface of a stainless steel substrate and cured to form multiple coatings, named Coating 1 to Coating 9. The amounts of polyisocyanate, polyol, and thiophene-based antifouling agent used in each coating, along with the corresponding curing conditions, are shown in Table 3 (unit: mmol / L). The organic solvent used to prepare Coatings 1, 5-9 was N,N-dimethylacetamide, and the organic solvents used to prepare Coatings 2-4 were N,N-dimethylformamide, anhydrous ethanol, and tetrahydrofuran, respectively. The nuclear magnetic resonance (NMR) spectra (using deuterated trifluoroacetic acid as solvent) and Fourier transform infrared (FTIR) spectra of Coatings 1, 5, and 9 were compared with those of Coatings 9. Figure 4 , Figure 5 The spectra shown are similar. The molecular weights of the polymers constituting coatings 1, 5, and 9 were determined to be 24281, 27274, and 25836, respectively.

[0086] Table 3. Raw material types, amounts, and reaction conditions for coatings 1 to 9 in Example 3.

[0087] Comparative Example 3

[0088] The coating preparation method provided in this comparative example is basically the same as that of coating 1, except that 2,5-thiophene dioxime is replaced with 2,3-dioxime-thiophene. The coating obtained in this comparative example is named coating 10.

[0089] Comparative Example 4

[0090] The coating preparation method provided in this comparative example is basically the same as that of coating 1, except that 2,5-thiophene dioxime is replaced with 2,5-furandicarboxaldehyde oxime. The coating obtained in this comparative example is named coating 11.

[0091] Comparative Example 5

[0092] The coating preparation method provided in this comparative example is basically the same as that of coating 1, except that 2,5-thiophene dioxime is omitted. The coating obtained in this comparative example is named coating 12.

[0093] The antibacterial properties of coatings 1 to 12 were tested according to the method of GB / T 21866-2008, and the mechanical properties, thermal stability, substrate adhesion, and antifouling effect in water of coatings 1 to 12 were tested according to the method of reference 2 (Chem. Eng. J., 2026, 531, 173640). The results are shown in Table 4.

[0094] According to the neutral salt spray test (NSS) method in GB / T 10125-2021 "Artificial Atmosphere Corrosion Test - Salt Spray Test", coatings 1 to 12 were formed on carbon steel plate (Q235) respectively, and the film thickness was controlled at 80±2μm. Salt spray tests were carried out on these coatings, and the results are shown in Table 4.

[0095] According to reference 2 (Chem. Eng. J., 2026, 531, 173640), coatings 1 to 12 were formed on carbon steel plate (Q235), and multiple antifouling test plates were subjected to static hanging tests in the Meishan sea area of ​​Ningbo (East China Sea). The antifouling effect was observed after 90 days.

[0096] Table 4 Performance test results of coatings 1 to 12 in Example 3 ;

[0097] Note: The data shown in the table above are the average values ​​after testing multiple samples.

[0098] It should be understood that the technical solution of this application is not limited to the specific implementation examples mentioned above. Any technical modifications made to the technical solution of this application without departing from the spirit and scope of protection of the claims shall fall within the scope of protection of this application.

Claims

1. Thiophene polyoxime urethane, characterized in that, The thiophene polyoxime ester has the structure shown in Formula I, Formula II or Formula III: ； Formula I; ； Formula II; ； Formula III; Where n is 10~20 and m is 16364~37821.

2. The method for preparing thiophene polyoxime urethane according to claim 1, characterized in that, include: Thiophene polyoxime ester is prepared by reacting a mixed reaction system containing at least polyisocyanate, polyol, thiophene antifouling agent and organic solvent. The thiophene-based antifouling agent has any of the following structures: 、 、 。 3. The preparation method according to claim 2, characterized in that: The molar ratio of polyisocyanate, polyol and thiophene-based antifouling agent is 100:0.01~99.99:0.01~9.99; and / or, the reaction temperature is 60~80℃ and the time is 2~7h; and / or, the reaction is carried out in a protective atmosphere.

4. The preparation method according to claim 3, characterized in that: The molar ratio of polyisocyanate, polyol and thiophene antifouling agent is 100:12.5~25:75~87.

5.

5. The preparation method according to any one of claims 2-4, characterized in that: The polyisocyanate includes one or more combinations of isophorone diisocyanate, hexamethylene diisocyanate, L-lysine diisocyanate, and 4,4-diisocyanate dicyclohexylmethane.

6. The preparation method according to any one of claims 2-4, characterized in that: The polyols include one or more combinations of polytetrahydrofuran diol, polycaprolactone diol, and ethylene glycol.

7. The preparation method according to any one of claims 2-4, characterized in that: The organic solvent includes one or more combinations of N,N-dimethylacetamide, N,N-dimethylformamide, and tetrahydrofuran.

8. A method for preparing an antifouling material, characterized in that, include: The antifouling material is prepared by mixing at least a polyisocyanate, a polyol, a thiophene-based antifouling agent, and an organic solvent, followed by a curing process. The thiophene-based antifouling agent has any of the following structures: 、 、 ； The curing temperature is 100~150℃.

9. The preparation method according to claim 8, characterized in that: The molar ratio of polyisocyanate, polyol and thiophene-based antifouling agent is 100:0.01~99.99:0.01~9.99; And / or, the polyisocyanate includes one or more combinations of isophorone diisocyanate, hexamethylene diisocyanate, L-lysine diisocyanate, and 4,4-diisocyanate dicyclohexylmethane; And / or, the polyol includes one or more combinations of polytetrahydrofuran diol, polycaprolactone diol, and ethylene glycol; And / or, the organic solvent includes one or more combinations of N,N-dimethylacetamide, N,N-dimethylformamide, and tetrahydrofuran; And / or, the curing time is 12~24h.

10. The preparation method according to claim 9, characterized in that: The molar ratio of polyisocyanate, polyol and thiophene antifouling agent is 100:12.5~25:75~87.

5.

11. Use of the thiophene polyoxime ester of claim 1 in the preparation of a product with antifouling function.

12. The use according to claim 11, characterized in that: The products with anti-fouling function include anti-fouling coatings.

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