Poly-schiff base / polyurea / polyurethane synergistically modified silicone-based hydrophilic-hydrophobic antifouling resin solution, and preparation method and application thereof

Abstract

The application discloses a polyschiff base / polyurea / polyurethane synergistically modified silicone-based hydrophilic-hydrophobic antifouling resin solution and a preparation method and application thereof. The resin solution is polyschiff base / polyurea / polyurethane synergistically modified silicone-based hydrophilic-hydrophobic antifouling resin and a solvent, and the antifouling resin has the structure shown in the following formula. The application realizes contact sterilization by using hydrophilic-hydrophobic chain segments in cooperation, the silicone elastomer provides physical resistance to fouling, dynamic chemical bonds endow controllability of coating thickness and degradation rate, and degradation products are natural products. The resin has excellent dynamic / static antifouling capacity, and has wide application prospects in the field of marine antifouling engineering.

Description

Technical Field

[0001] This invention belongs to the field of antifouling and antibacterial technology, specifically relating to a polySchiff base / polyurea / polyurethane synergistic modified organosilicon-based hydrophilic and hydrophobic antifouling resin, its preparation method and application. Background Technology

[0002] Marine biofouling refers to the phenomenon where microorganisms, algae, and invertebrates attach to, colonize, and cause damage to the surfaces of ships, underwater sensors, aquaculture cages, and other facilities. Globally, this causes direct and indirect economic losses amounting to tens of billions of US dollars annually, manifesting as increased ship drag, significantly increased fuel consumption (up to 40%), signal distortion in monitoring instruments, and accelerated corrosion of metal structures. With the deepening of marine economic activities and the increase in marine engineering facilities, developing efficient and long-lasting antifouling technologies has become crucial for ensuring the sustainable development of the marine industry.

[0003] The application of antifouling materials is currently the most economical, effective, and widely used technology for preventing marine biofouling. Since the international conventions have banned toxic antifouling agents such as tributyltin (TBT), the development of environmentally friendly antifouling coatings has become the mainstream direction. Among them, low surface energy organosilicon coatings, represented by polydimethylsiloxane (PDMS), have attracted much attention in the field of antifouling due to their excellent hydrophobicity, good biocompatibility, and fouling removal performance. Their antifouling mechanism mainly relies on low surface energy and high elastic modulus, making biological adhesion weak and allowing them to be removed under the shearing action of water flow. However, pure PDMS coatings still have obvious limitations in practical applications: First, their mechanical strength is generally low, making them prone to wear or physical damage in dynamic marine environments; second, under static or low-flow conditions, organic matter such as mucus secreted by fouling organisms can easily form a stable adhesive layer on their surface, leading to a sharp decline in antifouling performance, i.e., "static antifouling failure"; in addition, the single characteristic of low surface energy is insufficient to cope with the complex and diverse marine biofouling.

[0004] To overcome the aforementioned shortcomings, researchers often introduce functional segments into organosilicon systems through chemical modification. For example, patent CN118240463A discloses an organosilicon-modified polyurea polyurethane antifouling coating, comprising organosilicon-modified polyurea polyurethane and tannic acid. This polymer sequentially polymerizes polysiloxane, phenyl disulfide, and isocyanate tannic acid to form a composite antifouling coating with excellent mechanical properties and static antifouling strength, thus compensating for the insufficient mechanical properties of organosilicon coatings. Patents CN117126578B, CN117126604B, and CN118667114A disclose a polysiloxane-modified antifouling resin. This type of resin material contains amphiphilic segments, siloxane segments grafted with biocides, and a rigid molecular structure, while simultaneously enhancing the mechanical properties and active bactericidal properties of polysiloxane. However, these improvement schemes mostly focus on improving initial antifouling performance and mechanical strength, and the surface chemical structure of the coating usually remains static during service. When exposed to marine environments for extended periods, algae, bacteria, and their secreted extracellular polymeric substances (EPS) gradually form dense biofilms on the coating surface. These biofilms are difficult to remove through simple physical desorption mechanisms, leading to a decline in the antifouling performance of the coating over time and hindering long-term antifouling effectiveness. Therefore, developing an antifouling coating with dynamic surface regeneration capabilities, the ability to actively desorb initial biofilms, and good mechanical properties combined with environmental friendliness has become a pressing technical challenge in this field. Summary of the Invention

[0005] The main objective of this invention is to provide a polySchiff base / polyurea / polyurethane synergistic modified organosilicon-based hydrophilic and hydrophobic antifouling resin solution, its preparation method and application, in order to overcome the shortcomings of the prior art.

[0006] To achieve the aforementioned objectives, the technical solution adopted by this invention includes:

[0007] This invention provides a polySchiff base / polyurea / polyurethane synergistic modified silicone-based hydrophilic and hydrophobic antifouling resin solution, comprising: a polySchiff base / polyurea / polyurethane synergistic modified silicone-based hydrophilic and hydrophobic antifouling resin and a solvent, wherein the antifouling resin has a structure as shown in formula (I):

[0008]

[0009] Formula (I);

[0010] Wherein, R0 is selected from phenyl, aryl, or alkane groups; R1 and R2 are independently selected from monofunctional antibacterial / antifouling alcohols. and / or hydrophilic ethers with terminal hydroxyl groups p is selected from 4-150; R3, R7, and R8 are independently selected from alkyl groups; R4 is selected from methyl, vinyl, or phenyl groups; R5 is selected from difunctional aldehydes. R6 is selected from alkyl, olefinic, fluorinated alkyl or polyether segments; R9 is selected from phenyl and / or alkyl; m is selected from 3-51.

[0011] This invention also provides a method for preparing the aforementioned polySchiff base / polyurea / polyurethane synergistic modified organosilicon-based hydrophilic and hydrophobic antifouling resin solution, comprising:

[0012] Hydrophilic monofunctional monomers, hydrophobic monofunctional antibacterial / antifouling functional monomers, trifunctional isocyanate monomers, catalysts and solvents are mixed and reacted to prepare hydrophilic and hydrophobic modified isocyanate monomers.

[0013] The hydrophilic-hydrophobic modified isocyanate monomer, polysiloxane monomer and solvent are mixed and reacted to obtain a hydrophilic-hydrophobic modified organosilicon prepolymer;

[0014] Furthermore, the hydrophilic-hydrophobic modified organosilicon prepolymer is mixed with a bifunctional aldehyde compound and reacted to obtain a polySchiff base / polyurea / polyurethane synergistic modified organosilicon-based hydrophilic-hydrophobic antifouling resin solution.

[0015] This invention also provides a method for preparing a biodegradable hydrophilic / hydrophobic synergistic modified organosilicon-based antifouling coating, comprising:

[0016] Provides the aforementioned polySchiff base / polyurea / polyurethane synergistic modified organosilicon-based hydrophilic and hydrophobic antifouling resin solution;

[0017] Furthermore, the polySchiff base / polyurea / polyurethane synergistic modified silicone-based hydrophilic and hydrophobic antifouling resin solution is applied to the substrate surface and dried and cured to obtain a biodegradable hydrophilic / hydrophobic synergistic modified silicone-based antifouling coating.

[0018] The biodegradable hydrophilic / hydrophobic synergistic modified organosilicon-based antifouling coating is prepared by the method described above; preferably, the thickness of the biodegradable hydrophilic / hydrophobic synergistic modified organosilicon-based antifouling coating is 50-800 μm.

[0019] The embodiments of the present invention also provide the application of the aforementioned polySchiff base / polyurea / polyurethane synergistic modified organosilicon-based hydrophilic / hydrophobic antifouling resin solution or biodegradable hydrophilic / hydrophobic synergistic modified organosilicon-based antifouling coating in the field of antifouling or antibacterial in marine environments.

[0020] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0021] (1) The polySchiff base / polyurea / polyurethane synergistic modified organosilicon-based hydrophilic and hydrophobic antifouling resin prepared in this invention contains a dynamic chemical bond - an imine bond; the dynamic covalent properties of the imine bond (C=N) enable it to efficiently integrate hydrophilic and hydrophobic organosilicon polymer segments through a reversible crosslinking mechanism to form a three-dimensional network structure. This crosslinking effectively improves the thermal properties of the material composition; at the same time, the imine bond will spontaneously degrade into aldehyde small molecules in the seawater environment. The degradation rate of the coating can be controlled by regulating the content of the dynamic chemical bond, effectively avoiding the harm of marine microplastics.

[0022] (2) The polySchiff base / polyurea / polyurethane synergistic modified organosilicon hydrophilic and hydrophobic antifouling resin prepared in this invention mainly contains functional segments such as hydrophilic segments formed by polyethylene glycol monomethyl ether and hydrophobic segments formed by solanesol; in an aquatic environment, the hydrophilic segments migrate to the surface of the substrate, easily forming a surface hydration layer, reducing direct contact between bacteria and the substrate, and inhibiting bacterial adhesion. The hydrophobic long chain of solanesol can destroy the bacterial structure. By cleverly combining hydrophilic and hydrophobic segments, the polySchiff base / polyurea / polyurethane synergistic modified organosilicon hydrophilic and hydrophobic antifouling resin can have both passive protection and active sterilization properties.

[0023] (3) This invention constructs an interpenetrating network structure combining rigid segments (urea / urethane bonds) and flexible segments (siloxanes) through the synergistic chemical crosslinking of polyurea / polyurethane segments and polysiloxanes. Among them, the abundant urethane bonds and urea bonds in the polyurea / polyurethane structure can form strong hydrogen bond interactions, which significantly enhances the cohesive energy density of the material and overcomes the defects of poor mechanical strength and easy damage of traditional organosilicon coatings. The resulting resin coating has higher elongation at break and tensile strength while maintaining low surface energy characteristics. It can withstand complex marine working conditions such as water flow erosion, sand and gravel impact and equipment deformation, and greatly extend the service life of the coating in dynamic marine environments.

[0024] (4) By introducing dynamic chemical bonds of polySchiff base, this invention endows the coating surface with controllable degradation and dynamic reconstruction capabilities in seawater environment. When the hydrophilic and hydrophobic segments on the coating surface fail due to microbial adhesion or biofilm pollution, the imine bond can break under the action of weakly acidic microenvironment or seawater, and detach along with the surface deposits, realizing the "self-renewal of the coating skin". At the same time, the newly exposed dynamic segments inside the coating can migrate to the surface again, continuously constructing hydrophilic and hydrophobic microregions with antibacterial activity. This multi-dynamic synergistic mechanism of "degradation-reconstruction-migration" enables the coating to have the functions of active sterilization, fouling desorption and inhibition of biofilm formation, and is especially suitable for antifouling needs in long-term static immersion environment. Attached Figure Description

[0025] To more clearly illustrate the technical solutions in the embodiments of this application or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments recorded in this application. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0026] Figure 1 This is a schematic diagram of the preparation process of the polySchiff base / polyurea / polyurethane synergistic modified organosilicon-based hydrophilic and hydrophobic antifouling resin in a typical embodiment of the present invention.

[0027] Figure 2 These are plate count diagrams showing the resistance of the coatings prepared in Examples 1-3 and Comparative Examples 1-5 of this invention to Escherichia coli.

[0028] Figures 3a-3b These are the 1H NMR spectrum and infrared spectrum of the organosilicon-modified hydrophilic-hydrophobic polyurea-polyurethane prepared in Comparative Example 4 of this invention.

[0029] Figures 4a-4b These are the 1H NMR spectrum and infrared spectrum of the biodegradable organosilicon-modified polyurea-polyurethane prepared in Comparative Example 5 of this invention.

[0030] Figure 5 The infrared spectrum of the polySchiff base / polyurea / polyurethane synergistic modified organosilicon-based hydrophilic and hydrophobic antifouling resin prepared in Example 1 of this invention.

[0031] Figure 6 This is a UV transmittance diagram of the coating prepared in Example 1 of the present invention;

[0032] Figure 7 These are bacterial morphology images of the sample surface observed at a distance of 2 μm after the coatings in the comparative examples 1-5 of the present invention were contaminated in a PBS dispersion of 1*10^8 CFU / mL bacterial solution for 24 h. Detailed Implementation

[0033] In view of the deficiencies of the prior art, the inventors of this case, through long-term research and extensive practice, have proposed the technical solution of this invention. The technical solution of this invention will be clearly and completely described below. Obviously, the described embodiments are only some, not all, of the embodiments of this invention. All other embodiments obtained by those skilled in the art based on the embodiments of this invention without creative effort are within the scope of protection of this invention.

[0034] Specifically, as one aspect of the technical solution of this invention, a polySchiff base / polyurea / polyurethane synergistic modified organosilicon-based hydrophilic and hydrophobic antifouling resin solution includes: a polySchiff base / polyurea / polyurethane synergistic modified organosilicon-based hydrophilic and hydrophobic antifouling resin and a solvent, wherein the antifouling resin has a structure as shown in formula (I):

[0035]

[0036] Formula (I);

[0037] Wherein, R0 is selected from phenyl, aryl, or alkane groups; R1 and R2 are independently selected from monofunctional antibacterial / antifouling alcohols. and / or hydrophilic ethers with terminal hydroxyl groups p is selected from 4-150, preferably 5-50; R3, R7, and R8 are independently selected from alkyl groups; R4 is selected from methyl, vinyl, or phenyl groups; R5 is selected from difunctional aldehydes. R6 is selected from alkyl, olefinic, fluorinated alkyl or polyether segments; R9 is selected from phenyl and / or alkyl; m is selected from 3-51, preferably 4-20.

[0038] In some preferred embodiments, the antifouling resin comprises hydrophilic segments, hydrophobic segments, a crosslinking agent portion, an organosilicon segment, and a dynamic chemical bond segment; wherein the hydrophilic segments are derived from hydrophilic monofunctional monomers, the hydrophobic segments are derived from hydrophobic monofunctional antibacterial / antifouling functional monomers, the dynamic chemical bond segment is derived from difunctional aldehyde compounds; the crosslinking agent portion is derived from trifunctional isocyanate monomers; and the organosilicon segment is derived from polysiloxane monomers.

[0039] Another aspect of the present invention provides a method for preparing the aforementioned polySchiff base / polyurea / polyurethane synergistic modified organosilicon-based hydrophilic and hydrophobic antifouling resin solution, comprising:

[0040] Hydrophilic monofunctional monomers, hydrophobic monofunctional antibacterial / antifouling functional monomers, trifunctional isocyanate monomers, catalysts and solvents are mixed and reacted to prepare hydrophilic and hydrophobic modified isocyanate monomers.

[0041] The hydrophilic-hydrophobic modified isocyanate monomer, polysiloxane monomer and solvent are mixed and reacted to obtain a hydrophilic-hydrophobic modified organosilicon prepolymer;

[0042] Furthermore, the hydrophilic-hydrophobic modified organosilicon prepolymer is mixed with a bifunctional aldehyde compound and reacted to obtain a polySchiff base / polyurea / polyurethane synergistic modified organosilicon-based hydrophilic-hydrophobic antifouling resin solution.

[0043] In some preferred embodiments, the preparation process of the polySchiff base / polyurea / polyurethane synergistic modified organosilicon-based hydrophilic and hydrophobic antifouling resin in this invention is shown in the schematic diagram below. Figure 1 As shown.

[0044] In some preferred embodiments, the preparation method specifically includes:

[0045] (1) A hydrophilic monofunctional monomer, a hydrophobic monofunctional antibacterial / antifouling functional monomer, a trifunctional isocyanate monomer, a catalyst and a solvent are mixed and reacted at 20-100 °C for 1-24 h to obtain a hydrophilic-hydrophobic modified isocyanate monomer with NCO terminal groups.

[0046] (2) The hydrophilic-hydrophobic modified isocyanate monomer, polysiloxane monomer and solvent are mixed and reacted at 20-100 °C for 1-24 h to obtain hydrophilic-hydrophobic modified organosilicon prepolymer;

[0047] (3) The hydrophilic and hydrophobic modified organosilicon prepolymer is mixed with a bifunctional aldehyde compound and reacted at 40-120 °C for 1-48 h to obtain a polySchiff base / polyurea / polyurethane synergistic modified organosilicon hydrophilic and hydrophobic antifouling resin solution.

[0048] Furthermore, the solid content of the hydrophilic-hydrophobic modified isocyanate monomer with NCO terminal groups is 10-35 wt%.

[0049] Furthermore, the solid content of the hydrophilic-hydrophobic modified organosilicon prepolymer is 20-60 wt%.

[0050] Furthermore, the molar ratio of the hydrophobic monofunctional antibacterial / antifouling functional monomer, the hydrophilic monofunctional monomer, and the trifunctional isocyanate monomer is (0.5-1.5):(0.5-1.5):(2-3).

[0051] Furthermore, the molar ratio of the polysiloxane monomer to the trifunctional isocyanate monomer is (1-3):1.

[0052] Furthermore, the molar ratio of the bifunctional aldehyde compound to the polysiloxane monomer is (0.5-1.5):2.

[0053] Furthermore, the hydrophilic monofunctional monomer includes any one or more combinations of polyethylene glycol monomethyl ether, polypropylene oxide monomethyl ether, polypropylene glycol monomethyl ether, poly(2-ethyl-2-oxazoline) monomethyl ether, and polyetheramine (monoamino), and is not limited thereto.

[0054] Furthermore, the hydrophilic monofunctional monomer is polyethylene glycol monomethyl ether with a number average molecular weight of 500-2000.

[0055] Furthermore, the hydrophobic monofunctional antibacterial / antifouling functional monomer includes any one or more combinations of solanyl alcohol, geraniol, menthol, tea tree alcohol, dodecyl monool, linalool, fluorinated benzyl alcohol, cholesterol, and perfluorohexyl ethanol, and is not limited thereto.

[0056] Furthermore, the hydrophobic monofunctional antibacterial / antifouling functional monomer is any one or more combinations of solanesol, solanesol, geraniol, menthol, and dodecyl monool, and is not limited thereto.

[0057] Furthermore, the trifunctional isocyanate monomer includes any one or more combinations of triphenylmethane triisocyanate, isophorone diisocyanate trimer, hexamethylene diisocyanate trimer, L-lysine triisocyanate, and triphenylmethane triisocyanate, and is not limited thereto.

[0058] Furthermore, the trifunctional isocyanate monomer is hexamethylene diisocyanate trimer and / or isophorone triisocyanate, but is not limited thereto.

[0059] Furthermore, the polysiloxane monomer includes, but is not limited to, aminopropyl-terminated polydimethylsiloxane.

[0060] Furthermore, the number-average molecular weight of the aminopropyl-terminated polydimethylsiloxane is 500-3000.

[0061] Furthermore, the bifunctional aldehyde compounds include any one or more combinations of glyoxal, glutaraldehyde, o-phthalaldehyde, terephthalaldehyde, and polyethylene glycol dipropionaldehyde, and are not limited thereto.

[0062] Furthermore, the difunctional aldehyde compound is o-phthalaldehyde and / or terephthalaldehyde, but is not limited thereto.

[0063] Furthermore, the catalyst comprises any one or more combinations of dibutyltin dilaurate, dibutyltin diacetate, dibutyltin dioctanoate, dioctyltin dilaurate, dioctyltin diacetate, dioctyltin dioctanoate, dioctyltin dioctanoate, dioctyltin 2-ethylhexanoate, and tin naphthenate, and is not limited thereto.

[0064] Furthermore, the solvent includes any one or more combinations of acetone, tetrahydrofuran, dimethyl sulfoxide, toluene, and xylene, and is not limited thereto.

[0065] Furthermore, the solvent is any one or more combinations of tetrahydrofuran, toluene, and xylene, and is not limited thereto.

[0066] Furthermore, the reactions in steps (1), (2), and (3) are all carried out under a protective atmosphere with a stirring rate of 200-1000 r / min.

[0067] Another aspect of this invention provides a method for preparing a biodegradable hydrophilic / hydrophobic synergistic modified organosilicon-based antifouling coating, comprising:

[0068] Provides the aforementioned polySchiff base / polyurea / polyurethane synergistic modified organosilicon-based hydrophilic and hydrophobic antifouling resin solution;

[0069] Furthermore, the polySchiff base / polyurea / polyurethane synergistic modified silicone-based hydrophilic and hydrophobic antifouling resin solution is applied to the substrate surface and dried and cured to obtain a biodegradable hydrophilic / hydrophobic synergistic modified silicone-based antifouling coating.

[0070] In some preferred embodiments, the solid content of the polySchiff base / polyurea / polyurethane synergistic modified silicone-based hydrophilic and hydrophobic antifouling resin solution is 20-60 wt%.

[0071] In some preferred embodiments, the ambient temperature during drying and curing is 20-80°C.

[0072] Another aspect of the present invention provides a biodegradable hydrophilic / hydrophobic synergistic modified organosilicon-based antifouling coating prepared by the aforementioned preparation method.

[0073] In some preferred embodiments, the thickness of the biodegradable hydrophilic / hydrophobic synergistic modified silicone-based antifouling coating is 50-800 μm.

[0074] Another aspect of the present invention provides the application of the aforementioned polySchiff base / polyurea / polyurethane synergistic modified silicone-based hydrophilic / hydrophobic antifouling resin solution or biodegradable hydrophilic / hydrophobic synergistic modified silicone-based antifouling coating in the field of antifouling or antibacterial in marine environments.

[0075] The technical solution of the present invention will be further described in detail below with reference to several preferred embodiments and accompanying drawings. This embodiment is implemented on the premise of the technical solution of the invention, and provides detailed implementation methods and specific operation processes. However, the protection scope of the present invention is not limited to the following embodiments.

[0076] Unless otherwise specified, the experimental materials used in the examples below can be purchased from conventional biochemical reagent companies.

[0077] Example 1

[0078] Step 1: Solanesol is mixed evenly with polyethylene glycol monomethyl ether and excess hexaisocyanate, and reacted at 60°C for 18 hours to obtain a hydrophilic-hydrophobic modified polyurethane prepolymer with NCO-terminated groups. The reaction process is as follows:

[0079]

[0080] Among them, the number average molecular weight of polyethylene glycol monomethyl ether (mPEG) is 750, and the molar ratio of solanesol, polyethylene glycol monomethyl ether and hexaisocyanate is 1:1:2.

[0081] Step 2: The prepolymer described in Step 1 is reacted with aminopropyl-terminated polydimethylsiloxane at 60°C for 5 hours to crosslink and form a hydrophilic-hydrophobic modified organosilicon prepolymer. The reaction process is as follows:

[0082]

[0083] Among them, the number-average molecular weight of aminopropyl-terminated polydimethylsiloxane (ATP-PDMS) is 1000, and the molar ratio of ATP-PDMS to hexaisocyanate is 2:1;

[0084] Step 3: Add terephthalaldehyde and the catalyst dibutyltin dilaurate to the material synthesized in Step 2. The mixed components are reacted at 90°C for 24 hours to form a polySchiff base / polyurea / polyurethane synergistic modified organosilicon-based hydrophilic and hydrophobic antifouling resin. The reaction process is as follows:

[0085]

[0086] In this process, the molar ratio of terephthalaldehyde and ATP-PDMS is 1:2, hexaisocyanate is used as a crosslinking agent, solanesol is a hydrophobic monomer, polyethylene glycol monomethyl ether is a hydrophilic monomer, toluene is used as a solvent during polymerization, and steps 1, 2 and 3 are carried out under protective gas conditions with a stirring rate of 500-600 r / min.

[0087] The infrared spectrum of the polySchiff base / polyurea / polyurethane synergistic modified organosilicon-based hydrophilic and hydrophobic antifouling resin prepared in this embodiment is as follows: Figure 5 As shown.

[0088] Example 2

[0089] The method is the same as in Example 1, except that different amounts of polyethylene glycol monomethyl ether and aminopropyl-terminated polyethylene glycol monomethyl ether are used. The number average molecular weight of polyethylene glycol monomethyl ether (mPEG) is 350; the number average molecular weight of aminopropyl-terminated polydimethylsiloxane (ATP-PDMS) is 3000.

[0090] Example 3

[0091] The method is the same as in Example 1, except that different amounts of polyethylene glycol monomethyl ether and aminopropyl-terminated polyethylene glycol monomethyl ether are used. The number average molecular weight of polyethylene glycol monomethyl ether (mPEG) is 2000; the number average molecular weight of aminopropyl-terminated polydimethylsiloxane (ATP-PDMS) is 1000.

[0092] Comparative Example 1 (Non-degradable organosilicon-modified polyurea)

[0093] Organosilicon-modified polyurea:

[0094] 2 g of aminopropyl polydimethylsiloxane was added to 4 mL of tetrahydrofuran and then added to a reaction flask. Subsequently, isoflurane isocyanate dissolved in 4 mL of toluene was added dropwise to the reaction flask containing the amine monomer. The reaction was carried out at 60 °C for 12 h to obtain organosilicon-modified polyurea.

[0095] Comparative Example 2 (Non-degradable hydrophilic / hydrophobic modified polyurea / polyurethane)

[0096] Hydrophilic and hydrophobic modified polyurea-polyurethane

[0097] (1) Hydrophilic and hydrophobic modified polyurethane prepolymer: 0.63 g of solanine alcohol and 0.75 g of polyethylene glycol monomethyl ether dissolved in 5 mL of toluene were added dropwise to 1 g of hexaisocyanate containing 5 mL of toluene, and the reaction was carried out at 60 °C for 18 h.

[0098] (2) Hydrophilic-hydrophobic modified polyurea / polyurethane composition: 0.34 g of isoflavone diamine was dissolved in 5 mL of toluene, and then hydrophilic-hydrophobic modified polyurethane prepolymer was added dropwise. After heating to 60℃ and reacting for 12 h, hydrophilic-hydrophobic modified polyurea-polyurethane was synthesized.

[0099] Comparative Example 3 (Degradable hydrophilic-hydrophobic modified polyurea-polyurethane)

[0100] Synergistic modification of organosilicon-based hydrophilic and hydrophobic compositions using polySchiff base / polyurea / polyurethane

[0101] (1) Hydrophilic and hydrophobic modified polyurethane prepolymer: 0.63 g of solanine alcohol and 0.75 g of polyethylene glycol monomethyl ether dissolved in 5 mL of toluene were added dropwise to 1 g of hexaisocyanate containing 5 mL of toluene, and the mixture was reacted at 60 °C for 18 h to obtain the hydrophilic and hydrophobic modified polyurethane prepolymer.

[0102] (2) Hydrophilic-hydrophobic modified polyurea-polyurethane: 0.34 g of isoflavone diamine was dissolved in 5 mL of toluene, and then hydrophilic-hydrophobic modified polyurethane prepolymer was added dropwise. After heating to 60℃ and reacting for 12 h, hydrophilic-hydrophobic modified polyurea-polyurethane was synthesized.

[0103] (3) Degradable hydrophilic and hydrophobic modified polyurea-polyurethane: Add 0.27 g of terephthalaldehyde and heat at 90°C for 24 h.

[0104] Comparative Example 4 (Non-degradable organosilicon-modified hydrophilic-hydrophobic polyurea-polyurethane)

[0105] (1) Hydrophilic and hydrophobic modified polyurethane prepolymer: 0.63 g of solanine alcohol and 0.75 g of polyethylene glycol monomethyl ether dissolved in 5 mL of toluene were added dropwise to 1 g of hexaisocyanate containing 5 mL of toluene, and the reaction was carried out at 60 °C for 18 h.

[0106] (2) Organosilicon-modified hydrophilic-hydrophobic polyurea-polyurethane: 2 g of aminopropyl-terminated polydimethylsiloxane was dissolved in 10 mL of toluene, and then hydrophilic-hydrophobic modified polyurethane prepolymer was added dropwise. The reaction was carried out at 60 °C for 12 h to synthesize organosilicon-modified hydrophilic-hydrophobic polyurea-polyurethane. Its 1H NMR spectrum is shown below. Figure 3a As shown, the infrared spectrum is as follows Figure 3b As shown.

[0107] Comparative Example 5 (non-hydrophobic biodegradable silicone-modified polyurea-polyurethane)

[0108] (1) Hydrophilic and hydrophobic modified polyurethane prepolymer: 1.26 g of solanine alcohol dissolved in 5 mL of toluene was added dropwise to 1 g of hexaisocyanate containing 5 mL of toluene, and the reaction was carried out at 60 °C for 18 h.

[0109] (2) Organosilicon-modified polyurea-polyurethane: 2 g of aminopropyl-terminated polydimethylsiloxane was dissolved in 10 mL of toluene, and then hydrophilic and hydrophobic modified polyurethane prepolymer was added dropwise. The reaction was carried out at 60 °C for 12 h to synthesize organosilicon-modified polyurea-polyurethane.

[0110] (3) Biodegradable organosilicon-modified polyurea-polyurethane: 0.27 g of terephthalaldehyde was added, and the mixture was heated at 90 °C for 24 h to obtain biodegradable organosilicon-modified polyurea-polyurethane. Its 1H NMR spectrum is shown below. Figure 4a As shown, the infrared spectrum is as follows Figure 4b As shown.

[0111] The final products prepared in Examples 1-3 and Comparative Examples 1-5 were coated on the surface of the substrate and cured and dried at 60°C for 48 h to form a cured resin-based coating.

[0112] test:

[0113] Contact angle and antifouling performance tests used a glass slide as the substrate (thickness: 1 mm), with the film thickness controlled at 500 μm. Ultraviolet transmittance tests used a quartz glass slide as the substrate, with a blank quartz glass slide as the background. The blank sample in the scanning test was a blank glass sample.

[0114] Contact angle: Deionized water was dropped onto the surfaces of different sample control samples at room temperature, and the static contact angle of the droplets on the sample surfaces was then measured. Due to the presence of long-chain organosilicon segments and cross-linking units, the contact angles of Examples 1 and 2 both reached over 110°, exhibiting good hydrophobic properties.

[0115] Antifouling performance testing: After different samples were contaminated in PBS dispersion containing 1*10^8 CFU / mL bacterial solution for 24 h, the antibacterial rate of the samples was calculated using the plate count method. Plate count graphs of resistance to *E. coli* in Examples 1-3 and Comparative Examples 1-5 are shown below. Figure 2 As shown.

[0116] Nuclear magnetic resonance (NMR) structural testing: The uncured sample was dissolved in CDCl3 and then subjected to 1H NMR spectroscopy.

[0117] Infrared testing: The infrared peaks of the sample are observed using infrared spectroscopy. The presence of characteristic peaks of polyurea / polyurethane / imine bonds / organosilicon segments / hydrophilic and hydrophobic segments indicates the successful synthesis of the target product.

[0118] UV transmittance test: The transmittance of the cured resin coating applied to a quartz glass slide was tested in the range of 200-1000 nm. The UV transmittance curve of Example 1 is shown below. Figure 6 As shown, when the wavelength is greater than 600 nm, a transmittance of over 90% is obtained.

[0119] Scanning test: The bacterial morphology of the sample surface was observed at a distance of 2 μm after the sample had been contaminated in a PBS dispersion of 1*10^8 CFU / mL bacterial solution for 24 h using an electron scanning microscope. Figure 7 As shown. With Figure 2 Consistent with the colony distribution results observed using colony counting, only a very small number of bacteria were observed adhering to the surface in Examples 1, 2, and 3.

[0120] The coating performance test results of Example 1 and Comparative Examples 1-5 are shown in Table 1;

[0121] Table 1

[0122] Serial Number Project Indicators Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 1 Contact angle / ° 114 123 58 92 85 93 97 99 2 <![CDATA[Bacterial adhesion cell / cm 2 > 0.0 0.1 0.0 15.6 9.3 4.6 8.8 20.5 3 Antibacterial rate / % 99.9 98.8 99.9 56.2 75.1 85.3 80.5 4.2

[0123] The comparison between Examples 1-3 and Comparative Examples 1-5 shows that the functional segments (hydrophilic and hydrophobic segments, silicone segments, biodegradable segments, etc.) that make up the antifouling coating play a very important role in resisting bacterial adhesion and the hydrophobicity of the coating.

[0124] In addition, the inventors of this case also conducted experiments with other raw materials, process operations, and process conditions described in this specification, referring to the aforementioned embodiments, and obtained relatively ideal results in all cases.

[0125] It should be understood that the technical solutions of the present invention are not limited to the specific embodiments described above. Any technical modifications made to the technical solutions of the present invention without departing from the spirit and scope of the claims are within the scope of protection of the present invention.

Claims

1. A polySchiff base / polyurea / polyurethane synergistic modified organosilicon-based hydrophilic and hydrophobic antifouling resin solution, characterized in that, include: A polySchiff base / polyurea / polyurethane synergistic modified organosilicon-based hydrophilic and hydrophobic antifouling resin and a solvent, wherein the antifouling resin has a structure as shown in formula (I): ； Formula (I); R0 is selected from phenyl, aryl, or alkane groups; R1 and R2 are independently selected from monofunctional antibacterial / antifouling alcohols. and / or hydrophilic ethers with terminal hydroxyl groups p is selected from 4-150, preferably 5-50; R3, R7, and R8 are independently selected from alkyl groups; R4 is selected from methyl, vinyl, or phenyl groups; R5 is selected from difunctional aldehydes. R6 is selected from alkyl, olefinic, fluorinated alkyl or polyether segments; R9 is selected from phenyl and / or alkyl; m is selected from 3-51, preferably 4-20.

2. The polySchiff base / polyurea / polyurethane synergistic modified organosilicon-based hydrophilic and hydrophobic antifouling resin solution according to claim 1, characterized in that: The antifouling resin comprises hydrophilic segments, hydrophobic segments, a crosslinking agent portion, organosilicon segments, and dynamic chemical bond segments; wherein, the hydrophilic segments are derived from hydrophilic monofunctional monomers, the hydrophobic segments are derived from hydrophobic monofunctional antibacterial / antifouling functional monomers, the dynamic chemical bond segments are derived from difunctional aldehyde compounds; the crosslinking agent portion is derived from trifunctional isocyanate monomers; and the organosilicon segments are derived from polysiloxane monomers.

3. The method for preparing the polySchiff base / polyurea / polyurethane synergistic modified organosilicon-based hydrophilic and hydrophobic antifouling resin solution as described in claim 1 or 2, characterized in that, include: Hydrophilic monofunctional monomers, hydrophobic monofunctional antibacterial / antifouling functional monomers, trifunctional isocyanate monomers, catalysts and solvents are mixed and reacted to prepare hydrophilic and hydrophobic modified isocyanate monomers. The hydrophilic-hydrophobic modified isocyanate monomer, polysiloxane monomer and solvent are mixed and reacted to obtain a hydrophilic-hydrophobic modified organosilicon prepolymer; Furthermore, the hydrophilic-hydrophobic modified organosilicon prepolymer is mixed with a bifunctional aldehyde compound and reacted to obtain a polySchiff base / polyurea / polyurethane synergistic modified organosilicon-based hydrophilic-hydrophobic antifouling resin solution.

4. The preparation method according to claim 3, characterized in that, Specifically, it includes: (1) A hydrophilic monofunctional monomer, a hydrophobic monofunctional antibacterial / antifouling functional monomer, a trifunctional isocyanate monomer, a catalyst and a solvent are mixed and reacted at 20-100 °C for 1-24 h to obtain a hydrophilic-hydrophobic modified isocyanate monomer with NCO terminal groups. (2) The hydrophilic-hydrophobic modified isocyanate monomer, polysiloxane monomer and solvent are mixed and reacted at 20-100 °C for 1-24 h to obtain hydrophilic-hydrophobic modified organosilicon prepolymer; (3) The hydrophilic and hydrophobic modified organosilicon prepolymer is mixed with a bifunctional aldehyde compound and reacted at 40-120 °C for 1-48 h to obtain a polySchiff base / polyurea / polyurethane synergistic modified organosilicon hydrophilic and hydrophobic antifouling resin solution.

5. The preparation method according to claim 4, characterized in that: The molar ratio of the hydrophobic monofunctional antibacterial / antifouling functional monomer, the hydrophilic monofunctional monomer, and the trifunctional isocyanate monomer is (0.5-1.5):(0.5-1.5):(2-3). And / or, the molar ratio of the polysiloxane monomer to the trifunctional isocyanate monomer is (1-3):1; And / or, the molar ratio of the bifunctional aldehyde compound to the polysiloxane monomer is (0.5-1.5):2; And / or, the hydrophilic monofunctional monomer includes any one or more combinations of polyethylene glycol monomethyl ether, polypropylene oxide monomethyl ether, polypropylene glycol monomethyl ether, poly(2-ethyl-2-oxazoline) monomethyl ether, and polyetheramine (monoamino), preferably polyethylene glycol monomethyl ether with a number average molecular weight of 500-2000. And / or, the hydrophobic monofunctional antibacterial / antifouling functional monomer includes any one or more combinations of solanesol, geraniol, menthol, tea tree alcohol, dodecyl monool, linalool, fluorinated benzyl alcohol, cholesterol, and perfluorohexylethanol, preferably any one or more combinations of solanesol, geraniol, menthol, and dodecyl monool; And / or, the trifunctional isocyanate monomer includes any one or more combinations of triphenylmethane triisocyanate, isophorone diisocyanate trimer, hexamethylene diisocyanate trimer, L-lysine triisocyanate, and triphenylmethane triisocyanate, preferably hexamethylene diisocyanate trimer and / or isophorone triisocyanate. And / or, the polysiloxane monomer comprises aminopropyl-terminated polydimethylsiloxane; preferably, the number-average molecular weight of the aminopropyl-terminated polydimethylsiloxane is 500-3000. And / or, the bifunctional aldehyde compounds include any one or more combinations of glyoxal, glutaraldehyde, o-phthalaldehyde, terephthalaldehyde, and polyethylene glycol dipropionaldehyde, preferably o-phthalaldehyde and / or terephthalaldehyde; And / or, the catalyst comprises any one or more combinations of dibutyltin dilaurate, dibutyltin diacetate, dibutyltin dioctanoate, dioctyltin dilaurate, dioctyltin diacetate, dioctyltin dioctanoate, dioctyltin 2-ethylhexanoate, and tin naphthenate. And / or, the solvent includes any one or more combinations of acetone, tetrahydrofuran, dimethyl sulfoxide, toluene, and xylene, preferably any one or more combinations of tetrahydrofuran, toluene, and xylene.

6. The preparation method according to claim 4, characterized in that: The reactions in steps (1), (2), and (3) were all carried out under a protective atmosphere with a stirring rate of 200-1000 r / min.

7. A method for preparing a biodegradable, hydrophilic / hydrophobic synergistic modified organosilicon-based antifouling coating, characterized in that, include: Provides a polySchiff base / polyurea / polyurethane synergistic modified organosilicon-based hydrophilic and hydrophobic antifouling resin solution as described in claim 1 or 2; Furthermore, the polySchiff base / polyurea / polyurethane synergistic modified silicone-based hydrophilic and hydrophobic antifouling resin solution is applied to the substrate surface and dried and cured to obtain a biodegradable hydrophilic / hydrophobic synergistic modified silicone-based antifouling coating.

8. The preparation method according to claim 7, characterized in that: The solid content of the polySchiff base / polyurea / polyurethane synergistic modified organosilicon-based hydrophilic and hydrophobic antifouling resin solution is 20-60 wt%. And / or, the drying and curing temperature is 20-80℃.

9. A biodegradable hydrophilic / hydrophobic synergistic modified organosilicon-based antifouling coating prepared by the preparation method of claim 7 or 8; preferably, the thickness of the biodegradable hydrophilic / hydrophobic synergistic modified organosilicon-based antifouling coating is 50-800 μm.

10. The application of the polySchiff base / polyurea / polyurethane synergistic modified silicone-based hydrophilic / hydrophobic antifouling resin solution according to any one of claims 1-2 or the biodegradable hydrophilic / hydrophobic synergistic modified silicone-based antifouling coating according to any one of claims 7-8 in the field of antifouling or antibacterial in marine environments.

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