Degradable organosilicon hydrogel antifouling resin and preparation method and application thereof

Abstract

The application discloses a degradable organosilicon hydrogel antifouling resin and a preparation method and application thereof. The degradable organosilicon hydrogel antifouling resin has the structure shown in the following formula: wherein R0 is a multifunctional alcohol or ammonia structural unit, R1 is a diisocyanate structural unit, R2 is a hydrophilic chain segment structural unit, R3 is a structural unit containing a di-oxime functional group, R4 is a structural unit containing organosilicon, m, n and p are independently selected from 1 to 20, and q is selected from 1 to 10. The degradable organosilicon hydrogel antifouling resin in the application has the characteristics of low-surface antifouling materials, hydrogel antifouling materials and degradable antifouling materials on the basis of self-repairing at room temperature, has excellent antifouling effect and has a good application prospect.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of antifouling, and particularly relates to a degradable organosilicon hydrogel antifouling resin and a preparation method and application thereof. BACKGROUND

[0002] Marine antifouling materials can reduce the attachment of marine organisms, thus preventing phenomena such as the reduction of ship speed and the increase of fuel consumption caused by the attachment of marine organisms, and avoiding problems such as the blockage of seawater pipelines and aquaculture nets and the destruction of underwater facilities. Antifouling coatings containing organotin that appeared in the mid-20th century have good antifouling effect, but are harmful to the ocean, so the development of environmentally friendly new antifouling coatings has become the focus of domestic and foreign research on marine antifouling coatings.

[0003] Low-surface-energy antifouling coatings, hydrophilic (hydrogel) antifouling materials, and self-renewing antifouling materials are currently important environmentally friendly antifouling coatings. Low-surface-energy antifouling coatings use the low-surface-energy characteristics of the coating itself to make the attachment of fouling organisms to the surface of the coating difficult, and the fouling organisms are easily removed under the action of the shear force of ship sailing or scouring. At present, low-surface-energy antifouling coatings mainly include organofluorine systems and organosilicon systems, and the organosilicon system low-surface-energy antifouling coatings are more successful in applications on high-speed ship hulls, but the antifouling effect is not ideal in low-speed conditions.

[0004] Hydrogel is a three-dimensional network material formed by the interaction of a hydrophilic polymer crosslinked by physical or chemical action and water, and has the characteristics of swelling in water and not dissolving in water, and forms a hydration layer on the surface of the material. The dense hydration layer on the surface of the hydrogel material and the unstable surface of the material due to the low elastic modulus endow the hydrogel with great potential for preventing marine biofouling. The hydrogel polymers currently used for marine antifouling generally have problems such as poor mechanical properties and adhesion to substrates, easy brittleness when dehydrated, and insufficient long-term and broad-spectrum antifouling, which limit their practical applications.

[0005] Degradable marine antifouling polymer materials refer to polymer materials that can degrade in seawater, enzymes secreted by marine organisms, or in the bodies of marine organisms. The antifouling mechanism is that the surface of the material degrades, the degradation products continuously dissolve and fall off into seawater, causing the marine fouling organisms attached to the surface of the facility to be passively detached. At the same time, the continuous degradation exposes a new surface, which is constantly renewed, maintaining a relatively stable surface chemical and physical structure. Such materials have less environmental hazards and meet the requirements of environmentally friendly marine antifouling materials, and have good development prospects in marine antifouling materials. At present, degradable materials such as polycaprolactone (PCL), polylactic acid (PLA), and polyurethane are limited in applications due to problems such as high crystallinity, low hydrolysis rate, and insufficient antifouling performance.

[0006] Marine antifouling is a global problem, and the future of marine antifouling materials not only needs to meet the requirements of environmentally friendly materials, but also needs to be suitable for different marine environments. In the complex and changeable marine environment, the species, attachment growth habits and fouling degree of fouling organisms will change, and it is difficult to completely solve the problem of marine antifouling by relying solely on the design of materials with only one property. In addition, to cope with the damage of materials caused by construction and external impact, the self-repair of antifouling materials should also be considered at the beginning of material design. In order to cope with the above problems, one possible method is to design a multifunctional coating. For example: giving the traditional self-polishing material biodegradable function, further increasing the degradation pathway, improving the degradation capacity, and further cooperating with the use of antifouling agent, so that it can have a persistent and stable antifouling effect in static and dynamic marine environment; Or another method is to combine the surface morphology that is difficult for fouling organisms to attach, such as low surface energy material, with some suitable antifouling active factors, such as antibacterial agent, zwitterion or amphiphilic segment, to form an antifouling material; The biomimetic coating combines self-renewable materials, such as adding antifouling chemical structure to the surface with biomimetic antifouling, or combining fouling detachment type material with self-polishing material to form a composite coating. SUMMARY

[0007] The main purpose of the present application is to provide a degradable organosilicon hydrogel antifouling resin and its preparation method and application, so as to overcome the shortcomings of the prior art.

[0008] In order to achieve the above-mentioned purpose of the application, the technical scheme adopted by the present application comprises:

[0009] The present application provides a degradable organosilicon hydrogel antifouling resin, which has a structure as shown in formula (I):

[0010]

[0011] In the formula, R0 is a multifunctional alcohol or amine structural unit, and R0 is selected from R 10 is an aliphatic structure, and x is selected from 3 to 6;

[0012] R1 is a diisocyanate structural unit, and R1 is selected from R 11 is an aliphatic or aromatic alkane structure;

[0013] R2 is a hydrophilic segment structural unit, and R2 is selected from y is 1 to 5, and z is 1 to 250;

[0014] R3 is a di-oxime functional group containing structural unit, and R3 is selected from R 12aliphatic or aromatic alkane structure;

[0015] R4 is a structural unit comprising silicone, and R4 is selected from R 13 , R 14 are independently selected from methyl or phenyl, R 15 is an alkane segment, and w is selected from 10 to 200;

[0016] m, n, p are independently selected from 1 to 20, and q is selected from 1 to 10.

[0017] The embodiment of the present application also provides a preparation method of the aforementioned degradable silicone hydrogel antifouling resin, which comprises the following steps:

[0018] reacting a mixed reaction system comprising a hydrophilic monomer, a first multifunctional monomer, a silicone monomer, a dioxime monomer, an isocyanate monomer and a solvent under a protective gas to obtain a degradable silicone hydrogel antifouling resin prepolymer;

[0019] and mixing and reacting the degradable silicone hydrogel antifouling resin prepolymer with a second multifunctional monomer to obtain a degradable silicone hydrogel antifouling resin.

[0020] The embodiment of the present application also provides application of the aforementioned degradable silicone hydrogel antifouling resin in the field of antibacterial or antifouling on the surface of a substrate.

[0021] Compared with the prior art, the present application has the following beneficial effects:

[0022] (1) The present application can form an emulsion state of a hydrophilic phase-silicone phase or a silicone phase-hydrophilic phase in the reaction solution process, the silicone segment and the hydrophilic segment are linked to each other through a chemical bond, and a microphase separation structure is formed after forming a coating or a bulk material, the phase separation structure is divided into a hydrogel high-surface-energy phase and a silicone low-surface-energy phase, and the phase separation structure and size characteristics can be easily controlled by adjusting the content of the hydrophilic monomer and the hydrophobic monomer;

[0023] (2) The silicone hydrogel prepared by the present application contains a large amount of dynamic chemical bonds and hydrogen bonds, has self-repairing ability when damaged, and the self-healing ability can be adjusted by adjusting the content and strength of the dynamic chemical bonds and hydrogen bonds, which can effectively improve the applicability of the resin;

[0024] (3) The silicone hydrogel of the present application mainly contains amine ester groups, urea groups and oxime groups, these groups can be degraded in a marine environment, and the degradation rate can be adjusted by adjusting the content of the dynamic chemical bonds and the hydrophilicity, which can effectively avoid the harm of marine microplastics;

[0025] (4) The material prepared in the present application has excellent synergistic antifouling ability. The hydrogel layer formed by the hydrophilic phase is a good carrier of the hydration layer, can form a biological adhesion barrier to hinder the adhesion of microorganisms; the organic silicon high surface energy layer has a lower elastic modulus and a biological detachment barrier, so that once the organism adheres, it can be detached under the lower water flow scouring; the degradation characteristics of the resin can form a dynamic surface to actively remove the surface-adhered organisms; under the synergistic action of the three antifouling mechanisms, the antifouling efficiency is improved. BRIEF DESCRIPTION OF DRAWINGS

[0026] In order to more clearly illustrate the technical solutions in the embodiments of the present application or the prior art, the drawings needed to be used in the embodiments or the prior art description will be briefly introduced. Obviously, the drawings in the following description are only some embodiments described in the present application, and other drawings can be obtained by those skilled in the art without creative labor.

[0027] Figure 1 is a preparation flow chart of a typical antifouling resin / material / coating in the present application embodiment;

[0028] Figure 2 is a synthesis schematic diagram of a typical antifouling resin in the present application embodiment;

[0029] Figure 3 is a degradation schematic diagram of the antifouling resin in the present application typical embodiment in the water medium environment;

[0030] Figure 4 is an infrared absorption spectrum diagram of the degradable organic silicon hydrogel antifouling resin coating / block material prepared in the present application embodiment 1. DETAILED DESCRIPTION

[0031] In view of the above-mentioned defects and deficiencies of the existing degradable resin, organic silicon resin and hydrogel antifouling resin in the antifouling technology, the present application adopts a multi-element synergistic antifouling pollution control strategy, uses organic silicon and hydrogel as the main coating material, and connects each unit inside the resin through degradable urethane, urea group and oxime group, to provide a degradable organic silicon hydrogel antifouling resin with controllable degradation rate, adjustable mechanical strength and multi-element synergistic antifouling function.

[0032] The technical solutions of the present application will be described clearly and completely below. Obviously, the described embodiments are part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor belong to the scope of protection of the present application.

[0033] Specifically, as one aspect of the technical scheme of the present application, the degradable organosilica hydrogel antifouling resin has a structure as shown in formula (I):

[0034]

[0035] wherein R0 is a multifunctional alcohol or ammonia structural unit, and R0 is selected from R 10 is an aliphatic structure, and x is selected from 3-6;

[0036] R1 is a diisocyanate structural unit, and R1 is selected from R 11 is an aliphatic or aromatic alkane structure;

[0037] R2 is a hydrophilic chain segment structural unit, and R2 is selected from y is 1-5, and z is 1-250;

[0038] R3 is a di-oxime functional group-containing structural unit, and R3 is selected from R 12 is an aliphatic or aromatic alkane structure;

[0039] R4 is an organosilica-containing structural unit, and R4 is selected from R 13 , R 14 are independently selected from methyl or phenyl, and R 15 is an alkane chain segment, and w is selected from 10-200;

[0040] m, n, and p are independently selected from 1-20, and q is selected from 1-10.

[0041] In some preferred embodiments, the structure of the degradable organosilica hydrogel antifouling resin comprises a hydrophilic chain segment, an organosilica chain segment, a dynamic chemical bond chain segment, and a chemical crosslinking chain segment, wherein the hydrophilic chain segment mainly comprises a hydrophilic chain segment structural unit, the organosilica chain segment mainly comprises an organosilica structural unit, the dynamic chemical bond chain segment mainly comprises a di-oxime functional group-containing structural unit, and the chemical crosslinking chain segment mainly comprises a multifunctional alcohol structural unit or a multifunctional ammonia structural unit.

[0042] Further, in the structure of the degradable organosilica hydrogel antifouling resin, the content of the hydrophilic chain segment is 5wt%-75wt%, the content of the organosilica chain segment is 20wt%-85wt%, the content of the dynamic chemical bond chain segment is 5wt%-40wt%, and the content of the chemical crosslinking chain segment is 0.1wt%-10wt%.

[0043] Further, the content of the hydrophilic chain segment in the structure of the degradable organosilicon hydrogel antifouling resin is 10wt%-60wt%, the content of the organosilicon chain segment is 30wt%-70wt%, the content of the dynamic chemical bond chain segment is 10wt%-30wt%, and the content of the chemical cross-linking chain segment is 0.5wt%-5wt%.

[0044] In some preferred embodiments, the surface of the degradable organosilicon hydrogel antifouling resin has a contact angle with water of 150-30°.

[0045] In some preferred embodiments, the degradation rate of the degradable organosilicon hydrogel antifouling resin is 0.01-10mg cm -1 L -1 day -1 (the release concentration of the degradation unit per unit area).

[0046] In some preferred embodiments, the degradable organosilicon hydrogel antifouling resin has any one of the structures shown in the following formulae:

[0047]

[0048]

[0049] wherein R 11 is an aliphatic or aromatic alkane structure, m, n, p are independently selected from 1-20, and q is selected from 1-10.

[0050] In the present application, the degradable organosilicon hydrogel antifouling resin has a micro-phase separation structure, and the phase separation structure is divided into a hydrogel high-surface-energy phase and an organosilicon low-surface phase. The surface of the degradable organosilicon hydrogel antifouling resin has a contact angle with water of 150-30°.

[0051] Further, the degradable organosilicon hydrogel antifouling resin has degradable and self-repairing properties. The dynamic chemical bonds, hydrolysable urea groups and amine ester groups in the chain segment structure of the resin impart the degradable property of the resin, and the hydrogen bonds and dynamic chemical bonds in the chain segment structure of the resin impart the self-repairing property of the resin.

[0052] In the present application, by introducing degradable functional groups such as amine ester groups, urea groups and oxime groups into the main chain, an intrinsic self-repairing and main-chain degradable organosilicon hydrogel antifouling resin can be obtained. The synthesis process is as follows: Figure 2As shown. The degradable organosilicon hydrogel antifouling resin or coating prepared in this invention can achieve intrinsic self-repair at room temperature after being damaged, based on the reversible covalent bonds of amine oximes in the molecular structure and the numerous hydrogen bonds in the chain segments. The degradable organosilicon hydrogel antifouling resin or coating prepared in this invention can slowly hydrolyze in an aqueous or humid environment, and small molecule degradation products are slowly released from the resin. By controlling the ratio of degradable functional groups such as amine esters, urea groups, and oxime groups and the preparation process, the mechanical properties and degradation rate of the coating can be adjusted. The degradation process is as follows: Figure 3 As shown.

[0053] Another aspect of the present invention provides a method for preparing the aforementioned biodegradable organosilicon hydrogel antifouling resin, comprising:

[0054] Under a protective atmosphere, a mixed reaction system containing a hydrophilic monomer, a first multifunctional monomer, an organosilicon monomer, a dioxime monomer, an isocyanate monomer, and a solvent is reacted to prepare a biodegradable organosilicon hydrogel antifouling resin prepolymer.

[0055] Furthermore, the biodegradable silicone hydrogel antifouling resin prepolymer is mixed with a second multifunctional monomer and reacted to obtain the biodegradable silicone hydrogel antifouling resin.

[0056] In this invention, multifunctional amine or alcohol monomers act as crosslinking curing agents in the reaction system, playing a role in crosslinking curing and improving the toughness and strength of the product. However, they usually rapidly increase the viscosity of the reaction system during the reaction process, causing problems in the subsequent molding stage. In the preparation technology of the biodegradable organosilicon hydrogel antifouling resin involved in this invention, it is preferable to add multifunctional crosslinking monomers in batches during the prepolymerization stage and the molding stage. The key functions are: firstly, adding some multifunctional amine or alcohol monomers in the prepolymerization stage can promote and enhance the effective linkage between hydrophilic and hydrophobic segments and between them, stabilizing the state of the reaction system without rapidly increasing the viscosity; secondly, adding the remaining multifunctional monomers in the molding stage can accelerate the curing stage. Secondly, the addition of solvents in the preparation technology of organosilicon hydrogel resin plays a key role in reducing the viscosity of the reaction system, accelerating the rapid and uniform mixing of the reaction raw materials, and avoiding explosive polymerization caused by excessively fast reaction rates. It is worth mentioning that if the reaction system is a low-viscosity system composed entirely of liquid hydroxyl monomers, solvents may not be added.

[0057] Furthermore, the protective atmosphere includes, but is not limited to, a nitrogen atmosphere.

[0058] In some preferred embodiments, the preparation method specifically comprises: mixing a hydrophilic monomer, a first multi-functionality monomer, a silicone monomer, a di-oxime monomer and a solvent at 0-100°C in a protective atmosphere to form a mixed dispersion, and then adding an isocyanate monomer to form the mixed reaction system.

[0059] In some preferred embodiments, the reaction temperature of the mixed reaction system is 0-100°C, and the reaction time is 5 minutes to 5 days.

[0060] In some preferred embodiments, the preparation method specifically comprises: mixing the degradable silicone hydrogel antifouling resin prepolymer with a second multi-functionality monomer and reacting at 0-120°C for 5 minutes to 36 hours, and then applying the obtained mixture to the surface of a substrate or placing it in a mold and continuing to react at 0-120°C for 5 minutes to 72 hours to obtain a degradable silicone hydrogel antifouling resin; wherein the degradable silicone hydrogel antifouling resin comprises a degradable silicone hydrogel antifouling resin coating and / or a degradable silicone hydrogel antifouling resin bulk material.

[0061] In some preferred embodiments, the hydrophilic monomer comprises an amine or alcohol hydrophilic monomer, and the amine or alcohol hydrophilic monomer comprises any one or a combination of two or more of polyether amine, polyethylene imine, ethylenediamine, propylenediamine, diethylenetriamine, triethylenetetramine, polyethylene glycol, polypropylene glycol, polybutylene glycol, polyvinyl glycol, ethylene glycol, propylene glycol, and butylene glycol, without being limited thereto.

[0062] Further, the amine or alcohol hydrophilic monomer comprises any one or a combination of two or more of polyether amine, polyethylene glycol, polypropylene glycol, and polyethylene imine, without being limited thereto.

[0063] In some preferred embodiments, the first multi-functionality monomer comprises any one or a combination of two or more of tris(2-aminoethyl)amine, glycerol, pentaerythritol, trimethylolethane, xylitol, and sorbitol, without being limited thereto.

[0064] Further, the first multi-functionality monomer comprises any one or a combination of two or more of tris(2-aminoethyl)amine, glycerol, pentaerythritol, and trimethylolethane, without being limited thereto.

[0065] In some preferred embodiments, the silicone monomer comprises any one or a combination of two or more of aminopropyl-terminated polydimethylsiloxane, aminopropyl-terminated polymethylphenylsiloxane, hydrocarbyl-terminated polydimethylsiloxane, hydroxypropyl-terminated polydimethylsiloxane, hydrocarbyl-terminated polymethylphenylsiloxane, and hydroxypropyl-terminated polymethylphenylsiloxane, without being limited thereto.

[0066] Further, the organosilicon monomer includes any one of or a combination of two or more of aminopropyl-terminated polydimethylsiloxane, hydroxypropyl-terminated polydimethylsiloxane, and hydroxyalkyl-terminated polymethylphenylsiloxane, and is not limited thereto.

[0067] In some preferred embodiments, the di-oxime monomer includes any one of or a combination of two or more of glyoxime, dimethylglyoxime, pyruvic aldehyde di-oxime, 1,2-cycloheptanedione di-oxime, 9,10-phenanthrenequinone di-oxime, furil di-oxime, acenaphthenequinone di-oxime, p-benzoquinone di-oxime, and dimethylketone di-oxime, and is not limited thereto.

[0068] Further, the di-oxime monomer includes any one of or a combination of two or more of glyoxime, dimethylglyoxime, dimethylketone di-oxime, and p-benzoquinone di-oxime, and is not limited thereto.

[0069] In some preferred embodiments, the second multifunctional monomer is the same as or different from the first multifunctional monomer.

[0070] In some preferred embodiments, the solvent includes any one of or a combination of two or more of acetone, tetrahydrofuran, dichloromethane, trichloromethane, dimethylformamide, dimethylacetamide, toluene, xylene, n-butyl ether, and ethyl acetate, and is not limited thereto.

[0071] In some preferred embodiments, the content of the hydrophilic monomer in the mixed reaction system is 5 wt% to 75 wt%, the content of the organosilicon monomer is 20 wt% to 85 wt%, the content of the di-oxime monomer is 5 wt% to 40 wt%, and the content of the sum of the first multifunctional monomer and the second multifunctional monomer is 0.1 wt% to 10 wt%.

[0072] Further, the content of the hydrophilic monomer in the mixed reaction system is 10 wt% to 60 wt%, the content of the organosilicon monomer is 30 wt% to 70 wt%, the content of the di-oxime monomer is 10 wt% to 30 wt%, and the content of the sum of the first multifunctional monomer and the second multifunctional monomer is 0.5 wt% to 5 wt%.

[0073] In some preferred embodiments, the molar ratio of the first multifunctional monomer to the second multifunctional monomer is 1 to 10: 1 to 10.

[0074] Further, the molar ratio of the first multifunctional monomer to the second multifunctional monomer is 1 to 3: 1 to 3.

[0075] In some preferred embodiments, the content of the solvent in the mixed reaction system is 10 to 95 wt%.

[0076] Further, the content of the solvent in the mixed reaction system is 40 to 80 wt%.

[0077] Specifically, the preparation of the degradable organosilica hydrogel antifouling resin in the present application is shown in the following schematic diagram: Figure 1

[0078] In some more specific embodiments, the preparation method of the degradable organosilica hydrogel antifouling resin comprises:

[0079] (1) Pre-polymerization stage: completely dissolve the ammonia or alcohol hydrophilic monomer, part of the multi-functional monomer, the organosilica monomer, and the di-oxime monomer in a solvent to form a mixed solution / emulsion in a protective gas. Add the isocyanate monomer to the mixed solution / emulsion to form a mixed reaction system, and obtain a degradable organosilica hydrogel antifouling resin solution / pre-polymer after reaction, and the main chemical reaction process is shown in the following formula:

[0080]

[0081] (2) Forming stage: add the remaining multi-functional cross-linking monomer, and after a period of reaction, coat the degradable organosilica hydrogel antifouling resin solution / pre-polymer on the surface of a substrate or cast it in a mold, continue to react and remove the solvent, and obtain a degradable organosilica hydrogel antifouling resin coating / block material after cooling, and the chemical reaction process is shown in the following formula:

[0082]

[0083] wherein, R0, R1, R2, R3, R4, R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , m, n, p, q, w, and z are defined as described above. Specifically, the preparation method of the degradable organosilica hydrogel antifouling resin comprises:

[0084] (1) Pre-polymerization stage: completely dissolve the ammonia or alcohol hydrophilic monomer, part of the multi-functional monomer, the organosilica monomer, and the di-oxime monomer in a solvent to form a mixed solution / emulsion (the aforementioned mixed dispersion) in a protective gas, and the dissolution temperature is 0-100°C; add the isocyanate monomer to the mixed solution / emulsion to form a mixed reaction system, control the reaction temperature to be 0-100°C, and the reaction time is 5 min-5 d, to obtain a degradable organosilica hydrogel antifouling resin solution / pre-polymer.

[0085] ​(2) forming stage: adding the remaining multifunctional crosslinking monomer, after 5 min ~ 5 h of reaction, coating the degradable organosilicon hydrogel antifouling resin solution / prepolymer on the surface of the substrate or pouring in the mold, controlling the temperature at 0 ~ 100 DEG C, removing the solvent, continuing the reaction for 5 min ~ 48 h, and obtaining the degradable organosilicon hydrogel antifouling resin coating / block material after cooling.

[0086] Another aspect of the embodiment of the present application also provides the use of the aforementioned degradable organosilicon hydrogel antifouling resin in the field of antibacterial or antifouling on the surface of a substrate.

[0087] The organosilicon and the hydrogel in the degradable organosilicon hydrogel antifouling resin of the present application are used as the main coating material, the hydrogel forms a soft high potential hydration layer on the surface in the seawater environment, effectively blocking the adhesion of the fouling organisms, and the low surface energy and low elasticity of the organosilicon are conducive to the detachment of the fouling organisms under lower external force; the units in the resin are connected to each other through the degradable urethane, urea and oxime groups, and can be degraded in the environment, and the hydrogen bonds and the amine oxime groups can perform intrinsic self-repairing on the material.

[0088] The technical solutions of the present application will be further described in detail below in combination with several preferred embodiments and the accompanying drawings. The present embodiment is implemented on the premise of the technical solutions of the present application, and detailed implementation modes and specific operation processes are given, but the protection scope of the present application is not limited to the following embodiments.

[0089] The experimental materials used in the following embodiments are commercially available from conventional biochemical reagent companies, unless otherwise specified.

[0090] Embodiment 1

[0091] (1) prepolymerization stage: at room temperature, polyethylene glycol, glycerol (50% of the planned amount), butandione and amino-terminated dimethylsiloxane are dissolved in tetrahydrofuran, and stirring is continued for more than half an hour to form an emulsion. Subsequently, the isocyanate monomer is added to the mixed solution / emulsion to form a mixed reaction system, and the reaction is carried out at room temperature for 24 h. After the reaction, the degradable organosilicon hydrogel antifouling resin solution / prepolymer is obtained, as shown in Figure 4 .

[0092] (2) forming stage: adding the remaining multifunctional crosslinking monomer glycerol, after 1 h of reaction, coating the degradable organosilicon hydrogel antifouling resin solution / prepolymer on the surface of the substrate or pouring in the mold, continuing the reaction at 50 DEG C for 12 h and removing the solvent, further reacting at 80 DEG C for 12 h, and obtaining the degradable organosilicon hydrogel antifouling resin coating / block material after cooling, and the structure of the prepared poly-Schiff base polymer is shown in the following formula:

[0093]

[0094] wherein R 11 is an aliphatic or aromatic alkane structure, in this embodiment, the alkane structure after reaction of isophorone diisocyanate is m, n, p are independently selected from 1-20, and q is selected from 1-10.

[0095] The infrared absorption spectrum of the obtained degradable organosilicon hydrogel antifouling resin coating / block material in this embodiment is shown in Figure 4 The contact angle of the obtained degradable organosilicon hydrogel antifouling resin coating / block material (the content of amino-terminated dimethylsiloxane in the resin segment is 50%) in this embodiment is 71°; after the degradable organosilicon hydrogel antifouling resin coating / block material is soaked in water for 7 days, the contact angle is 55°; the degradable organosilicon hydrogel antifouling resin coating prepared with a thickness of about 100 μm is placed in water for 24 h, and the release concentration of butanedione oxime per unit area on each coating is about 0.5 mg / L; at room temperature, the coating is subjected to a small knife scratch damage test, and the coating scratches are basically healed within 48 hours.

[0096] Antibacterial and antialgal performance: the degradable organosilicon hydrogel antifouling resin coating / block material (the content of amino-terminated dimethylsiloxane in the resin segment is 50%) and glass are placed in Chlorella, and after 7 days, the anti-Chlorella adhesion rate on the surface of the degradable organosilicon hydrogel antifouling resin coating is about 85% compared with the glass control group. The anti-Chlorella adhesion rate refers to the reduction rate of Chlorella on the surface of the poly-Schiff base polymer coating compared with the control group (glass), and the anti-Chlorella adhesion rate = (1 - the number of algae on the surface of the poly-Schiff base polymer coating / the number of algae on the surface of the glass) x 100%.

[0097] This embodiment illustrates that the technology can conveniently prepare antifouling materials with degradability and self-healing by introducing hydrophilic segments, organosilicon segments, covalent bond segments and crosslinking segments in the molecular structure segments.

[0098] Example 2

[0099] The preparation method of this embodiment is basically the same as that of Example 1, except that the content of amino-terminated dimethylsiloxane in the resin segment is adjusted to 25% and 75%, respectively.

[0100] The contact angles of the two kinds of degradable organosilicon hydrogel antifouling resin coating / block materials obtained in this embodiment (the content of butanedione monoxime in the resin segment is 12% and 5% respectively) are 74° and 68° respectively; after the two kinds of degradable organosilicon hydrogel antifouling resin coating / block materials (the content of butanedione monoxime in the resin segment is 12% and 5% respectively) are soaked in water for 7 days, the contact angles are 53° and 57° respectively; the butanedione monoxime release concentration per unit area on each coating is about 0.8 mg / L and 0.39 mg / L respectively after the prepared degradable organosilicon hydrogel antifouling resin antifouling coating with a thickness of about 100 μm is placed in water for 24 h;

[0101] Antibacterial and antialgal performance: the two kinds of degradable organosilicon hydrogel antifouling resin coating / block materials (the content of butanedione monoxime in the resin segment is 12% and 5% respectively) and glass are placed in chlorella, and after 7 days, the anti-chlorella adhesion rate on the surface of the degradable organosilicon hydrogel antifouling resin coating is about 89% and 75% respectively compared with the glass control group.

[0102] The embodiment technology shows that by controlling the content of the hydrophilic segment and the organosilicon segment in the organic resin, the degradation rate, hydrophilic and hydrophobic properties and antifouling ability of the organosilicon hydrogel resin can be effectively regulated.

[0103] Example 3

[0104] The preparation method of this embodiment is basically the same as that of Example 1, except that the content of butanedione monoxime in the resin segment is adjusted to 12% and 5% respectively.

[0105] The contact angles of the two kinds of degradable organosilicon hydrogel antifouling resin coating / block materials obtained in this embodiment (the content of butanedione monoxime in the resin segment is 12% and 5% respectively) are 74° and 68° respectively; after the two kinds of degradable organosilicon hydrogel antifouling resin coating / block materials (the content of butanedione monoxime in the resin segment is 12% and 5% respectively) are soaked in water for 7 days, the contact angles are 53° and 57° respectively; the butanedione monoxime release concentration per unit area on each coating is about 0.8 mg / L and 0.39 mg / L respectively after the prepared degradable organosilicon hydrogel antifouling resin antifouling coating with a thickness of about 100 μm is placed in water for 24 h;

[0106] The embodiment technology shows that by controlling the content of the reversible covalent bond monomer in the organic resin, the degradation rate, self-healing ability and antifouling ability of the organosilicon hydrogel resin can be effectively regulated.

[0107] Example 4

[0108] The preparation method of this example is basically the same as that of Example 1, except that the hydrophilic segment is adjusted to be a polyether amine, the solvent is acetone, and after the isocyanate monomer is added to the mixed solution / emulsion to form a mixed reaction system, the reaction is carried out at room temperature for 12 h. After the reaction, a degradable organosilica hydrogel antifouling resin solution / prepolymer is obtained. The degradable organosilica hydrogel antifouling resin solution / prepolymer is coated on the surface of a substrate or cast in a mold, and the reaction is continued at 50°C for 12 hours and the solvent is removed. Further reaction is carried out at 80°C for 12 h, and after cooling, a degradable organosilica hydrogel antifouling resin coating / block material is obtained. The structure of the prepared poly-Schiff base macromolecule is shown in formula (12):

[0109]

[0110] wherein, R 11 is an aliphatic or aromatic alkane structure. In this example, the alkane structure after reaction of isophorone diisocyanate is m, n, p are independently selected from 1 to 20, and q is selected from 1 to 10.

[0111] The contact angle of the degradable organosilica hydrogel antifouling resin coating / block material obtained in this example is 81°, respectively. After soaking the degradable organosilica hydrogel antifouling resin coating / block material in water for 7 days, the contact angle is 69°. The release concentration of butanedione oxime per unit area on the degradable organosilica hydrogel antifouling resin antifouling coating with a thickness of about 100 μm is about 0.42 mg / L after being placed in water for 24 h.

[0112] This example illustrates that by controlling the properties of the hydrophilic monomers in the organosilica hydrogel resin, the degradation rate, hydrophilic / hydrophobic properties, and other properties of the organosilica hydrogel resin can be effectively controlled.

[0113] Example 5

[0114] The preparation method of this example is basically the same as that of Example 1, except that the chemical crosslinking segment is adjusted to be tris(2-aminoethyl)amine, and the preparation technology is also basically the same, as follows:

[0115] (1) Prepolymerization stage: at room temperature, polyethylene glycol, butanedione oxime, and amino-terminated dimethylsiloxane are dissolved in tetrahydrofuran with continuous stirring for more than half an hour to form an emulsion. Then, the isocyanate monomer is added to the mixed solution / emulsion to form a mixed reaction system, and the reaction is carried out at room temperature for 24 h. After the reaction, a degradable organosilica hydrogel antifouling resin solution / prepolymer is obtained.

[0116] (2) molding stage: adding tri(2-aminoethyl)amine monomer to continue the reaction for 30 min, coating the degradable organosilica hydrogel antifouling resin solution / prepolymer on the surface of the substrate or pouring into the mold, continuing the reaction at 50°C for 12 h and removing the solvent, further reacting at 80°C for 12 h, and obtaining the degradable organosilica hydrogel antifouling resin coating / block material after cooling, and the structure of the prepared poly-Schiff base macromolecule is shown in the following formula:

[0117]

[0118] wherein R 11 is an aliphatic or aromatic alkane structure, and in the present embodiment, the alkane structure after the reaction of isophorone diisocyanate is m, n, and p are independently selected from 1 to 20, and q is selected from 1 to 10.

[0119] The contact angle of the degradable organosilica hydrogel antifouling resin coating / block material obtained in the present embodiment is 70°; after the degradable organosilica hydrogel antifouling resin coating / block material is immersed in water for 7 days, the contact angles are 54°, respectively; and after the prepared degradable organosilica hydrogel antifouling resin antifouling coating with a thickness of about 100 μm is placed in water for 24 h, the release concentration of butanedione oxime per unit area on the coating is about 0.55 mg / L, respectively.

[0120] The present embodiment illustrates that tri(2-aminoethyl)amine is a primary amine crosslinking monomer, which has high reactivity with isocyanate, so that all the tri(2-aminoethyl)amine is added in the molding stage, instead of being added in batches in different stages. By controlling the properties of the crosslinking monomers in the organosilica hydrogel resin, the degradation rate, hydrophilic / hydrophobic properties, and other properties of the organosilica hydrogel resin can be effectively regulated.

[0121] Example 6

[0122] The preparation method of the present embodiment is basically the same as that of Example 1, except that the degradable segments (dioxygen monomers) are respectively adjusted to 1,2-cycloheptanedione dioxygen and p-benzoquinone dioxygen, and the preparation technology is basically the same, and the specific process is as follows:

[0123] (1) Prepolymerization stage: at room temperature, polyethylene glycol, glycerol (50% of the planned amount), 1,2-cycloheptanedione dioxygen or p-benzoquinone dioxygen, and amino-terminated dimethylsiloxane are dissolved in tetrahydrofuran, and stirring is continued for more than half an hour to form an emulsion. Subsequently, the isocyanate monomer is added to the mixed solution / emulsion to form a mixed reaction system, and the reaction is carried out at 0°C for 5 days. After the reaction, a degradable organosilica hydrogel antifouling resin solution / prepolymer is obtained.

[0124] (2) shaping stage: adding the rest of the multi-functional cross-linking monomer glycerol, after 1 h of reaction, the degradable organosilica hydrogel antifouling resin solution / prepolymer is coated on the surface of the substrate or cast in a mold, and the reaction is continued at 50 °C for 12 h and the solvent is removed, and further reaction is carried out at 80 °C for 12 h, and after cooling, the degradable organosilica hydrogel antifouling resin coating / block material is obtained. The structure of the poly-Schiff base macromolecule prepared by using 1,2-cycloheptanedione dioxime as the degradable monomer is as shown in the following formula:

[0125]

[0126] The structure of the poly-Schiff base macromolecule prepared by using p-benzoquinone dioxime as the degradable monomer is as shown in the following formula:

[0127]

[0128] wherein, R 11 is an aliphatic or aromatic alkane structure, and in this embodiment, the alkane structure after the reaction of isophorone diisocyanate is m, n, and p are independently selected from 1 to 20, and q is selected from 1 to 10.

[0129] The contact angles of the degradable organosilica hydrogel antifouling resin coating / block material obtained in this embodiment are 74° and 73°, respectively; after the degradable organosilica hydrogel antifouling resin coating / block material is immersed in water for 7 days, the contact angles are 58° and 56°, respectively; the prepared degradable organosilica hydrogel antifouling resin antifouling coating with a thickness of about 100 μm is placed in water for 24 h, and the release concentrations of 1,2-cycloheptanedione dioxime and p-benzoquinone dioxime per unit area on the coating are about 0.61 mg / L and 0.46 mg / L, respectively;

[0130] This embodiment illustrates that the butanedione dioxime in Example 1, the 1,2-cycloheptanedione dioxime in this embodiment, and the p-benzoquinone dioxime in this embodiment are all dioxime cross-linking monomers, and thus can react with isocyanate groups to produce degradable dynamic covalent bonds. Compared with butanedione dioxime, the alkane groups in the 1,2-cycloheptanedione dioxime and the p-benzoquinone dioxime in this embodiment account for a larger proportion, and the polarity is smaller, and the contact angle is larger. Therefore, by controlling the properties of the degradable monomers in the organosilica hydrogel resin, the degradation rate, hydrophilicity and other properties of the organosilica hydrogel resin can be effectively regulated.

[0131] Example 7

[0132] The preparation method of this embodiment is basically the same as that of Example 1, except that the first multi-functional cross-linking monomer is adjusted to be tri(2-aminoethyl)amine, and the second multi-functional monomer is still glycerol, wherein the molar ratio of tri(2-aminoethyl)amine to glycerol is 1:1, and the preparation technology is basically the same, except that the specific differences are as follows:

[0133] (1) Pre-polymerization stage: At room temperature, polyethylene glycol, tris(2-aminoethyl)amine (50% of the planned molar amount), butanedione and amino-terminated dimethylsiloxane were dissolved in tetrahydrofuran, and stirring was continued for more than half an hour to form an emulsion. Subsequently, the isocyanate monomer was added to the mixed solution / emulsion to form a mixed reaction system, which was reacted at 100°C for 5 min. After the reaction, a degradable organosilica hydrogel antifouling resin solution / prepolymer was obtained.

[0134] (2) Molding stage: The multifunctional crosslinking monomer glycerol (50% of the planned molar amount) was added, and after 1 h of reaction, the degradable organosilica hydrogel antifouling resin solution / prepolymer was coated on the surface of a substrate or cast in a mold, and the reaction was continued at 50°C for 12 h and the solvent was removed, and further reaction was carried out at 80°C for 12 h. After cooling, a degradable organosilica hydrogel antifouling resin coating / block material was obtained, and the structure of the prepared poly-Schiff base macromolecule is shown in the following formula:

[0135]

[0136] wherein R11 is an aliphatic or aromatic alkane structure, which in this embodiment is the alkane structure after reaction of isophorone diisocyanate m, n, p are independently selected from 1 to 20, and q is selected from 1 to 10.

[0137] The properties of the degradable organosilica hydrogel antifouling resin coating / block material obtained in this embodiment are basically the same as those in Example 1 and Example 5, and the contact angle is 70°. After the degradable organosilica hydrogel antifouling resin coating / block material was soaked in water for 7 days, the contact angle was 55°. The degradable organosilica hydrogel antifouling resin antifouling coating prepared with a thickness of about 100 μm was placed in water for 24 h, and the butanedione release concentration per unit area on each coating was about 0.53 mg / L.

[0138] This embodiment illustrates that compared with glycerol, tris(2-aminoethyl)amine is a primary amine crosslinking monomer with high reactivity with isocyanate. In the preparation of the degradable organosilica hydrogel antifouling resin coating, the type and amount of the multifunctional crosslinking monomer can be flexibly controlled to control the reaction process and material properties.

[0139] Example 8

[0140] The preparation method of this example is basically the same as that of Example 1, except that the isorone diisocyanate segment is adjusted to p-phenylene diisocyanate, the solvent is acetone, and after the isocyanate monomer is added to the mixed solution / emulsion to form a mixed reaction system, the reaction is carried out at 10°C for 12h. After the reaction, a degradable organosilica hydrogel antifouling resin solution / prepolymer is obtained. The degradable organosilica hydrogel antifouling resin solution / prepolymer is coated on the surface of a substrate or cast in a mold, and the reaction is continued at 40°C for 12 hours and the solvent is removed, and further reaction is carried out at 60°C for 12h. After cooling, a degradable organosilica hydrogel antifouling resin coating / block material is obtained, and the structure of the prepared poly-Schiff base macromolecule is shown in formula (12):

[0141]

[0142] wherein R 11 is an aliphatic or aromatic alkane structure, and in this example, the alkane structure after reaction of p-phenylene diisocyanate is m, n, p are independently selected from 1-20, and q is selected from 1-10.

[0143] The contact angle of the degradable organosilica hydrogel antifouling resin coating / block material obtained in this example is 83°, respectively. After immersing this degradable organosilica hydrogel antifouling resin coating / block material in water for 7 days, the contact angle is 68°. The degradable organosilica hydrogel antifouling resin antifouling coating prepared in this example has a thickness of about 100μm, and after being placed in water for 24h, the release concentration of butanedione oxime per unit area on the coating is about 0.39mg / L, respectively.

[0144] This example illustrates that by controlling the properties of diisocyanate monomers in organosilica hydrogel resin, the reaction rate, degradation rate, hydrophilic / hydrophobic properties, etc. of organosilica hydrogel resin can be controlled.

[0145] Comparative Example 1

[0146] Linear organosilica hydrogel

[0147] (1) Prepolymerization stage: At room temperature, polyethylene glycol, butanedione oxime and amino-terminated dimethylsiloxane are dissolved in tetrahydrofuran, and stirring is continued for more than half an hour to form an emulsion. Subsequently, the isocyanate monomer is added to the mixed solution / emulsion to form a mixed reaction system, and the reaction is carried out at room temperature for 24h. After the reaction, a degradable organosilica hydrogel antifouling resin solution is obtained.

[0148] (2) Molding stage: The degradable organosilicon hydrogel antifouling resin solution / prepolymer is coated on the surface of the substrate or cast in a mold, the reaction is continued at 50°C for 12 h and the solvent is removed, and further reaction is carried out at 80°C for 12 h, and after cooling, a linear degradable organosilicon hydrogel antifouling resin coating / block material is obtained. The prepared linear organosilicon hydrogel structure is shown in the following formula:

[0149]

[0150] Comparative Example 2

[0151] Organosilicon hydrogel without dynamic covalent bond

[0152] The preparation method of the present comparative example is basically the same as that of Comparative Example 1, except that no butandial (dynamic covalent bond monomer) is added in the raw material ratio, and an organosilicon hydrogel resin without dynamic covalent bond monomer is used. The chemical reaction of the obtained degradable hydrogel resin is shown in the following formula:

[0153]

[0154] Comparative Example 3

[0155] Degradable hydrogel resin

[0156] The preparation method of the present comparative example is basically the same as that of Comparative Example 1, except that no amino-terminated dimethylsiloxane (hydrophobic monomer) is added in the raw material ratio, and a degradable hydrogel resin is obtained. The chemical reaction of the obtained degradable hydrogel resin is shown in the following formula:

[0157]

[0158] Comparative Example 4

[0159] Degradable organosilicon resin

[0160] The preparation method of the present comparative example is basically the same as that of Comparative Example 1, except that no polyethylene glycol (hydrophilic monomer) is added in the raw material ratio, and a degradable organosilicon resin is obtained. The chemical structure of the obtained degradable organosilicon resin is shown in the following formula:

[0161]

[0162] In the chemical structural formula of the present comparative example, R0, R1, R2, R3, R4, R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , m, n, p, q, w and z are defined as described above.

[0163] The resins provided by the above-mentioned example 1 and comparative examples 1-4 were made into coating layers for performance testing, and the main comparison results are as follows:

[0164] Serial number Self-repairing ability at room temperature Contact angle (°) Degradation rate Strength (ranking) Example 1 Good 71 Moderate 3 Comparative Example 1 Good 66 Faster 5 Comparative Example 2 None 68 Very slow 2 Comparative Example 3 Good 22 Fast 1 Comparative Example 4 Good 109 Slower 4

[0165] Comparative example technical description: Comparative examples 1-4 can be used as a comparison of examples 1-3. Comparative example 1 lacks a multi-functional ammonia or alcohol cross-linking monomer, and the resin structure is linear. Compared with example 1, the resin structure strength is lower and the hydrolysis is faster; Comparative example 2 does not add an oxime reversible covalent bond monomer, so that the self-repairing ability at room temperature is insufficient and the degradation rate in water medium is very slow; Comparative example 3 has no organic silicon segment, which is a pure hydrogel coating. Because the hydrogel has a reversible covalent bond, it has a certain self-repairing ability and can be degraded in water medium; Comparative example 4 has no hydrophilic segment, which is a hydrophobic silicone resin. Because the reversible covalent bond is introduced into the resin structure, it has a certain self-repairing ability and degradable ability in water medium.

[0166] In addition, the inventors of the present case also refer to the foregoing examples, and have carried out tests with other raw materials, process operations and process conditions described in the specification, and have obtained relatively ideal results.

[0167] It should be understood that the technical solutions of the present application are not limited to the specific implementation cases described above. Any technical modification made according to the technical solutions of the present application without departing from the purpose of the present application and the scope protected by the claims falls within the protection scope of the present application.

Claims

1. A biodegradable organosilicon hydrogel antifouling resin, characterized in that, The biodegradable silicone hydrogel antifouling resin has the structure shown in formula (I): Formula (I) Wherein, R0 is a multifunctional alcohol or amine structural unit, and R0 is selected from... or R 10 It is an aliphatic structure, and x is selected from 3 to 6; R1 is a diisocyanate structural unit, and R1 is selected from... R 11 It has an aliphatic or aromatic alkane structure; R2 is a hydrophilic chain segment structural unit, and R2 is selected from... or y is 1~5, z is 1~250; R3 is a structural unit containing a dioxime functional group, and R3 is selected from... R 12 It has an aliphatic or aromatic alkane structure; R4 is a structural unit containing organosilicon, and R4 is selected from... or R 13 R 14 Independently selected from methyl or phenyl, R 15 is an alkane segment, and w is selected from 10 to 200; m, n, and p are independently selected from 1 to 20, and q is selected from 1 to 10.

2. The biodegradable organosilicon hydrogel antifouling resin according to claim 1, characterized in that: The structure of the biodegradable organosilicon hydrogel antifouling resin includes hydrophilic segments, organosilicon segments, dynamic chemical bond segments, and chemical crosslinking segments; wherein, the hydrophilic segments are hydrophilic segment structural units, the organosilicon segments are organosilicon structural units, the dynamic chemical bond segments are dioxime functional group structural units, and the chemical crosslinking segments are multifunctional alcohol structural units or multifunctional amine structural units.

3. The biodegradable organosilicon hydrogel antifouling resin according to claim 2, characterized in that: The biodegradable organosilicon hydrogel antifouling resin contains 5wt%~75wt% hydrophilic segments, 20wt%~85wt% organosilicon segments, 5wt%~40wt% dynamic chemical bond segments, and 0.1wt%~10wt% chemical crosslinking segments.

4. The biodegradable organosilicon hydrogel antifouling resin according to claim 3, characterized in that: The biodegradable organosilicon hydrogel antifouling resin has a hydrophilic chain content of 10wt%~60wt%, an organosilicon segment content of 30wt%~70wt%, a dynamic chemical bond segment content of 10wt%~30wt%, and a chemical crosslinking segment content of 0.5wt%~5wt%.

5. The biodegradable organosilicon hydrogel antifouling resin according to claim 1, characterized in that: The contact angle between the surface of the biodegradable silicone hydrogel antifouling resin and water is 150~30°.

6. The biodegradable organosilicon hydrogel antifouling resin according to claim 1, characterized in that: The degradation rate of the biodegradable silicone hydrogel antifouling resin is 0.01~10 mg·cm⁻¹. -2 ·day -1 .

7. The biodegradable organosilicon hydrogel antifouling resin according to claim 1, characterized in that: The biodegradable silicone hydrogel antifouling resin has any of the structures shown in the following formulas: Among them, R 11 It has an aliphatic or aromatic alkane structure, where m, n, and p are independently selected from 1 to 20, and q is selected from 1 to 10.

8. The method for preparing the biodegradable organosilicon hydrogel antifouling resin according to any one of claims 1-7, characterized in that, include: Under a protective atmosphere, a mixed reaction system comprising a hydrophilic monomer, a first multifunctional monomer, an organosilicon monomer, a dioxime monomer, an isocyanate monomer, and a solvent is reacted to prepare a biodegradable organosilicon hydrogel antifouling resin prepolymer; wherein the hydrophilic monomer comprises an amine or alcohol hydrophilic monomer, and the amine or alcohol hydrophilic monomer comprises any one or a combination of two or more of polyetheramine, polyethyleneimine, ethylenediamine, propylenediamine, diethylenetriamine, triethylenetetramine, polyethylene glycol, polypropylene glycol, polybutanediol, polypentylene glycol, ethylene glycol, propylene glycol, and butanediol; the first multifunctional monomer comprises any one or a combination of two or more of tris(2-aminoethyl)amine, glycerol, pentaerythritol, trimethylolethane, xylitol, and sorbitol. Furthermore, the biodegradable silicone hydrogel antifouling resin prepolymer is mixed with and reacted with a second multifunctional monomer to obtain a biodegradable silicone hydrogel antifouling resin; wherein the second multifunctional monomer is the same as or different from the first multifunctional monomer.

9. The preparation method according to claim 8, characterized in that, Specifically, it includes: In a protective atmosphere, the hydrophilic monomer, the first multifunctional monomer, the organosilicon monomer, the dioxime monomer, and the solvent are thoroughly mixed at 0~100°C to form a mixed dispersion, and then the isocyanate monomer is added to form the mixed reaction system.

10. The preparation method according to claim 8, characterized in that: The reaction temperature of the mixed reaction system is 0~100℃, and the reaction time is 5min~5 days.

11. The preparation method according to claim 8, characterized in that, Specifically, it includes: The biodegradable silicone hydrogel antifouling resin prepolymer is mixed with a second multifunctional monomer and reacted at 0-120°C for 5 min-36 h. The resulting mixture is then applied to a substrate surface or placed in a mold and reacted at 0-120°C for another 5 min-72 h to obtain the biodegradable silicone hydrogel antifouling resin. The biodegradable silicone hydrogel antifouling resin includes a biodegradable silicone hydrogel antifouling resin coating and / or a biodegradable silicone hydrogel antifouling resin bulk material.

12. The preparation method according to claim 8, characterized in that: The ammonia or alcohol hydrophilic monomers are any one or a combination of two or more of polyetheramine, polyethylene glycol, polypropylene glycol, and polyethyleneimine.

13. The preparation method according to claim 8, characterized in that: The first multifunctional monomer is any one or a combination of two or more of tris(2-aminoethyl)amine, glycerol, pentaerythritol, and trimethylolpropane.

14. The preparation method according to claim 8, characterized in that: The organosilicon monomer includes any one or a combination of two or more of aminopropyl-terminated polydimethylsiloxane, aminopropyl-terminated polymethylphenylsiloxane, hydroxyalkyl-terminated polydimethylsiloxane, and hydroxyalkyl-terminated polymethylphenylsiloxane.

15. The preparation method according to claim 14, characterized in that: The organosilicon monomer is any one or a combination of two or more of aminopropyl-terminated polydimethylsiloxane, hydroxypropyl-terminated polydimethylsiloxane, and hydroxyalkyl-terminated polymethylphenylsiloxane.

16. The preparation method according to claim 8, characterized in that: The dioxime monomers include any one or a combination of two or more of the following: glyoxime, dimethylglyoxime, acetone aldehyde dioxime, 1,2-cycloheptadecane dioxime, 9,10-phenanthroline dioxime, furozyloyl dioxime, acenaphthoquinone dioxime, p-benzoquinone dioxime, and dimethyl ketone dioxime.

17. The preparation method according to claim 16, characterized in that: The dioxime monomer is any one or a combination of two or more of the following: dioxime, dimethyldioxime, dimethyl ketone dioxime, and p-benzoquinone dioxime.

18. The preparation method according to claim 8, characterized in that: The solvent includes any one or a combination of two or more of the following: acetone, tetrahydrofuran, dichloromethane, chloroform, dimethylformamide, dimethylacetamide, toluene, xylene, n-butyl ether, and ethyl acetate.

19. The preparation method according to claim 8, characterized in that: The content of hydrophilic monomer in the mixed reaction system is 5wt%~75wt%, the content of organosilicon monomer is 20wt%~85wt%, the content of dioxime monomer is 5wt%~40wt%, and the content of the sum of the first polyfunctional monomer and the second polyfunctional monomer is 0.1wt%~10wt%.

20. The preparation method according to claim 19, characterized in that: The content of hydrophilic monomer in the mixed reaction system is 10wt%~60wt%, the content of organosilicon monomer is 30wt%~70wt%, the content of dioxime monomer is 10wt%~30wt%, and the content of the sum of the first polyfunctional monomer and the second polyfunctional monomer is 0.5wt%~5wt%.

21. The preparation method according to claim 8, characterized in that: The molar ratio of the first multifunctional monomer to the second multifunctional monomer is 1~10:1~10.

22. The preparation method according to claim 21, characterized in that: The molar ratio of the first multifunctional monomer to the second multifunctional monomer is 1~3:1~3.

23. The preparation method according to claim 8, characterized in that: The solvent content in the mixed reaction system is 10~95wt%.

24. The preparation method according to claim 23, characterized in that: The solvent content in the mixed reaction system is 40~80wt%.

25. The application of the biodegradable silicone hydrogel antifouling resin according to any one of claims 1-7 in the field of antibacterial or antifouling of substrate surfaces.

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