Multifunctional synergistic antifouling degradable polyurethane resin as well as preparation method and application thereof

Abstract

The invention discloses multifunctional synergistic antifouling degradable polyurethane resin as well as a preparation method and application thereof. The degradable polyurethane resin is prepared from the following components in parts by mass: 20 to 70 parts of degradable polyester, 10 to 60 parts of diisocyanate, 5 to 30 parts of functional small molecular alcohol, 4 to 25 parts of small molecular alcohol, 5 to 20 parts of tertiary amine monomer, 0.1 to 1 part of catalyst and 100 to 500 parts of solvent. A side chain with sterilization and anti-fouling functions is introduced into the polyurethane material through the functional chain extender, and the static anti-fouling capacity of the material can be effectively improved. The multifunctional synergic anti-fouling controllable degradation polyurethane material has good sterilization, anti-fouling and surface self-renewal performance, the anti-fouling capacity of the material can be guaranteed under different conditions, and the multifunctional synergic anti-fouling controllable degradation polyurethane material has excellent mechanical performance and anti-fouling performance and has the advantages of being simple in preparation method, convenient to construct and the like.

Description

Technical Field

[0001] The invention relates to the technical field of marine antifouling materials, and in particular to a multifunctional synergistic antifouling degradable polyurethane resin and a preparation method and application thereof. Background Art

[0002] In the process of marine industry and maritime activities, marine engineering equipment and facilities will inevitably encounter the problem of marine biofouling, which will increase the resistance of ships, reduce the speed, increase energy consumption and greenhouse gas emissions; accelerate the corrosion of the metal surface of marine equipment, reduce the stability and safety of the structure, and shorten the service life; block the circulation pipelines and filters of nuclear power plants, reduce the efficiency of heat exchange, and affect the normal operation of energy facilities such as wave power generation platforms and tidal generators; and block the mesh of deep-sea aquaculture cages, hinder the exchange of oxygen and nutrients, and reduce aquaculture production, thereby causing huge economic losses. However, due to the complexity of the marine environment and the diversity of fouling organisms, marine anti-fouling is extremely challenging and has always been an international problem.

[0003] At present, the most economical, effective and simple way to solve the problem of marine biofouling is to use antifouling materials. However, current antifouling materials often need to be compounded with environmentally friendly antifouling agents, which have problems such as short antifouling period, weak static antifouling ability, and insufficient eco-friendliness. Therefore, developing a multifunctional synergistic antifouling material to improve the static antifouling ability of the system and extend its service life is of great significance to national defense construction, marine resource development and environmental protection. Summary of the invention

[0004] The primary purpose of the present invention is to overcome the shortcomings and deficiencies of the prior art and to provide a multifunctional synergistic antifouling controllably degradable polyurethane material.

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

[0006] The third object of the present invention is to provide the application of the above-mentioned multifunctional synergistic antifouling controllably degradable polyurethane material.

[0007] The purpose of the present invention is achieved through the following technical solutions: A multifunctional synergistic antifouling controllably degradable polyurethane material is prepared from the following components in parts by weight: 20-70 parts of biodegradable polyester; 10-60 parts of diisocyanate; 5-30 parts of functional small molecule alcohol; 4-25 parts of small molecule alcohol; 5-20 parts of tertiary amine monomer; Catalyst 0.1-1 part; Solvent A 100-500 parts.

[0008] Further prepared from the following components in parts by weight: 30-50 parts of biodegradable polyester; 30-50 parts of diisocyanate; 5-16 parts of functional small molecule alcohol; 4-15 parts of small molecule alcohol; 5-20 parts of tertiary amine monomer; Catalyst 0.1-0.3 parts; Solvent A 100-300 parts.

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

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

[0011] Further, the diisocyanate includes at least one of isophorone diisocyanate (IPDI), toluene diisocyanate (TDI), dicyclohexylmethane diisocyanate (HMDI), diphenylmethane diisocyanate (MDI) and lysine diisocyanate (LDI); further includes at least one of 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 weight: 20 to 50 parts of 3-mercapto-1,2-propylene glycol; 25-50 parts of vinyl chloroacetate; Photoinitiator 0.5-2 parts; Solvent B 80-200 parts.

[0013] Further prepared from the following components in parts by weight: 30-40 parts of 3-mercapto-1,2-propylene glycol; 35-45 parts of vinyl chloroacetate; 0.5-1.5 parts of photoinitiator; Solvent B 100-200 parts.

[0014] Furthermore, the photoinitiator includes at least one of 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-morpholinyl-1-propanone; and further includes benzoin dimethyl ether.

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

[0016] Furthermore, the functional small molecule alcohol is prepared by a thiol-ene click reaction, comprising the following steps: 3-Mercapto-1,2-propylene glycol, vinyl chloroacetate, a photoinitiator and a solvent B are mixed, an inert gas is bubbled in to remove oxygen in the system, and then the mixture is reacted under ultraviolet light, and a functional small molecule alcohol is obtained after purification and drying.

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

[0018] Furthermore, the introducing of the inert gas is for 10 to 30 minutes; further, the introducing of the inert gas is for 30 minutes.

[0019] Furthermore, the reaction conditions under ultraviolet light are: the ultraviolet light wavelength is 245-365nm, and the ultraviolet light intensity is 80-100mW / cm 2 , react for 20 to 60 minutes; further, the wavelength of ultraviolet light is 245 to 365 nm, and the intensity of ultraviolet light is 80 to 100 mW / cm 2 , react for 30 minutes.

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

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

[0022] Further prepared from the following components in parts by weight: 110-160 parts of silane acrylate monomer; 20-26 parts of dimethylamine; Solvent C 120-160 parts.

[0023] Furthermore, the acrylic silane monomer includes at least one of trimethylsilyl acrylate, triisopropylsilyl acrylate, and tri-n-butylsilyl acrylate; and further includes triisopropylsilyl acrylate.

[0024] Furthermore, the solvent C comprises tetrahydrofuran.

[0025] Furthermore, the preparation of the tertiary amine monomer comprises the following steps: In an ice bath, a dimethylamine solution is slowly added dropwise to the acrylic silane ester monomer, and the addition is allowed to react. After the addition is completed, the solution is heated to room temperature and the reaction is continued. After the reaction is completed, the solution is purified and dried to obtain a tertiary amine monomer product.

[0026] Furthermore, the time of adding and reacting is 2 to 5 hours; further preferably, it is 3 hours.

[0027] Furthermore, the continued reaction time is 12 to 24 hours; furthermore, 12 hours.

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

[0029] Furthermore, the solvent A comprises at least one of toluene, tetrahydrofuran, xylene, isopropanol, n-butanol, isobutanol, acetone, butanone, ethyl acetate, butyl acetate and dimethyl sulfoxide; more preferably comprises 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 controllably degradable polyurethane material comprises the following steps: (1) dehydrating the biodegradable 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 for reaction, and after the reaction is completed, precipitating and drying to obtain a controllably degradable polyurethane product; (3) The controllably degradable polyurethane product is dissolved in solvent A, a tertiary amine monomer is added to the solution, and the mixture is reacted under an inert gas atmosphere. After the reaction is completed, the mixture is purified and dried to obtain a controllably degradable polyurethane resin.

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

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

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

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

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

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

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

[0038] Furthermore, the precipitation in step (2) is performed using n-hexane.

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

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

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

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

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

[0044] The application of the above-mentioned multifunctional synergistic antifouling controllably degradable polyurethane material in the preparation of antifouling products.

[0045] Furthermore, the antifouling product includes an antifouling coating.

[0046] Principle of the present invention: The multifunctional synergistic antifouling controllably degradable polyurethane material disclosed in the present invention first obtains a polyurethane product by polymerizing a degradable polyester, a diisocyanate, a functional small molecule alcohol and a small molecule alcohol, and then introduces a hydrolyzable monomer (as shown in Formula 1) through reaction. The side group of the polyurethane antifouling material is a bactericidal quaternary ammonium cationic structure, and can be hydrolyzed under the induction of seawater to generate zwitterions with antifouling ability (as shown in Formula 2), thereby 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 the degradation of the main chain in seawater. The polyurethane material combines the multifunctional antifouling of bactericidal, antifouling and surface self-renewal, effectively improving the static antifouling ability of the material and extending the service life of static marine engineering equipment.

[0047] Formula 1.

[0048] Formula 2.

[0049] The multifunctional synergy means that on the one hand, 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 to generate zwitterions under the induction of seawater, which can inhibit the adhesion of fouling organisms; further, the polyurethane main chain contains degradable segments, which form a continuously self-renewing bactericidal and anti-fouling 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, resulting in the failure of the anti-fouling function; the multifunctional synergistic anti-fouling controllably degradable polyurethane material can improve the material's anti-fouling ability and extend the material's service life.

[0050] The multifunctional synergistic antifouling controllably degradable polyurethane material prepared by the present invention has excellent mechanical properties, degradation properties, and antifouling properties. The polyester main chain can be degraded into non-toxic small molecules in seawater, reflecting its environmental friendliness, and can be widely used in the field of marine antifouling coatings.

[0051] Compared with the prior art, the present invention has the following advantages and effects: (1) The multifunctional synergistic antifouling controllably degradable polyurethane material disclosed in the present invention utilizes the degradation characteristics of the degradable polyester soft segment in its main chain to achieve the antifouling function. No antifouling agent is required, and the material can be degraded into non-toxic small molecules, thus being environmentally friendly.

[0052] (2) The multifunctional synergistic antifouling controllably degradable polyurethane material disclosed in the present invention contains a bactericidal quaternary ammonium cationic structure and can be hydrolyzed to generate zwitterions with antifouling ability under the induction of seawater. 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. The polyurethane material has a more excellent static antifouling effect and a longer service life in a complex marine environment.

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

[0054] (4) The multifunctional synergistic antifouling controllably degradable polyurethane material disclosed in the present invention has a simple preparation method and good antifouling effect. The material has broad application prospects in the field of environmentally friendly marine antifouling. DETAILED DESCRIPTION

[0055] The present invention is further described in detail below in conjunction with the examples, but the embodiments of the present invention are not limited thereto. The experimental methods in the following examples where specific experimental conditions are not specified are usually carried out under conventional experimental conditions or according to the experimental conditions recommended by the manufacturer. The materials, reagents, etc. used, unless otherwise specified, can all be obtained commercially.

[0056] Example Preparation of multifunctional synergistic antifouling controllably degradable polyurethane material The preparation of a multifunctional synergistic antifouling controllable degradable polyurethane material comprises the following steps: S1. Preparation of functional small molecule alcohol: 10.8 g of 3-mercapto-1,2-propylene glycol, 12.0 g of vinyl chloroacetate, 0.35 g of initiator benzoin dimethyl ether and 50 ml of solvent tetrahydrofuran were mixed, and inert gas was bubbled for 30 min to remove oxygen in the system. Then, the system was cured in a UV curing box under UV light conditions (UV wavelength of 350 nm, intensity of 100 mW / cm 2 ) and reacted for 30 minutes, and after purification and drying, a functional small molecule alcohol was obtained. The feed ratio of 3-mercapto-1,2-propylene glycol and vinyl chloroacetate was 1:1.

[0057] S2. Preparation of tertiary amine monomer: Slowly drop a tetrahydrofuran solution of dimethylamine (wherein the content of dimethylamine is 0.45g; the content of tetrahydrofuran is 2.73g) into 2.28g of triisopropylsilyl acrylate monomer under an ice bath, dropwise and react for 3h. After the dropwise addition is completed, the reaction solution is heated to room temperature and the reaction is continued for 12h. After the reaction is completed, the product of tertiary amine monomer is purified and dried to obtain the product. Other silyl acrylate monomers and dimethylamine are added at a molar ratio of 1:1.

[0058] S3. Preparation of controllable degradable polyurethane product A: evacuate the degradable polyester under vacuum conditions at 110°C for 2 hours to remove moisture and obtain a dehydrated product; then reduce the reaction temperature to 80°C, add diisocyanate and half of the total solvent, prepolymerize for 2 hours under nitrogen atmosphere and stirring conditions to obtain a polyurethane prepolymer; then add functional small molecule alcohol, small molecule alcohol, catalyst and half of the total solvent, control the temperature at 80±5°C and stir the reaction for 3 hours, and after the reaction is completed, precipitate with n-hexane and dry in vacuum to obtain a controllable degradable polyurethane product A.

[0059] S4. Dissolve the entire amount of product A obtained in step S3 in dimethyl sulfoxide solvent, add a tertiary amine monomer in an equal molar ratio to the functional small molecule alcohol after it is fully dissolved, and stir the reaction at 80°C under a nitrogen atmosphere for 12 hours. After the reaction is completed, purify and dry to obtain a multifunctional synergistic anti-fouling controllably degradable polyurethane resin material PU.

[0060] Examples 1 to 6 are all prepared according to the above-mentioned method for preparing the multifunctional synergistic antifouling controllably degradable polyurethane material, wherein the mass fractions of each component of 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 1; six multifunctional synergistic antifouling controllably degradable polyurethane resin materials PU-1 to PU-6 of Examples 1 to 6 are prepared through steps S1 to S4.

[0061] Comparative Example 1 The preparation of the polyurethane resin material comprises the following steps: Steps S1 to S2 are the same as in Examples 1 to 6; Step S3: Preparation of PU: Vacuum the degradable polyester under vacuum conditions at 110°C for 2h to remove moisture and obtain a dehydrated product; then reduce the reaction temperature to 80°C, add diisocyanate and half of the total amount of solvent, prepolymerize for 2h under nitrogen atmosphere and stirring conditions to obtain a polyurethane prepolymer; then add zwitterionic small molecule alcohol, small molecule alcohol, catalyst dibutyltin dilaurate and half of the total amount of solvent, control the temperature at 80±5°C and stir for 3h, precipitate with n-hexane after the reaction, and vacuum dry to obtain a controllable degradable polyurethane product, that is, obtain a polyurethane resin material PU-7. The mass fractions of each component of the raw materials used to prepare the polyurethane resin in step S3 are shown in Table 2.

[0062] The preparation of the zwitterionic small molecule alcohol comprises the following steps: Add 10 g of diethanolamine into a 100 ml three-necked round-bottom flask. In an oil bath at 35°C and N2, use a constant pressure dropping funnel to drop 11 g of ethyl acrylate into the flask drop by drop while stirring. Stir overnight to obtain a colorless liquid. Then, perform reduced pressure distillation at 60°C to remove excess ethyl acrylate to obtain the desired zwitterionic small molecule alcohol.

[0063] Comparative Example 2 The preparation of the polyurethane resin material comprises the following steps: Steps S1 to S2 are the same as in Examples 1 to 6; Step S3: Preparation of PU: Evacuate polytetrahydrofuran under vacuum conditions at 110°C for 2 hours to remove moisture and obtain a dehydrated product; then reduce the reaction temperature to 80°C, add diisocyanate and half of the total amount of solvent, and prepolymerize for 2 hours under nitrogen atmosphere and stirring to obtain a polyurethane prepolymer; then add functional small molecule alcohol, small molecule alcohol, catalyst and half of the total amount of solvent, control the temperature at 80±5°C and stir the reaction for 3 hours, and after the reaction is completed, precipitate with n-hexane and vacuum dry to obtain a controllable degradable polyurethane product A.

[0064] S4: The product A obtained in step S3 is dissolved in dimethyl sulfoxide solvent, and after fully dissolved, a tertiary amine monomer is added in an equal molar ratio to the functional small molecule alcohol, and stirred for reaction at 80°C under a nitrogen atmosphere for 12 hours. After the reaction is completed, the polyurethane resin material PU-8 is obtained by purification and drying. The mass fractions of the components are shown in Table 2.

[0065] The mass fractions of each component of 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.

[0066] Comparative Example 3 Steps S1 to S2 are the same as in Examples 1 to 6; Step S3: Preparation of PU: Vacuum the degradable polyester under vacuum conditions at 110°C for 2h to remove moisture and obtain a dehydrated product; then reduce the reaction temperature to 80°C, add diisocyanate and half of the total solvent, prepolymerize for 2h under nitrogen atmosphere and stirring conditions to obtain a polyurethane prepolymer; then add functional small molecule alcohol, small molecule alcohol, catalyst and half of the total solvent, control the temperature at 80±5°C and stir for 3h, precipitate with n-hexane after the reaction, and vacuum dry to obtain a controllable degradable polyurethane product, that is, obtain a polyurethane resin material PU-9. The mass fractions of each component of the raw materials used to prepare the polyurethane resin in step S3 are shown in Table 2.

[0067] Comparative Example 4 Steps S1 to S2 are the same as in Examples 1 to 6; Step S3: Preparation of PU: Polytetrahydrofuran is evacuated under vacuum conditions at 110°C for 2h to remove moisture and obtain a dehydrated product; then the reaction temperature is lowered to 80°C, diisocyanate and half of the total amount of solvent are added, and prepolymerization is carried out for 2h under nitrogen atmosphere and stirring to obtain a polyurethane prepolymer; then functional small molecule alcohol, small molecule alcohol, catalyst and half of the total amount of solvent are added, and the temperature is controlled at 80±5°C and stirred for 3h. After the reaction is completed, n-hexane is used for precipitation and vacuum drying to obtain a controllable degradation polyurethane product, that is, a polyurethane resin material PU-10. The mass fractions of each component of the raw materials used to prepare the polyurethane resin in step S3 are shown in Table 2.

[0068] Comparative Example 5 Steps S1 to S4 are the same as in Examples 1 to 6, to obtain polyurethane resin material PU-11. The mass fractions of each component of the raw material 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 are the same as in Examples 1 to 6, to obtain polyurethane resin material PU-12. The mass fractions of each component of the raw material used to prepare the polyurethane resin in step S3 and the mass fractions of each component in step S4 are shown in Table 2.

[0070] Table 1 Table 2 Performance Testing The adhesion of the multifunctional synergistic antifouling controllably degradable polyurethane material to the substrate in the embodiment is measured by a pull-out method, referring to GB / T 5210, the test area is a circular area with a diameter of 20 mm, and the pull-out rate is set to 0.2 MPa / s. Five different areas are tested for each sample, and the average value is taken as the test result.

[0071] The antibacterial performance test of the multifunctional synergistic antifouling controllably degradable polyurethane material in the embodiment refers to GB / T21866-2008.

[0072] In the self-renewal rate test of the multifunctional antifouling controllable degradable polyurethane material in the embodiment, the mass loss rate of the coating after immersion in ASW for 30 days is used to measure its self-renewal rate. The greater the mass loss rate, the faster the self-renewal rate of the material, and vice versa. The self-renewal rate test experimental process refers to 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 protein resistance of the multifunctional antifouling controllable degradable polyurethane material in the embodiment was evaluated by quartz crystal balance (QCM-D), and the frequency change △f was used to evaluate the protein resistance effect. The more the △f value decreased, the more protein adsorption, and vice versa. The anti-protein adsorption test experimental process refers to Ma J, Ma C, Zhang G. Degradable Polymer with Protein Resistance in a Marine Environment[J]. Langmuir, 2015, 31(23):6471-6478. The actual sea antifouling effect test of the multifunctional synergistic antifouling controllable degradable polyurethane material in the embodiment refers to GB / T5370-2007 "Antifouling paint sample shallow sea immersion test method", and the antifouling effect of the material is uniformly judged by a 100-point scoring standard. The higher the score, the better the antifouling effect; conversely, the worse the antifouling effect.

[0073] The performance test results of the controllable degradation 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 implementation modes of the present invention, but the implementation modes of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention should be equivalent replacement methods and are included in the protection scope of the present invention.

Claims

1. A multifunctional synergistic antifouling controllably degradable polyurethane material, characterized in that: Prepared from the following components in parts by weight: 20-70 parts of biodegradable polyester; 10-60 parts of diisocyanate; 5-30 parts of functional small molecule alcohol; 4-25 parts of low molecular weight alcohol; 5-20 parts of tertiary amine monomer; Catalyst 0.1-1 part; 100 to 500 parts of solvent.

2. The multifunctional synergistic antifouling controllably degradable polyurethane material according to claim 1, characterized in that: The degradable polyester contains terminal hydroxyl groups; The molecular weight of the degradable polyester is 1×10 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 controllably degradable polyurethane material according to claim 2, characterized in that: The degradable polyester comprises at least one of polylactic acid, polycaprolactone and poly 3-hydroxybutyrate; The molecular weight of the degradable polyester is 1×10 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 controllably degradable polyurethane material according to claim 1, characterized in that: The functional small molecule alcohol is prepared from the following components in parts by weight: 20 to 50 parts of 3-mercapto-1,2-propylene glycol; 25-50 parts of vinyl chloroacetate; Photoinitiator 0.5-2 parts; 80 to 200 parts of solvent.

5. The multifunctional synergistic antifouling controllably degradable polyurethane material according to claim 4, characterized in that: The photoinitiator comprises at least one of 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-morpholinyl-1-propanone; The functional small molecule alcohol is prepared by a thiol-ene click reaction, comprising the following steps: 3-mercapto-1,2-propylene glycol, vinyl chloroacetate, a photoinitiator and solvent B are mixed, an inert gas is bubbled in to remove oxygen in the system, and then the mixture is reacted under ultraviolet light, and a functional small molecule alcohol is obtained after purification and drying; The small molecule alcohol includes at least one of ethylene glycol, 1,4-butanediol and 1,3-propylene glycol.

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

7. The multifunctional synergistic antifouling controllably degradable polyurethane material according to claim 6, characterized in that: The acrylic silane monomer includes at least one of trimethylsilyl acrylate, triisopropylsilyl acrylate, and tri-n-butylsilyl acrylate; The preparation of the tertiary amine monomer comprises the following steps: In an ice bath, a dimethylamine solution is slowly added dropwise to the acrylic silane ester monomer, and the addition is allowed to react. After the addition is completed, the solution is heated to room temperature and the reaction is continued. After the reaction is completed, the solution is purified and dried to obtain a tertiary amine monomer product.

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

9. The method for preparing the multifunctional synergistic antifouling controllably degradable polyurethane material according to any one of claims 1 to 8, characterized in that: The following steps are involved: (1) dehydrating the biodegradable 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, reacting, and precipitating and drying after the reaction to obtain a controllably degradable polyurethane product; (3) The controllably degradable polyurethane product is dissolved in solvent A, a tertiary amine monomer is added to the solution, and the mixture is reacted under an inert gas atmosphere. After the reaction is completed, the mixture is purified and dried to obtain a controllably degradable polyurethane resin.

10. Use of the multifunctional synergistic antifouling controllably degradable polyurethane material according to any one of claims 1 to 8 in the preparation of antifouling products.

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