Multifunctional synergistic antifouling degradable polyurethane resin, preparation method and application thereof

Abstract

The application discloses a multifunctional synergistic antifouling degradable polyurethane resin and a preparation method and application thereof. The resin is prepared from the following components in mass fractions: degradable polyester 20-70 parts, diisocyanate 10-60 parts, functional small-molecule alcohol 5-30 parts, small-molecule alcohol 4-25 parts, tertiary amine monomer 5-20 parts, catalyst 0.1-1 part and solvent 100-500 parts. The application introduces side chains with sterilization and antifouling functions into the polyurethane material through a functional chain extender, so that the static antifouling capacity of the material can be effectively improved. The multifunctional synergistic antifouling controllable degradable polyurethane material has good sterilization, antifouling and surface self-renewal performances, can guarantee the antifouling capacity of the material under different conditions, has excellent mechanical properties and antifouling performance, and has the advantages of simple preparation method, convenient construction and the like.

Description

TECHNICAL FIELD

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

[0002] In the process of marine industry and maritime activities, marine engineering equipment and facilities inevitably encounter the problem of marine biofouling. Marine biofouling can increase the resistance of ship navigation, reduce the speed of navigation, 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 circulating pipeline and filter screen of nuclear power plants, reduce the heat exchange efficiency, and affect the normal operation of energy facilities such as wave power generation platforms and tidal power generation units; also block the mesh of deep-sea net cages, hinder the exchange of oxygen and nutrients, and reduce the yield of aquaculture, etc., thereby causing huge economic losses. However, due to the complexity of the marine environment and the diversity of fouling organisms, marine antifouling is extremely challenging and has been an international problem.

[0003] At present, the most economical, effective and simple method 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 for use, and there are problems such as short antifouling period, weak static antifouling ability, and insufficient ecological friendliness. Therefore, it is of great significance to develop a multifunctional synergistic antifouling material to improve the static antifouling ability of the system and prolong the service life for national defense construction, marine resource development and environmental protection, etc. SUMMARY

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

[0005] The second purpose of the present application is to provide a preparation method of the multifunctional synergistic antifouling controllable degradable polyurethane material.

[0006] The third purpose of the present application is to provide an application of the multifunctional synergistic antifouling controllable degradable polyurethane material.

[0007] The purposes of the present application are achieved by the following technical solutions:

[0008] A multifunctional synergistic antifouling controllable degradable polyurethane material is prepared from the following components in mass fraction:

[0009] 20-70 parts of degradable polyester;

[0010] 10-60 parts of diisocyanate;

[0011] 5-30 parts of functional small molecule alcohol;

[0012] a small molecule alcohol 4-25 parts;

[0013] a tertiary amine monomer 5-20 parts;

[0014] a catalyst 0.1-1 part;

[0015] a solvent A 100-500 parts.

[0016] Further prepared from the following mass parts of each component:

[0017] a degradable polyester 30-50 parts;

[0018] a diisocyanate 30-50 parts;

[0019] a functional small molecule alcohol 5-16 parts;

[0020] a small molecule alcohol 4-15 parts;

[0021] a tertiary amine monomer 5-20 parts;

[0022] a catalyst 0.1-0.3 parts;

[0023] a solvent A 100-300 parts.

[0024] The degradable polyester contains a terminal hydroxyl group, and further includes at least one of polylactic acid, polycaprolactone and poly-3-hydroxybutyric acid; and more further includes at least one of polylactic acid and polycaprolactone.

[0025] Further, the molecular weight of the degradable polyester is 1x10 3 -5x10 3 g / mol, and more further 1x10 3 -3x10 3 g / mol.

[0026] Further, the diisocyanate includes at least one of isophorone diisocyanate (IPDI), toluene diisocyanate (TDI), dicyclohexyl methane diisocyanate (HMDI), diphenyl methane diisocyanate (MDI) and lysine diisocyanate (LDI); and more further includes at least one of isophorone diisocyanate (IPDI), lysine diisocyanate (LDI), toluene diisocyanate (TDI) and dicyclohexyl methane diisocyanate (HMDI).

[0027] Further, the functional small molecule alcohol is prepared from the following mass parts of each component:

[0028] 3-mercapto-1,2-propanediol 20-50 parts;

[0029] vinyl chloroacetate 25-50 parts;

[0030] photoinitiator 0.5-2 parts;

[0031] solvent B 80-200 parts.

[0032] Further, the components are prepared in the following mass parts:

[0033] 3-mercapto-1,2-propanediol 30-40 parts;

[0034] vinyl chloroacetate 35-45 parts;

[0035] photoinitiator 0.5-1.5 parts;

[0036] solvent B 100-200 parts.

[0037] Further, the photoinitiator includes at least one of 2,4,6(trimethylbenzoyl) diphenyl phosphine oxide, 2-hydroxy-2-methyl-1-phenyl-1-propanone, benzoin dimethyl ether, benzophenone and 2-methyl-1-[4-methylthiophenyl]-2-morpholinyl-1-propanone; further further includes benzoin dimethyl ether.

[0038] Further, the solvent B includes at least one of toluene, tetrahydrofuran, xylene, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, acetone, butanone, ethyl acetate and butyl acetate; further further includes tetrahydrofuran.

[0039] Further, the functional small molecule alcohol is prepared by a thiol-ene click reaction, including the following steps:

[0040] 3-mercapto-1,2-propanediol, vinyl chloroacetate, photoinitiator and solvent B are mixed, inert gas is bubbled to remove oxygen contained in the system, then reacted under ultraviolet light, and the functional small molecule alcohol is obtained after purification and drying.

[0041] Further, the molar ratio of 3-mercapto-1,2-propanediol to vinyl chloroacetate is 1:1.

[0042] Further, the inert gas is bubbled for 10-30 min; further further for 30 min.

[0043] Further, the reaction under ultraviolet light is under the following conditions: ultraviolet light wavelength is 245-365 nm, ultraviolet light intensity is 80-100 mW / cm 2 , and the reaction is for 20-60 min; further further: ultraviolet light wavelength is 245-365 nm, ultraviolet light intensity is 80-100 mW / cm 2 , and the reaction is for 30 min.

[0044] Further, the small molecule alcohol includes at least one of ethylene glycol, 1,4-butanediol and 1,3-propanediol.

[0045] Further, the tertiary amine monomer is prepared from the following components by mass fraction:

[0046] acrylic silane ester monomer 80-160 parts;

[0047] dimethylamine 20-40 parts;

[0048] solvent C 80-160 parts.

[0049] Further, the tertiary amine monomer is prepared from the following components by mass fraction:

[0050] acrylic silane ester monomer 110-160 parts;

[0051] dimethylamine 20-26 parts;

[0052] solvent C 120-160 parts.

[0053] Further, the acrylic silane monomer includes at least one of trimethylsilane acrylate, triisopropylsilane acrylate and tri-n-butylsilane acrylate; and further includes triisopropylsilane acrylate.

[0054] Further, the solvent C includes tetrahydrofuran.

[0055] Further, the preparation of the tertiary amine monomer includes the following steps:

[0056] Slowly drop the solution of dimethylamine in the acrylic silane ester monomer under ice bath, drop and react, continue to react after the solution is raised to room temperature after the dropping is completed, purify, dry after the reaction is completed, and the tertiary amine monomer product is obtained.

[0057] Further, the time for dropping and reacting is 2-5 h; and further 3 h.

[0058] Further, the time for continuing to react is 12-24 h; and further 12 h.

[0059] Further, the catalyst includes at least one of dibutyltin dilaurate, di-n-octyltin dilaurate, dibutyltin diacetate, stannous octoate, monobutyl tin oxide and dibutyltin maleate; and further includes dibutyltin dilaurate.

[0060] Further, the solvent A includes at least one of toluene, tetrahydrofuran, dimethylbenzene, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, acetone, butanone, ethyl acetate, butyl acetate and dimethyl sulfoxide; more preferably includes at least one of tetrahydrofuran, ethyl acetate, n-butyl alcohol, isobutyl alcohol, acetone and dimethyl sulfoxide.

[0061] The preparation method of the multifunctional synergistic antifouling controllable degradable polyurethane material described above comprises the following steps:

[0062] (1) The degradable polyester is subjected to dehydration treatment under vacuum conditions to obtain a dehydration product; under the conditions of inert gas and stirring, diisocyanate and solvent A are added to the dehydration product to obtain a polyurethane prepolymer by reaction;

[0063] (2) The polyurethane prepolymer is added with a functional small molecule alcohol, a small molecule alcohol, a catalyst and solvent A to react, and after the reaction is completed, precipitation and drying are performed to obtain a controllable degradable polyurethane product;

[0064] (3) The controllable degradable polyurethane product is dissolved in solvent A, and a tertiary amine monomer is added to the solution to react under an inert gas atmosphere, and after the reaction is completed, purification and drying are performed to obtain a controllable degradable polyurethane resin.

[0065] Further, the dehydration treatment condition in step (1) is 80-130°C under vacuum dehydration treatment for 1-3h; more further is 110°C under vacuum dehydration treatment for 2h.

[0066] Further, the reaction condition in step (1) is 60-100°C stirring reaction for 3-5h; more further is 70°C stirring reaction for 2h.

[0067] Further, the addition amount of the solvent A in step (1) is added to make the solid content in the reaction system 20%-50%.

[0068] Further, the solvent A in step (1) includes at least one of tetrahydrofuran, ethyl acetate, n-butyl alcohol, isobutyl alcohol and acetone.

[0069] Further, the reaction condition in step (2) is 60-120°C stirring reaction for 1-3h; more further is 80°C stirring reaction for 3h.

[0070] Further, the addition amount of the solvent A in step (2) is added to make the solid content in the reaction system 20%-50%.

[0071] Further, the solvent A in step (2) includes at least one of tetrahydrofuran, ethyl acetate, n-butyl alcohol, isobutyl alcohol and acetone.

[0072] Further, the precipitation in step (2) is precipitation with n-hexane.

[0073] Further, the drying in step (2) is vacuum drying at 60 DEG C.

[0074] Further, the reaction condition in step (3) is 60-100 DEG C for 12-24 h; further, 80 DEG C for 12 h.

[0075] Further, the mass fraction of solvent A in step (3) is 50-200 parts; further, 100 parts.

[0076] Further, solvent A in step (3) comprises dimethyl sulfoxide.

[0077] Further, the drying in step (3) is vacuum drying.

[0078] The above multifunctional synergistic antifouling controllable degradable polyurethane material is applied to the preparation of antifouling products.

[0079] Further, the antifouling product comprises antifouling paint.

[0080] Principle of the present application:

[0081] The multifunctional synergistic antifouling controllable degradable polyurethane material disclosed in the present application is first obtained by degradable polyester, diisocyanate, functional small molecule alcohol and small molecule alcohol polymerization to obtain a polyurethane product, and then a hydrolysable monomer (as shown in formula 1) is introduced by reaction. The side group of the polyurethane antifouling material is a bactericidal quaternary ammonium type cation structure, and can be hydrolyzed to generate a zwitterion (as shown in formula 2) with antifouling ability under the induction of seawater, thereby enhancing the antifouling ability of the system. The main chain of the polyurethane antifouling material is a degradable polyester segment, which degrades in seawater to form a bactericidal-antifouling dynamic surface that is constantly renewed. The polyurethane material combines the multifunctional antifouling of bactericidal, antifouling and surface self-renewal, effectively improves the static antifouling ability of the material, and prolongs the service life of static service marine equipment.

[0082]

[0083] Formula 1.

[0084]

[0085] Formula 2.

[0086] The multifunctional synergy refers to that the material contains quaternary ammonium cation structure on one hand, which has a killing effect on the fouling organisms; and on the other hand, the material can hydrolyze to generate zwitterions under the induction of seawater, which can inhibit the adhesion of the fouling organisms; further, the polyurethane main chain contains degradable segments, which can form a dynamic surface of sterilization-anti-fouling that is constantly renewed through degradation, so that the material can effectively avoid the covering of impurities such as oil stains, sea mud and inorganic substances on the surface of the coating, resulting in the failure of the anti-fouling function; the multifunctional synergistic anti-fouling controllable degradable polyurethane material can improve the anti-fouling ability of the material and prolong the service life of the material.

[0087] The multifunctional synergistic anti-fouling controllable degradable polyurethane material prepared by the application has excellent mechanical properties, degradation properties and anti-fouling properties, the polyester main chain can be degraded into non-toxic small molecules in seawater, which embodies the environmental friendliness, and can be widely applied in the field of marine anti-fouling coatings.

[0088] The application has the following advantages and effects compared with the prior art:

[0089] (1) The multifunctional synergistic anti-fouling controllable degradable polyurethane material disclosed by the application realizes the anti-fouling function by using the degradation characteristics of the degradable polyester soft segment in the main chain, does not need to compound an anti-fouling agent, and can be degraded into non-toxic small molecules, which has outstanding environmental friendliness.

[0090] (2) The multifunctional synergistic anti-fouling controllable degradable polyurethane material disclosed by the application contains bactericidal quaternary ammonium cation structure, and can hydrolyze to generate zwitterions with anti-fouling ability under the induction of seawater, and the existence of the degradable main chain makes the material form a dynamic surface of sterilization-anti-fouling that is constantly renewed, which further enhances the anti-fouling ability of the system, and the polyurethane material has more excellent static anti-fouling effect and longer service life in the complex marine environment.

[0091] (3) The multifunctional synergistic anti-fouling controllable degradable polyurethane material disclosed by the application has good mechanical properties, and can meet the application in marine anti-fouling coatings.

[0092] (4) The preparation method of the multifunctional synergistic anti-fouling controllable degradable polyurethane material disclosed by the application is simple, and the material has good anti-fouling effect, which has a broad application prospect in the field of environment-friendly marine anti-fouling. DETAILED DESCRIPTION

[0093] The application will be further described in detail below in combination with examples, but the implementation of the application is not limited thereto. The test methods in the following examples are generally carried out according to conventional test conditions or according to the test conditions suggested by the manufacturer, unless the specific test conditions are specified. The materials, reagents and the like used are commercially available, unless otherwise specified.

[0094] Preparation of multifunctional synergistic antifouling controllable degradable polyurethane material

[0095] Preparation of multifunctional synergistic antifouling controllable degradable polyurethane material, comprising the following steps:

[0096] S1. Preparation of functional small molecule alcohol: 10.8 g of 3-mercapto-1, 2-propanediol, 12.0 g of vinyl chloroacetate, 0.35 g of initiator benzoin dimethyl ether, and 50 ml of solvent tetrahydrofuran are mixed, inert gas is bubbled for 30 min to remove oxygen in the system, then ultraviolet light is irradiated in an ultraviolet curing box (ultraviolet light wavelength is 350 nm, intensity is 100 mW / cm 2 ) for 30 min, and after purification and drying, the functional small molecule alcohol is obtained. The feeding ratio of 3-mercapto-1, 2-propanediol to vinyl chloroacetate is 1:1 according to the reaction molar ratio.

[0097] S2. Preparation of tertiary amine monomer: under ice bath, 2.28 g of triisopropyl silane acrylate monomer is slowly added dropwise with dimethylamine tetrahydrofuran solution (wherein the content of dimethylamine is 0.45 g; the content of tetrahydrofuran is 2.73 g), dropwise addition and reaction for 3 h, after the dropwise addition is completed, the reaction solution is raised to room temperature and continues to react for 12 h, after the reaction is completed, purification and drying are carried out, and the tertiary amine monomer product is obtained. The feeding ratio of other silane acrylate monomers to dimethylamine is also 1:1 according to the molar ratio.

[0098] S3. Preparation of controllable degradable polyurethane product A: the degradable polyester is vacuumed at 110°C for 2 h under vacuum condition to remove moisture to obtain a dehydrated product; then the reaction temperature is reduced to 80°C, half of the total amount of diisocyanate and solvent is added, and pre-polymerization is carried out for 2 h under nitrogen atmosphere and stirring condition to obtain a polyurethane prepolymer; then the 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 for stirring reaction for 3 h, after the reaction is completed, the product is precipitated with n-hexane and vacuum dried to obtain the controllable degradable polyurethane product A.

[0099] S4. The product A obtained in step S3 is dissolved in dimethyl sulfoxide solvent, after sufficient dissolution, tertiary amine monomer with the same molar ratio as the functional small molecule alcohol is added, and stirring reaction is carried out at 80°C under nitrogen atmosphere for 12 h, after the reaction is completed, purification and drying are carried out, and the multifunctional synergistic antifouling controllable degradable polyurethane resin material PU is obtained.

[0100] The preparation methods of the multifunctional synergistic antifouling controllable degradable polyurethane materials in Examples 1-6 are as follows: the mass fractions of the components used in the preparation of the polyurethane resin in step S3 and the mass fractions of the components in step S4 are shown in Table 1; the multifunctional synergistic antifouling controllable degradable polyurethane resin materials PU-1-PU-6 in Examples 1-6 are prepared through steps S1-S4.

[0101] Comparative Example 1

[0102] The preparation of the polyurethane resin material includes the following steps:

[0103] Steps S1-S2 are the same as in Examples 1-6.

[0104] Step S3: Preparation of PU: The degradable polyester is vacuumed at 110°C for 2h to remove moisture to obtain a dehydrated product; then the reaction temperature is lowered to 80°C, half of the total amount of diisocyanate and solvent is added, and pre-polymerization is carried out under nitrogen atmosphere and stirring for 2h to obtain a polyurethane prepolymer; then the zwitterionic small molecule alcohol, small molecule alcohol, catalyst dibutyltin dilaurate, and half of the total amount of solvent are added, and the temperature is controlled at 80±5°C for stirring reaction for 3h; after the reaction is completed, it is precipitated with n-hexane and vacuum dried to obtain a controllable degradable polyurethane product, i.e., the polyurethane resin material PU-7. The mass fractions of the components used in the preparation of the polyurethane resin in step S3 are shown in Table 2.

[0105] The preparation of the zwitterionic small molecule alcohol includes the following steps:

[0106] 10 g of diethanolamine is added to a 100 ml three-necked round-bottom flask, and 11 g of ethyl acrylate is added dropwise into the flask using a constant pressure dropping funnel under stirring at 35°C in an oil bath and under N2, and the mixture is stirred overnight to obtain a colorless liquid; then, excess ethyl acrylate is removed by vacuum distillation at 60°C to obtain the desired zwitterionic small molecule alcohol.

[0107] Comparative Example 2

[0108] The preparation of the polyurethane resin material includes the following steps:

[0109] Steps S1-S2 are the same as in Examples 1-6.

[0110] Step S3: Preparation of PU: The polytetrahydrofuran was vacuumed at 110°C for 2h to remove moisture to obtain a dehydrated product; then the reaction temperature was lowered to 80°C, and half of the total amount of solvent and diisocyanate were added, and pre-polymerization was carried out under nitrogen atmosphere and stirring for 2h to obtain a polyurethane prepolymer; then the functional small molecule alcohol, small molecule alcohol, catalyst and half of the total amount of solvent were added, and the temperature was controlled at 80±5°C for stirring reaction for 3h, and after the reaction was completed, it was precipitated with n-hexane and vacuum dried to obtain a controllable degradable polyurethane product A.

[0111] S4: The product A obtained in step S3 was dissolved in dimethyl sulfoxide solvent, and after sufficient dissolution, a tertiary amine monomer in an equimolar ratio with the functional small molecule alcohol was added, and stirring reaction was carried out at 80°C under nitrogen atmosphere for 12h, and after the reaction was completed, it was purified and dried to obtain a polyurethane resin material PU-8. The mass fractions of the components are shown in Table 2.

[0112] The mass fractions of the components used in the preparation of the polyurethane resin in step S3 and the mass fractions of the components in step S4 are shown in Table 2.

[0113] Comparative Example 3

[0114] Steps S1-S2 are the same as Examples 1-6;

[0115] Step S3: Preparation of PU: The degradable polyester was vacuumed at 110°C for 2h to remove moisture to obtain a dehydrated product; then the reaction temperature was lowered to 80°C, and half of the total amount of solvent and diisocyanate were added, and pre-polymerization was carried out under nitrogen atmosphere and stirring for 2h to obtain a polyurethane prepolymer; then the functional small molecule alcohol, small molecule alcohol, catalyst and half of the total amount of solvent were added, and the temperature was controlled at 80±5°C for stirring reaction for 3h, and after the reaction was completed, it was precipitated with n-hexane and vacuum dried to obtain a controllable degradable polyurethane product, i.e. a polyurethane resin material PU-9. The mass fractions of the components used in the preparation of the polyurethane resin in step S3 are shown in Table 2.

[0116] Comparative Example 4

[0117] Steps S1-S2 are the same as Examples 1-6;

[0118] Step S3: Preparation of PU: The polytetrahydrofuran was vacuumed at 110°C for 2h to remove moisture to obtain a dehydrated product; then the reaction temperature was reduced to 80°C, and half of the total amount of diisocyanate and solvent was added, and pre-polymerization was carried out under nitrogen atmosphere and stirring for 2h to obtain a polyurethane prepolymer; then the functional small molecule alcohol, small molecule alcohol, catalyst and half of the total amount of solvent were added, and the temperature was controlled at 80±5°C for stirring reaction for 3h, and after the reaction was completed, it was precipitated with n-hexane and vacuum dried to obtain a controllable degradable polyurethane product, i.e. a polyurethane resin material PU-10. The mass fraction of each component of the raw materials used in the preparation of the polyurethane resin in step S3 is shown in Table 2.

[0119] Comparative Example 5

[0120] Steps S1-S4 are the same as in Examples 1-6, and a polyurethane resin material PU-11 is obtained. The mass fraction of each component of the raw materials used in the preparation of the polyurethane resin in step S3 and the mass fraction of each component in step S4 are shown in Table 2.

[0121] Comparative Example 6

[0122] Steps S1-S4 are the same as in Examples 1-6, and a polyurethane resin material PU-12 is obtained. The mass fraction of each component of the raw materials used in the preparation of the polyurethane resin in step S3 and the mass fraction of each component in step S4 are shown in Table 2.

[0123] Table 1

[0124]

[0125] Table 2

[0126] Performance Test

[0127] The adhesion of the multifunctional synergistic antifouling controllable degradable polyurethane material in the examples to the substrate was measured by the pull-off method, referring to GB / T 5210, and the test area was a circular area with a diameter of 20mm, and the pull-off rate was set at 0.2MPa / s. Five different areas of each sample were tested, and the average value was taken as the test result.

[0128] The antibacterial performance of the multifunctional synergistic antifouling controllable degradable polyurethane material in the examples was tested according to GB / T 21866-2008.

[0129] The self-renewal rate of the multifunctional synergistic antifouling controllable degradable polyurethane material in the examples was tested by measuring the mass loss rate of the coating after 30 days of immersion in ASW. The greater the mass loss rate, the faster the self-renewal rate of the material, and vice versa. The self-renewal rate test 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.

[0130] The anti-protein performance of the multifunctional synergistic antifouling controllable degradable polyurethane material in the examples was evaluated by quartz crystal microbalance (QCM-D), and the frequency change Δf was used to evaluate the anti-protein effect. The greater the Δf value, the more protein adsorption, and vice versa. The anti-protein adsorption test 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.

[0131] The real sea antifouling effect test of the multifunctional synergistic antifouling controllable degradable polyurethane material in the examples refers to GB / T5370-2007 “Antifouling paint panel shallow sea immersion test method”. The antifouling effect of the material is judged by the percentage score standard. The higher the score, the better the antifouling effect; otherwise, the worse the antifouling effect.

[0132] 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.

[0133] Table 3

[0134]

[0135] The above embodiments are the preferred embodiments of the present application, but the embodiments of the present application are not limited to the above embodiments, and any changes, modifications, substitutions, combinations, simplifications, etc. made without departing from the spirit and principles of the present application should be equivalent replacement manners and should be included in the protection scope of the present application.

Claims

1. A multifunctional, synergistic, and controllable biodegradable polyurethane material, characterized in that, Prepared from the following components in parts by mass: 20-70 parts of biodegradable polyester; 10-60 parts of diisocyanate; 5-30 parts of functional small molecule alcohols; 4-25 parts of small molecule diols; 5-20 parts of tertiary amine monomer; Catalyst 0.1 to 1 part; Solvent: 100-500 parts; The biodegradable polyester contains terminal hydroxyl groups; The biodegradable polyester has a molecular weight of 1×10⁻⁶. 3 ~3×10 3 g / mol; 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 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 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. The preparation method of the aforementioned multifunctional synergistic antifouling controllable degradable polyurethane material includes the following steps: (1) Dehydrate the biodegradable polyester under vacuum conditions to obtain a dehydrated product; add diisocyanate and solvent 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 diol, catalyst and solvent to polyurethane prepolymer, react, precipitate and dry after reaction to obtain controllable degradable polyurethane product. (3) Dissolve the controllable degradable polyurethane product in a solvent, add a tertiary amine monomer to the solution, react under an inert gas atmosphere, and purify and dry after the reaction to obtain the controllable degradable polyurethane resin.

2. The multifunctional synergistic antifouling controlled-degradable polyurethane material according to claim 1, characterized in that, 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 1, characterized in that, The biodegradable polyester includes at least one of polylactic acid, polycaprolactone, and poly(3-hydroxybutyrate); 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: 20-50 parts of 3-mercapto-1,2-propanediol; Vinyl chloroacetate 25-50 parts; Photoinitiator 0.5–2 parts; Solvent: 80-200 parts.

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 small molecule diols 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 portions of Grade II A; Solvent: 80-160 parts.

7. The multifunctional synergistic antifouling controlled-degradable polyurethane material according to claim 6, characterized in that, The acrylate silane monomers include at least one of trimethyl acrylate, triisopropyl acrylate, and tri-n-butyl acrylate.

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 controllable 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 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 diol, catalyst and solvent to polyurethane prepolymer, react, precipitate and dry after reaction to obtain controllable degradable polyurethane product. (3) Dissolve the controllable degradable polyurethane product in a solvent, add a tertiary amine monomer to the solution, react under an inert gas atmosphere, and purify and dry after the reaction to obtain the 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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