Multifunctional synergistic antifouling degradable polyurethane resin, preparation method therefor and use thereof

Abstract

Disclosed are a multifunctional synergistic antifouling degradable polyurethane resin, a preparation method therefor, and a use thereof. It is prepared from the following components in parts by mass: 20-70 parts of a degradable polyester, 10-60 parts of a diisocyanate, 5-30 parts of a functional small-molecule alcohol, 4-25 parts of a small-molecule alcohol, 5-20 parts of a tertiary amine monomer, 0.1-1 part of a catalyst, and 100-500 parts of a solvent. The present invention introduces a side chain having bactericidal and antifouling functions into a polyurethane material by means of a functional chain extender, thereby effectively enhancing the static antifouling capability of the material. The multifunctional synergistic antifouling controllably degradable polyurethane material has good bactericidal, antifouling and surface self-renewal properties, can ensure the antifouling capability of the material under different conditions, and has excellent mechanical properties and antifouling performance, as well as advantages such as a simple preparation method and convenient application.

Description

A multifunctional, synergistic antifouling biodegradable polyurethane resin, its preparation method and application Technical Field

[0001] This invention relates to the field of marine antifouling materials technology, and in particular to a multifunctional synergistic antifouling biodegradable polyurethane resin, its preparation method, and its application. Background Technology

[0002] The ocean is rich in oil, gas, mineral, and renewable energy resources, making it a treasure trove of resources and a vital area for national security. Building a maritime power has become a crucial national strategy. However, in the course of marine industry and maritime activities, marine engineering equipment and facilities inevitably encounter the problem of marine biofouling. Marine biofouling increases ship drag, reduces speed, increases energy consumption and greenhouse gas emissions; accelerates corrosion of the metal surfaces of marine equipment, reducing structural stability and safety, and shortening service life; clogs the circulation pipelines and filters of nuclear power plants, reducing heat exchange efficiency and affecting the normal operation of energy facilities such as wave power platforms and tidal generators; and clogs the mesh of deep-sea aquaculture cages, hindering the exchange of oxygen and nutrients, reducing aquaculture yields, and causing huge economic losses. However, due to the complexity of the marine environment and the diversity of fouling organisms, marine pollution prevention is extremely challenging and has always been an international problem.

[0003] Currently, the most economical, effective, and simple method to solve the problem of marine biofouling is the use of antifouling materials. However, current antifouling materials often require the use of compound environmentally friendly antifouling agents, resulting in problems such as short antifouling duration, weak static antifouling capability, and insufficient eco-friendliness. Therefore, developing a multifunctional synergistic antifouling material to improve the static antifouling capability and extend the service life of the system is of great significance to national defense, marine resource development, and environmental protection. Summary of the Invention

[0004] The primary objective of this invention is to overcome the shortcomings and deficiencies of the prior art and provide a multifunctional, synergistic, and controllable degradable polyurethane material for stain prevention.

[0005] The second objective of this invention is to provide a method for preparing the above-mentioned multifunctional synergistic antifouling controllable degradable polyurethane material.

[0006] A third objective of this invention is to provide the application of the aforementioned multifunctional, synergistic, and controllable degradable polyurethane material.

[0007] The objective of this invention is achieved through the following technical solution: A multifunctional, synergistic, and controllable degradable polyurethane material, prepared from the following components in parts by weight:

[0008] Further prepared from the following components in parts by mass:

[0009] The biodegradable polyester contains terminal hydroxyl groups and further includes at least one of polylactic acid, polycaprolactone, and poly-3-hydroxybutyrate; and even further includes at least one of polylactic acid and polycaprolactone.

[0010] Furthermore, the molecular weight of the biodegradable polyester is 1×10⁻⁶. 3 ~5×10 3 g / mol, and further to 1×10 3 ~3×10 3 g / mol.

[0011] Further, the diisocyanate includes at least one selected from isophorone diisocyanate (IPDI), toluene diisocyanate (TDI), dicyclohexylmethane diisocyanate (HMDI), diphenylmethane diisocyanate (MDI), and lysine diisocyanate (LDI); and even more specifically, at least one selected from isophorone diisocyanate (IPDI), lysine diisocyanate (LDI), toluene diisocyanate (TDI), and dicyclohexylmethane diisocyanate (HMDI).

[0012] Furthermore, the functional small molecule alcohol is prepared from the following components in parts by mass:

[0013] It is further prepared from the following components in parts by weight:

[0014] Furthermore, the photoinitiator comprises at least one selected from 2,4,6-(trimethylbenzoyl)diphenylphosphine oxide, 2-hydroxy-2-methyl-1-phenyl-1-propanone, benzoin dimethyl ether, benzophenone, and 2-methyl-1-[4-methylthiophenyl]-2-morpholino-1-propanone; and even further, it comprises benzoin dimethyl ether.

[0015] Furthermore, solvent B includes at least one of toluene, tetrahydrofuran, xylene, isopropanol, n-butanol, isobutanol, acetone, butanone, ethyl acetate, and butyl acetate; and even further includes tetrahydrofuran.

[0016] Furthermore, the functional small molecule alcohol is prepared by a mercapto-olefin click reaction, comprising the following steps: mixing 3-mercapto-1,2-propanediol, vinyl chloroacetate, photoinitiator and solvent B, bubbling with an inert gas to remove oxygen contained in the system, and then reacting under ultraviolet light, and obtaining the functional small molecule alcohol after purification and drying.

[0017] Furthermore, the molar ratio of 3-mercapto-1,2-propanediol to vinyl chloroacetate is 1:1.

[0018] Furthermore, the inert gas is introduced for 10 to 30 minutes; even further, it is introduced for 30 minutes.

[0019] Furthermore, the conditions for the reaction under ultraviolet light irradiation are: ultraviolet light wavelength of 245–365 nm and ultraviolet light intensity of 80–100 mW / cm². 2 The reaction time is 20–60 min; further, the ultraviolet light wavelength is 245–365 nm, and the ultraviolet light intensity is 80–100 mW / cm². 2 React for 30 minutes.

[0020] Furthermore, the small molecule alcohol includes at least one of ethylene glycol, 1,4-butanediol, and 1,3-propanediol.

[0021] Further, the tertiary amine monomer is prepared from the following components in parts by mass: 80-160 parts of silane acrylate monomer; 20-40 parts of dimethylamine; and 80-160 parts of solvent C.

[0022] It is further prepared from the following components in parts by weight: 110-160 parts of silane acrylate monomer; 20-26 parts of dimethylamine; and 120-160 parts of solvent C.

[0023] Furthermore, the acrylate silane monomer includes at least one of trimethyl acrylate, triisopropyl acrylate, and tri-n-butyl acrylate; and even further includes triisopropyl acrylate.

[0024] Furthermore, the solvent C comprises tetrahydrofuran.

[0025] Furthermore, the preparation of the tertiary amine monomer includes the following steps: a solution of dimethylamine is slowly added dropwise to a silane acrylate monomer under ice bath conditions, and the addition and reaction are carried out. After the addition is completed, the solution is raised to room temperature and the reaction continues. After the reaction is completed, the product is purified and dried to obtain the tertiary amine monomer product.

[0026] Furthermore, the time for the dropwise addition and reaction is 2 to 5 hours; even further, it is 3 hours.

[0027] Furthermore, the duration of the continued reaction is 12–24 hours; even further, it is 12 hours.

[0028] Furthermore, the catalyst comprises at least one of dibutyltin dilaurate, di-n-octyltin dilaurate, dibutyltin diacetate, stannous octoate, monobutyltin oxide, and dibutyltin maleate; and even more particularly, dibutyltin dilaurate.

[0029] Further, solvent A includes at least one of toluene, tetrahydrofuran, xylene, isopropanol, n-butanol, isobutanol, acetone, butanone, ethyl acetate, butyl acetate, and dimethyl sulfoxide; more preferably, it includes at least one of tetrahydrofuran, ethyl acetate, n-butanol, isobutanol, acetone, and dimethyl sulfoxide.

[0030] The preparation method of the above-mentioned multifunctional synergistic antifouling controllable degradable polyurethane material includes the following steps: (1) Dehydrating the degradable polyester under vacuum conditions to obtain a dehydrated product; adding diisocyanate and solvent A to the dehydrated product under inert gas and stirring conditions to react and obtain a polyurethane prepolymer; (2) Adding functional small molecule alcohol, small molecule alcohol, catalyst and solvent A to the polyurethane prepolymer to react, and after the reaction, precipitating and drying to obtain a controllable degradable polyurethane product; (3) Dissolving the controllable degradable polyurethane product in solvent A, adding tertiary amine monomer to the solution, reacting under an inert gas atmosphere, and after the reaction, purifying and drying to obtain a controllable degradable polyurethane resin.

[0031] Further, the dehydration treatment conditions in step (1) are: dehydration treatment under vacuum at 80-130°C for 1-3 hours; even further, dehydration treatment under vacuum at 110°C for 2 hours.

[0032] Furthermore, the reaction conditions described in step (1) are: stirring at 60-100°C for 3-5 hours; and even further, stirring at 70°C for 2 hours.

[0033] Further, the amount of solvent A added in step (1) is such that the solid content in the reaction system is 20% to 50%.

[0034] Further, solvent A in step (1) includes at least one of tetrahydrofuran, ethyl acetate, n-butanol, isobutanol and acetone.

[0035] Furthermore, the reaction conditions described in step (2) are: stirring at 60-120°C for 1-3 hours; even further, stirring at 80°C for 3 hours.

[0036] Further, the amount of solvent A added in step (2) is such that the solid content in the reaction system is 20% to 50%.

[0037] Further, solvent A in step (2) includes at least one of tetrahydrofuran, ethyl acetate, n-butanol, isobutanol, and acetone.

[0038] Furthermore, the precipitation mentioned in step (2) is precipitated with n-hexane.

[0039] Furthermore, the drying described in step (2) is vacuum drying at 60°C.

[0040] Furthermore, the reaction conditions described in step (3) are: 60-100℃ for 12-24h; even further, 80℃ for 12h.

[0041] Furthermore, the mass fraction of solvent A mentioned in step (3) is 50 to 200 parts; even further, it is 100 parts.

[0042] Furthermore, solvent A in step (3) includes dimethyl sulfoxide.

[0043] Furthermore, the drying described in step (3) is vacuum drying.

[0044] The above-mentioned multifunctional synergistic antifouling controlled biodegradable polyurethane material is used in the preparation of antifouling products.

[0045] Furthermore, the antifouling product includes antifouling coatings.

[0046] The principle of this invention: The multifunctional synergistic antifouling controllable degradable polyurethane material disclosed in this invention is first obtained by polymerizing degradable polyester, diisocyanate, functional small molecule alcohol, and small molecule alcohol to obtain a polyurethane product. Subsequently, a hydrolyzable monomer (as shown in Formula 1) is introduced through a reaction. The side groups of the polyurethane antifouling material are bactericidal quaternary ammonium cationic structures, and can be hydrolyzed under seawater induction to generate zwitterions with antifouling capabilities (as shown in Formula 2), enhancing the antifouling ability of the system. The main chain of the polyurethane antifouling material is a degradable polyester segment, which forms a continuously self-renewing bactericidal-antifouling dynamic surface through main chain degradation in seawater. The polyurethane material, through the combination of bactericidal, antifouling, and surface self-renewal multifunctional antifouling, effectively improves the static antifouling ability of the material and extends the service life of statically operating marine engineering equipment.

[0047] Formula 1.

[0048] Equation 2.

[0049] The aforementioned multifunctional synergy refers to the fact that the material contains a quaternary ammonium cationic structure, which has a killing effect on fouling organisms; on the other hand, the material can be hydrolyzed under seawater induction to generate zwitterions, which can inhibit the adhesion of fouling organisms; furthermore, the polyurethane main chain contains biodegradable segments, which form a continuously self-renewing bactericidal-antifouling dynamic surface through degradation, which can effectively prevent impurities such as oil, sea mud, and inorganic matter in the marine environment from covering the coating surface and causing the antifouling function to fail; the aforementioned multifunctional synergistic antifouling controllable degradable polyurethane material can improve the antifouling ability of the material and extend the service life of the material.

[0050] The multifunctional synergistic antifouling controllable degradable polyurethane material prepared by this invention has excellent mechanical properties, degradation properties, and antifouling properties. The polyester backbone can be degraded into non-toxic small molecules in seawater, demonstrating its environmental friendliness and enabling its wide application in the field of marine antifouling coatings.

[0051] The present invention has the following advantages and effects compared with the prior art: (1) The multifunctional synergistic antifouling controllable degradable polyurethane material disclosed in the present invention utilizes the degradation characteristics of the degradable polyester soft segments in its main chain to achieve the antifouling function, without the need for compound antifouling agents, and the material can be degraded into non-toxic small molecules, with outstanding environmental friendliness.

[0052] (2) The multifunctional synergistic antifouling controllable degradable polyurethane material disclosed in this invention contains a bactericidal quaternary ammonium cationic structure, and can be hydrolyzed under seawater induction to generate zwitterions with antifouling ability. At the same time, the presence of the degradable main chain enables the material to form a self-renewing bactericidal-antifouling dynamic surface, further enhancing the antifouling ability of the system. This polyurethane material has a better static antifouling effect and a longer service life in complex marine environments.

[0053] (3) The multifunctional synergistic antifouling controllable degradable polyurethane material disclosed in this invention has good mechanical properties and can meet the application requirements in marine antifouling coatings.

[0054] (4) The preparation method of the multifunctional synergistic antifouling controllable degradable polyurethane material disclosed in this invention is simple and has a good antifouling effect. This material has broad application prospects in the field of environmentally friendly marine antifouling. Detailed Implementation

[0055] The present invention will be further described in detail below with reference to embodiments, but the implementation of the present invention is not limited thereto. Test methods in the following embodiments that do not specify specific experimental conditions are generally performed under conventional experimental conditions or according to the manufacturer's recommended experimental conditions. Unless otherwise specified, the materials and reagents used are commercially available.

[0056] Example: Preparation of a Multifunctional Synergistic Antifouling Controlled Degradable Polyurethane Material The preparation of a multifunctional synergistic antifouling controlled degradable polyurethane material includes the following steps: S1. Preparation of functional small molecule alcohol: 10.8g of 3-mercapto-1,2-propanediol, 12.0g of vinyl chloroacetate, 0.35g of initiator benzoin dimethyl ether, and 50ml of solvent tetrahydrofuran are mixed. An inert gas is bubbled through the mixture for 30min to remove oxygen from the system. Subsequently, the mixture is cured under ultraviolet light (UV wavelength 350nm, intensity 100mW / cm²) in an ultraviolet curing chamber. 2 The reaction was carried out for 30 minutes, and after purification and drying, a functional small molecule alcohol was obtained. The 3-mercapto-1,2-propanediol and vinyl chloroacetate were added in a molar ratio of 1:1.

[0057] S2. Preparation of tertiary amine monomer: A tetrahydrofuran solution of dimethylamine (0.45 g of dimethylamine and 2.73 g of tetrahydrofuran) was slowly added dropwise to 2.28 g of triisopropylsilane acrylate monomer in an ice bath. The addition was allowed to proceed for 3 hours. After the addition was complete, the reaction solution was brought to room temperature and the reaction continued for 12 hours. After the reaction was completed, the solution was purified and dried to obtain the tertiary amine monomer product. Other silane acrylate monomers and dimethylamine were added in a 1:1 molar ratio.

[0058] S3. Preparation of controllable degradable polyurethane product A: The degradable polyester was vacuum-treated at 110°C for 2 hours to remove moisture, resulting in a dehydrated product. Subsequently, the reaction temperature was lowered to 80°C, and diisocyanate and half the total solvent were added. The mixture was prepolymerized under nitrogen atmosphere and stirring for 2 hours to obtain a polyurethane prepolymer. Then, functional small molecule alcohol, small molecule alcohol, catalyst, and half the total solvent were added. The temperature was controlled at 80±5°C and stirred for 3 hours. After the reaction was completed, the mixture was precipitated with n-hexane and vacuum dried to obtain controllable degradable polyurethane product A.

[0059] S4. Dissolve the product A obtained in step S3 in dimethyl sulfoxide solvent. After complete dissolution, add a tertiary amine monomer in an equimolar ratio with the functional small molecule alcohol. Stir and react at 80°C under a nitrogen atmosphere for 12 hours. After the reaction is completed, purify and dry to obtain the multifunctional synergistic antifouling controllable degradable polyurethane resin material PU.

[0060] Examples 1 to 6 were prepared according to the above-mentioned method for preparing multifunctional synergistic antifouling controllable degradable polyurethane materials. The mass fractions of each component of the raw materials used in step S3 to prepare the polyurethane resin and the mass fractions of each component in step S4 are shown in Table 1. Six kinds of multifunctional synergistic antifouling controllable degradable polyurethane resin materials PU-1 to PU-6 of Examples 1 to 6 were prepared through steps S1 to S4.

[0061] Comparative Example 1: Preparation of polyurethane resin material, including the following steps: Steps S1-S2 are the same as in Examples 1-6; Step S3: Preparation of PU: Degradable polyester is vacuum-treated at 110°C for 2 hours to remove moisture, resulting in a dehydrated product; then the reaction temperature is lowered to 80°C, and diisocyanate and half the total solvent are added. Prepolymerization is carried out under nitrogen atmosphere and stirring for 2 hours to obtain a polyurethane prepolymer; then zwitterionic small molecule alcohol, small molecule alcohol, catalyst dibutyltin dilaurate, and half the total solvent are added. The temperature is controlled at 80±5°C and stirred for 3 hours. After the reaction, the product is precipitated with n-hexane and vacuum dried to obtain a controllable degradable polyurethane product, i.e., polyurethane resin material PU-7. The mass fractions of each component of the raw materials used in step S3 to prepare the polyurethane resin are shown in Table 2.

[0062] The preparation of the zwitterionic small molecule alcohol includes the following steps: 10g of diethanolamine is added to a 100ml three-necked round-bottom flask. Under the conditions of oil bath at 35℃ and N2, 11g of ethyl acrylate is added dropwise to the flask using a constant pressure dropping funnel while stirring. The mixture is stirred overnight to obtain a colorless liquid. Subsequently, a vacuum distillation operation is performed at 60℃ to remove excess ethyl acrylate, thereby obtaining the desired zwitterionic small molecule alcohol.

[0063] Comparative Example 2: Preparation of polyurethane resin material, including the following steps: Steps S1 to S2 are the same as in Examples 1 to 6; Step S3: Preparation of PU: Polytetrahydrofuran was vacuum-treated at 110°C for 2 hours to remove moisture and obtain a dehydrated product; then the reaction temperature was lowered to 80°C, and diisocyanate and half the total solvent were added. Prepolymerization was carried out under nitrogen atmosphere and stirring for 2 hours to obtain a polyurethane prepolymer; then functional small molecule alcohol, small molecule alcohol, catalyst and half the total solvent were added, and the temperature was controlled at 80±5°C and stirred for 3 hours. After the reaction, hexane was used for precipitation and vacuum drying to obtain controllable degradable polyurethane product A.

[0064] S4: The product A obtained in step S3 was completely dissolved in dimethyl sulfoxide solvent. After complete dissolution, a tertiary amine monomer was added in an equimolar ratio with the functional small molecule alcohol. The mixture was stirred and reacted at 80°C under a nitrogen atmosphere for 12 hours. After the reaction was completed, the product was purified and dried to obtain polyurethane resin material PU-8. The mass fraction of each component is shown in Table 2.

[0065] The mass fractions of each component of the raw materials used in step S3 to prepare the polyurethane resin and the mass fractions of each component in step S4 are shown in Table 2.

[0066] Comparative Example 3: Steps S1-S2 are the same as in Examples 1-6; Step S3: Preparation of PU: The biodegradable polyester was vacuum-treated at 110°C for 2 hours to remove moisture, resulting in a dehydrated product; then the reaction temperature was lowered to 80°C, and diisocyanate and half the total solvent were added. Prepolymerization was carried out under nitrogen atmosphere and stirring for 2 hours to obtain a polyurethane prepolymer; then, functional small molecule alcohol, small molecule alcohol, catalyst, and half the total solvent were added, and the reaction was stirred at 80±5°C for 3 hours. After the reaction, the product was precipitated with n-hexane and vacuum dried to obtain a controllable biodegradable polyurethane product, i.e., polyurethane resin material PU-9. The mass fractions of each component of the raw materials used in the preparation of the polyurethane resin in step S3 are shown in Table 2.

[0067] Comparative Example 4: Steps S1-S2 are the same as in Examples 1-6; Step S3: Preparation of PU: Polytetrahydrofuran was vacuum-treated at 110°C for 2 hours to remove moisture, yielding a dehydrated product; then the reaction temperature was lowered to 80°C, and diisocyanate and half the total solvent were added. Prepolymerization was carried out under nitrogen atmosphere and stirring for 2 hours to obtain a polyurethane prepolymer; then, functional small molecule alcohol, small molecule alcohol, catalyst, and half the total solvent were added, and the reaction was stirred at 80±5°C for 3 hours. After the reaction, the product was precipitated with n-hexane and vacuum dried to obtain a controllable degradable polyurethane product, i.e., polyurethane resin material PU-10. The mass fractions of each component of the raw materials used in step S3 to prepare the polyurethane resin are shown in Table 2.

[0068] Comparative Example 5: Steps S1 to S4 were the same as in Examples 1 to 6, resulting in polyurethane resin material PU-11. The mass fractions of each component in the raw materials used to prepare the polyurethane resin in step S3 and the mass fractions of each component in step S4 are shown in Table 2.

[0069] Comparative Example 6: Steps S1 to S4 were the same as in Examples 1 to 6, resulting in polyurethane resin material PU-12. The mass fractions of each component of the raw materials used in step S3 to prepare the polyurethane resin and the mass fractions of each component in step S4 are shown in Table 2.

[0070] Table 1 Table 2 In the performance testing examples, the adhesion of the multifunctional, synergistic antifouling, controllable degradable polyurethane material to the substrate was measured by the pull-out method, referring to GB / T 5210. The test area was a circular region with a diameter of 20 mm, and the pull-out rate was set to 0.2 MPa / s. Five different regions were tested for each sample, and the average value was taken as the test result.

[0071] The antibacterial performance test of the multifunctional synergistic antifouling controlled degradable polyurethane material in the embodiments was conducted in accordance with GB / T 21866-2008.

[0072] In the self-renewal rate test of the multifunctional synergistic antifouling controllable degradable polyurethane material in the embodiment, the self-renewal rate was measured by the mass loss rate of the coating after immersion in ASW for 30 days. The larger the mass loss rate, the faster the self-renewal rate of the material, and vice versa. The self-renewal rate test experimental procedure was based on Pan J, Xie Q, Chiang H, et al. “From the Nature for the Nature”: An Eco-Friendly Antifouling Coating Consisting of Poly(lactic acid)-Based Polyurethane and Natural Antifoulant[J].ACS Sustainable Chemistry & Engineering, 2020, 8(3):1671-1678. The anti-protein performance of the multifunctional synergistic antifouling controllable degradable polyurethane material in the embodiment was evaluated by a quartz crystal balance (QCM-D). The anti-protein effect was evaluated by the frequency change Δf. The greater the decrease in Δf value, the more protein adsorbed, and vice versa. The anti-protein adsorption test procedure was performed according to Ma J, Ma C, Zhang G. Degradable Polymer with Protein Resistance in a Marine Environment[J]. Langmuir, 2015, 31(23):6471-6478. In the examples, the antifouling effect test of the multifunctional synergistic antifouling controllable degradable polyurethane material in the sea was conducted according to GB / T 5370-2007 "Antifouling Paint Sample Shallow Sea Immersion Test Method". The antifouling effect of the material was uniformly evaluated using a percentage-based scoring system. A higher score indicates a better antifouling effect; conversely, a lower score indicates a worse antifouling effect.

[0073] The performance test results of the controllable degradable polyurethane resins PU1-PU6 prepared in Examples 1-6 and the products PU7-PU10 prepared in Comparative Examples 1-4 are shown in Table 3.

[0074] Table 3 The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of the present invention shall be considered equivalent substitutions and shall be included within the protection scope of the present invention.

Claims

1. A multifunctional, synergistic, and controllable biodegradable polyurethane material, characterized in that, Prepared from the following components in parts by mass:

2. The multifunctional synergistic antifouling controlled-degradable polyurethane material according to claim 1, characterized in that, The biodegradable polyester contains terminal hydroxyl groups; The biodegradable polyester has a molecular weight of 1×10⁻⁶. 3 ~5×10 3 g / mol; The diisocyanate includes at least one of isophorone diisocyanate, toluene diisocyanate, dicyclohexylmethane diisocyanate, diphenylmethane diisocyanate, and lysine diisocyanate.

3. The multifunctional synergistic antifouling controlled-degradable polyurethane material according to claim 2, characterized in that, The biodegradable polyester includes at least one of polylactic acid, polycaprolactone, and poly(3-hydroxybutyrate); The biodegradable polyester has a molecular weight of 1×10⁻⁶. 3 ~3×10 3 g / mol; The diisocyanate includes at least one of isophorone diisocyanate, lysine diisocyanate, toluene diisocyanate, and dicyclohexylmethane diisocyanate.

4. The multifunctional synergistic antifouling controlled-degradable polyurethane material according to claim 1, characterized in that, The functional small molecule alcohol is prepared from the following components in parts by mass:

5. The multifunctional synergistic antifouling controlled-degradable polyurethane material according to claim 4, characterized in that, The photoinitiator includes at least one selected from 2,4,6-(trimethylbenzoyl)diphenylphosphine oxide, 2-hydroxy-2-methyl-1-phenyl-1-propanone, benzoin dimethyl ether, benzophenone, and 2-methyl-1-[4-methylthiophenyl]-2-morpholino-1-propanone; The functional small molecule alcohol is prepared via a thiol-alkene click reaction, comprising the following steps: 3-Mercapto-1,2-propanediol, vinyl chloroacetate, photoinitiator and solvent B were mixed and bubbled with an inert gas to remove oxygen in the system. The mixture was then reacted under ultraviolet light and purified and dried to obtain a functional small molecule alcohol. The small molecule alcohols include at least one of ethylene glycol, 1,4-butanediol and 1,3-propanediol.

6. The multifunctional synergistic antifouling controlled-degradable polyurethane material according to claim 1, characterized in that, The tertiary amine monomer is prepared from the following components in parts by mass: 80-160 parts of silane acrylate monomer; 20-40 parts of dimethylamine; Solvent: 80-160 parts.

7. The multifunctional synergistic antifouling controlled-degradable polyurethane material according to claim 6, characterized in that, The silane acrylate monomers include at least one of trimethyl acrylate, triisopropyl acrylate, and tri-n-butyl acrylate; The preparation of the tertiary amine monomer includes the following steps: A solution of dimethylamine was slowly added dropwise to the silane acrylate monomer under ice bath conditions. The addition and reaction were carried out simultaneously. After the addition was completed, the solution was brought to room temperature and the reaction continued. After the reaction was completed, the product was purified and dried to obtain the tertiary amine monomer product.

8. The multifunctional synergistic antifouling controlled-degradable polyurethane material according to claim 1, characterized in that, The catalyst includes at least one of dibutyltin dilaurate, di-n-octyltin dilaurate, dibutyltin diacetate, stannous octoate, monobutyltin oxide, and dibutyltin maleate.

9. A method for preparing the multifunctional synergistic antifouling controlled-degradable polyurethane material according to any one of claims 1 to 8, characterized in that, Includes the following steps: (1) Dehydrate the biodegradable polyester under vacuum conditions to obtain a dehydrated product; add diisocyanate and solvent A to the dehydrated product under inert gas and stirring conditions to react and obtain a polyurethane prepolymer. (2) Add functional small molecule alcohol, small molecule alcohol, catalyst and solvent A to polyurethane prepolymer, react, precipitate and dry after reaction to obtain controllable degradable polyurethane product. (3) Dissolve the controllable degradable polyurethane product in solvent A, add tertiary amine monomer to the solution, react under an inert gas atmosphere, purify and dry after the reaction is completed to obtain controllable degradable polyurethane resin.

10. The application of the multifunctional synergistic antifouling controlled-degradable polyurethane material according to any one of claims 1 to 8 in the preparation of antifouling products.

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