Pressure-resistant and anti-permeation deep-sea intrinsic antifouling polyurethane as well as preparation method and application of pressure-resistant and anti-permeation deep-sea intrinsic antifouling polyurethane

Abstract

The invention discloses a pressure-resistant and anti-permeation deep sea intrinsic antifouling poly-fatty ammonia glycol as well as a preparation method and application of the pressure-resistant and anti-permeation deep sea intrinsic antifouling poly-fatty ammonia glycol. The deep-sea intrinsic antifouling poly-fatty amino vinegar comprises polymer soft segments, antibacterial hard segments and polyiso-oxoacid chain segments, wherein the polymer soft segments, the antibacterial hard segments and the polyiso-oxoacid chain segments are alternately distributed; wherein the antibacterial hard segment comprises a barking group two-fat unit. The antibacterial hard segment in the deep-sea intrinsic antifouling poly-fatty ammonia endows the poly-fatty ammonia glucoside with a fouling organism contact killing function, and the barking ring and the poly-fatty ammonia glucoside synergistically endow the deep-sea intrinsic antifouling poly-fatty ammonia glucoside with high pressure resistance and high permeability; meanwhile, the deep-sea intrinsic antifouling poly-fatty ammonia glucoside is suitable for surface antifouling of thousand-deep-sea environment equipment, can resist deep washing high pressure and seawater permeation, and can effectively prevent adhesion of deep washing bacteria and fouling organisms.

Description

Technical Field

[0001] The invention belongs to the technical field of antifouling, and specifically relates to a deep-sea intrinsic antifouling polyoxime urethane with pressure resistance and anti-permeability, and a preparation method and application thereof. Background Art

[0002] Marine biofouling is currently one of the most important factors affecting ships and marine engineering equipment, causing marine economic losses. The cost of transportation delays, hull repair, maintenance and cleaning caused by the attachment and accumulation of marine microorganisms, animals and plants is as high as 150 billion US dollars each year. The active antifouling strategy of coating the surface with antifouling paint is the simplest, most economical and efficient way to solve marine fouling. However, the antifouling performance of most antifouling coatings currently comes from the antifouling agents with toxic properties doped in the coating, especially the currently widely used cuprous oxide and some antifouling agents containing metallic zinc. The release of these antifouling agents into seawater will cause great risks and harm to the marine environment, ecological structure and human health. Therefore, the development of antifouling resins with intrinsic antibacterial properties has become one of the important methods to solve this problem.

[0003] At present, there are only a few countries in the world that can independently develop 10,000-meter manned submersibles. At the same time, the development of submersible surface protection (anti-corrosion / anti-fouling) coatings is crucial. However, since the pressure under the deep sea is hundreds or thousands of times the atmospheric pressure on the surface, and can even reach hundreds of atmospheres, the coating needs to have extremely high strength and mechanical properties to withstand such high pressure. At the same time, it is necessary to prevent water molecules from penetrating into the coating under such high pressure, causing the coating to fail and peel off. This brings great difficulty and challenges to the development of anti-fouling coatings on the surface of submersibles. Summary of the invention

[0004] The main purpose of the present invention is to provide a deep-sea intrinsic antifouling polyoxime urethane with pressure resistance and anti-permeability and a preparation method and application thereof, so as to overcome the shortcomings of the prior art.

[0005] In order to achieve the above-mentioned invention object, the technical solution adopted by the present invention includes:

[0006] An embodiment of the present invention provides a deep-sea intrinsic antifouling polyoxime urethane that is pressure-resistant and anti-permeability, comprising: a polymer soft segment, an antibacterial hard segment and a polyisocyanate segment, wherein the polymer soft segment, the antibacterial hard segment and the polyisocyanate segment are alternately distributed; wherein the antibacterial hard segment comprises a furanyl dioxime unit.

[0007] The embodiment of the present invention also provides a method for preparing the aforementioned pressure-resistant and anti-permeability deep-sea intrinsic antifouling polyoxime urethane, which comprises:

[0008] Conducting a prepolymerization reaction of a prepolymerization system comprising polyisocyanate, a soft segment polymer, a catalyst and a solvent to obtain a prepolymer;

[0009] And, the compound used to form the antibacterial hard segment is dissolved in a solvent and mixed with the prepolymer to carry out polymerization reaction to prepare the deep-sea intrinsic antifouling polyoxime urethane.

[0010] The embodiment of the present invention also provides the use of the aforementioned pressure-resistant and permeability-resistant deep-sea intrinsic antifouling polyoxime urethane in the preparation of high-pressure-resistant, permeability-resistant and antifouling paint or coating for the surface of deep-sea environment equipment.

[0011] Compared with the prior art, the present invention has the following beneficial effects:

[0012] (1) Compared with the resin of traditional antifouling coatings, the deep-sea intrinsic antifouling polyoxime urethane in the present invention has intrinsic antifouling properties, and can effectively kill fouling organisms adhering to the surface through the furan dioxime bactericidal unit in the molecular chain segment;

[0013] (2) Compared with traditional antifouling coating resins, the deep-sea intrinsic antifouling polyoxime urethane in the present invention has high strength and pressure resistance and can withstand hundreds of atmospheric pressures in the deep sea;

[0014] (3) Compared with traditional antifouling coating resins, the deep-sea intrinsic antifouling polyoxime urethane in the present invention has high anti-penetration performance and can effectively prevent the penetration of water molecules in the deep sea. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments recorded in the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0016] Figure 1 is the nuclear magnetic resonance hydrogen spectrum of the deep-sea intrinsic antifouling polyoxime urethane sample in Example 1 of the present invention;

[0017] Figure 2a-2k It is a graph of the bactericidal performance of the coating prepared from the epoxy board of the present invention, Examples 1-6 and Comparative Examples 1-4;

[0018] Figure 3a and Figure 3b 1 is a tensile stress-strain curve diagram of the samples in Examples 1-6 of the present invention and Comparative Examples 1-4;

[0019] Figure 4a and Figure 4b It is a graph of the water swelling ratio of the samples in Examples 1-6 of the present invention and Comparative Examples 1-4. DETAILED DESCRIPTION

[0020] In view of the defects of the prior art, the inventors of this case have proposed the technical solution of the present invention after long-term research and extensive practice. The main purpose is to introduce furan dioxime bactericidal units into polyoxime urethane to improve the contact killing property of polyoxime urethane. In addition, the furan ring and the polyoxime urethane structure synergistically give it high pressure resistance and high permeability.

[0021] The technical solution of the present invention will be described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0022] Specifically, as one aspect of the technical solution of the present invention, a pressure-resistant and anti-permeability deep-sea intrinsic antifouling polyoxime urethane comprises: a polymer soft segment, an antibacterial hard segment and a polyisocyanate segment, wherein the polymer soft segment, antibacterial hard segment and polyisocyanate segment are alternately distributed; wherein the antibacterial hard segment comprises a furanyl dioxime unit.

[0023] The deep-sea intrinsic antifouling polyoxime urethane in the present invention is composed of a soft segment, an antibacterial hard segment and a polyisocyanate segment, wherein the furan dioxime hard segment with bactericidal properties gives the polyoxime urethane a contact-killing function for fouling organisms, and the furan ring and the polyoxime urethane structure synergistically give it high pressure resistance and high permeability. The intrinsic antifouling polyoxime urethane is suitable for antifouling of the surface of deep-sea environment equipment, and can not only resist deep-sea high pressure and seawater penetration, but also effectively prevent the adhesion of deep-sea bacteria and fouling organisms.

[0024] In some preferred embodiments, the polymer soft segment is derived from a soft segment polymer, which includes a combination of any one or more polymers selected from tetrakis dimethyl ether glycol, polycaprolactone alcohol, poly(ethylene adipate), polyhydroxyalkanoate, and bisphenol A polyoxypropylene ether, and is not limited thereto.

[0025] Furthermore, the molecular weight of the soft segment polymer is 500 to 20,000 g / mol.

[0026] In some preferred embodiments, the source of the furanyl dioxime unit includes any one of the following compounds or a combination of two or more thereof:

[0027]

[0028] Wherein, the values ​​of x and y are 0 to 5, and M is selected from Cu, Zn or Ag.

[0029] In some preferred embodiments, the polyisocyanate segment is derived from a polyisocyanate, and the polyisocyanate includes any one or more combinations of diphenylmethane diisocyanate (MDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), toluene diisocyanate (TDI), naphthalene 1,5-diisocyanate (NDI), dicyclohexylmethane-4,4′-diisocyanate (HMDI), meta-xylylene diisocyanate (XDI), tetramethyl meta-xylylene diisocyanate (TMXDI), 1,4-cyclohexane diisocyanate (CHDI), methylcyclohexane diisocyanate (HTDI), 1,4-phenylene diisocyanate (PPDI), norbornane dimethylene isocyanate (NBDI), and L-lysine diisocyanate (LDI), and is not limited thereto.

[0030] In some preferred embodiments, the molar ratio of the polymer soft segment, the antibacterial hard segment and the polyisocyanate segment in the deep-sea intrinsic antifouling polyoxime urethane is 1:0.5:1 to 1:2:4.

[0031] Another aspect of the embodiments of the present invention further provides a method for preparing the aforementioned pressure-resistant and anti-permeability deep-sea intrinsic antifouling polyoxime urethane, which comprises:

[0032] Conducting a prepolymerization reaction of a prepolymerization system comprising polyisocyanate, a soft segment polymer, a catalyst and a solvent to obtain a prepolymer;

[0033] And, the compound used to form the antibacterial hard segment is dissolved in a solvent and mixed with the prepolymer to carry out polymerization reaction to prepare the deep-sea intrinsic antifouling polyoxime urethane.

[0034] In some preferred embodiments, the catalyst includes any one of dibutyltin dilaurate, stannous octoate, dibutyltin didodecylsulfide, dibutyltin diacetate, or a combination of two or more thereof, and is not limited thereto.

[0035] In some preferred embodiments, the solvent includes any one or more combinations of ethanol, methanol, isopropanol, toluene, xylene, n-hexane, cyclohexane, ether, petroleum ether, dichloromethane, chloroform, carbon tetrachloride, ethyl acetate, tetrahydrofuran, acetonitrile, N,N-dimethylformamide, and N,N-dimethylacetamide, and is not limited thereto.

[0036] In some preferred embodiments, the compound for forming the antibacterial hard segment is selected from any one or a combination of two or more of the following compounds:

[0037]

[0038] Wherein, the values ​​of x and y are 0 to 5, and M is selected from Cu, Zn or Ag.

[0039] In some preferred embodiments, the molar ratio of the polyisocyanate, the soft segment polymer and the catalyst is 1-4:1:0.2.

[0040] In some preferred embodiments, the molar ratio of the compound for forming the antibacterial hard segment to the prepolymer is 0.5-2:2-5.

[0041] In some preferred embodiments, the prepolymerization temperature is 50°C to 90°C.

[0042] Furthermore, the temperature of the prepolymerization reaction is 70°C.

[0043] In some preferred embodiments, the prepolymerization reaction time is 3 h to 12 h.

[0044] Furthermore, the prepolymerization reaction time is 5 hours.

[0045] In some preferred embodiments, the polymerization reaction temperature is 50°C to 90°C.

[0046] Furthermore, the polymerization reaction temperature is 70°C.

[0047] In some preferred embodiments, the polymerization reaction time is 3 h to 12 h.

[0048] Furthermore, the polymerization reaction time is 5 hours.

[0049] In some preferred embodiments, the preparation method further comprises: after the polymerization reaction is completed, vacuum drying the obtained product.

[0050] Furthermore, the vacuum drying treatment is performed at a temperature of 90° C. to 150° C. and for a time of 24 h to 96 h.

[0051] Furthermore, the preparation method further comprises: after the polymerization reaction is completed, vacuum drying the obtained product; wherein the temperature of the vacuum drying is 90° C. and the time is 24 hours.

[0052] In some more specific implementations, the method for preparing the pressure-resistant and anti-permeability deep-sea intrinsic antifouling polyoxime urethane comprises:

[0053] (1) Dissolve polyisocyanate and dibutyltin dilaurate (DBTDL) in a solvent and add them to the soft segment polymer, and stir at 70°C for 5 hours to synthesize a prepolymer.

[0054] (2) The antibacterial hard segment was dissolved in a solvent and added to the prepolymer, and stirred at 70° C. for 5 h to obtain the target product.

[0055] (3) The target product is dried under vacuum at 90° C. for more than 24 h to obtain polyoxime urethane.

[0056] The deep-sea intrinsic antifouling polyoxime aminoester in the present invention has a good bactericidal effect on Escherichia coli, Pseudomonas, Vibrio, Achromobacter, Flavobacterium, Spirillum, Micrococcus, Sarcina, Bacillus, Corynebacterium, Cynomolgus, Nocardia, and Streptomyces.

[0057] Another aspect of the embodiments of the present invention further provides the use of the aforementioned deep-sea intrinsic antifouling polyoxime urethane in the preparation of high-pressure-resistant, anti-penetration antifouling paint or coating for the surface of deep-sea environment equipment.

[0058] The technical solution of the present invention is further described in detail below in conjunction with several preferred embodiments and drawings. This embodiment is implemented on the premise of the technical solution of the invention, and a detailed implementation method and specific operation process are given, but the protection scope of the present invention is not limited to the following embodiments.

[0059] Unless otherwise specified, the experimental materials used in the following examples can be purchased from conventional biochemical reagent companies.

[0060] Example 1

[0061] Preparation of polyoxime urethane based on furan dioxime:

[0062] (1) Prepare the following reactants: polytetramethyl ether diol, isophorone diisocyanate, dibutyltin dilaurate (DBTDL), 2,5-furandicarboxaldehyde oxime, the molecular structure of which is shown in the following formula;

[0063]

[0064] (2) 0.5 g of isophorone diisocyanate and 0.05 g of dibutyltin dilaurate (DBTDL) were dissolved in a solvent and added to 6 g of polytetrakis dimethyl ether glycol. The mixture was stirred at 70° C. for 5 h to synthesize a prepolymer.

[0065] (3) Dissolve 0.2 g of furan dioxime in a solvent and add the mixture to the prepolymer. Stir the mixture at 70° C. for 5 h to obtain the target product.

[0066] (4) The target product is dried under vacuum at 90° C. for more than 24 hours to obtain a deep-sea intrinsic antifouling polyoxime urethane, the structural formula of which is shown in FIG. (1):

[0067] Formula (1)

[0068] Figure 1 This is the hydrogen nuclear magnetic resonance spectrum of the deep-sea intrinsic antifouling polyoxime urethane prepared in this example.

[0069] Example 2

[0070] Preparation of polyoxime urethane based on furan dioxime:

[0071] (1) preparing the following reactants: polytetramethyl ether glycol, diphenylmethane diisocyanate, dibutyltin dilaurate (DBTDL), and 2,5-furandicarboxaldehyde oxime;

[0072] (2) 0.5 g of diphenylmethane diisocyanate and 0.05 g of dibutyltin dilaurate (DBTDL) were dissolved in a solvent and added to 4.5 g of polytetrakis dimethyl ether glycol. The mixture was stirred at 70° C. for 5 h to synthesize a prepolymer.

[0073] (3) Dissolve 0.2 g of furan dioxime in a solvent and add the mixture to the prepolymer. Stir the mixture at 70° C. for 5 h to obtain the target product.

[0074] (4) The target product is dried under vacuum at 90° C. for more than 24 hours to obtain a deep-sea intrinsic antifouling polyoxime urethane, the structural formula of which is shown in FIG. (2):

[0075] Formula (2)

[0076]

[0077] Example 3

[0078] Preparation of polyoxime urethane based on furan dioxime:

[0079] (1) preparing the following reactants: polycaprolactone alcohol, isophorone diisocyanate, dibutyltin dilaurate (DBTDL), and 2,5-furandicarboxaldehyde oxime;

[0080] (2) 0.5 g of isophorone diisocyanate and 0.05 g of dibutyltin dilaurate (DBTDL) were dissolved in a solvent and added to 8 g of polycaprolactone alcohol. The mixture was stirred at 70° C. for 5 h to synthesize a prepolymer.

[0081] (3) Dissolve 0.2 g of furan dioxime in a solvent and add the mixture to the prepolymer. Stir the mixture at 70° C. for 5 h to obtain the target product.

[0082] (4) The target product is dried under vacuum at 90° C. for more than 24 hours to obtain a deep-sea intrinsic antifouling polyoxime urethane, the structural formula of which is shown in FIG. (3):

[0083] Formula (3)

[0084] Example 4

[0085] Preparation of polyoxime urethane based on furan dioxime:

[0086] (1) preparing the following reactants: bisphenol A polyoxypropylene ether, diphenylmethane diisocyanate, dibutyltin dilaurate (DBTDL), and 2,5-furandicarboxaldehyde oxime;

[0087] (2) 0.5 g of diphenylmethane diisocyanate and 0.05 g of dibutyltin dilaurate (DBTDL) were dissolved in a solvent and added to 8.5 g of bisphenol A polyoxypropylene ether. The mixture was stirred at 70° C. for 5 h to synthesize a prepolymer.

[0088] (3) Dissolve 0.2 g of furan dioxime in a solvent and add the mixture to the prepolymer. Stir the mixture at 70° C. for 5 h to obtain the target product.

[0089] (4) The target product is dried under vacuum at 90° C. for more than 24 hours to obtain a polyoxime urethane resin, the structural formula of which is shown in FIG. (4):

[0090]

[0091] Example 5

[0092] Preparation of polyoxime urethane based on furan dioxime:

[0093] (1) preparing the following reactants: polytetrakis dimethyl ether glycol, dicyclohexylmethane-4,4′-diisocyanate, dibutyltin dilaurate (DBTDL), and 2,5-furandicarboxaldehyde oxime;

[0094] (2) 0.5 g of dicyclohexylmethane-4,4′-diisocyanate and 0.05 g of dibutyltin dilaurate (DBTDL) were dissolved in a solvent and added to 5.5 g of polytetrakis dimethyl ether glycol. The mixture was stirred at 70° C. for 5 h to synthesize a prepolymer.

[0095] (3) Dissolve 0.2 g of furan dioxime in a solvent and add the mixture to the prepolymer. Stir the mixture at 70° C. for 5 h to obtain the target product.

[0096] (4) The target product is dried under vacuum at 90° C. for more than 24 hours to obtain a deep-sea intrinsic antifouling polyoxime urethane, the structural formula of which is shown in FIG. (5):

[0097] Formula (5)

[0098] Example 6

[0099] Preparation of polyoxime urethane based on furan dioxime:

[0100] (1) Prepare the following reactants: poly(ethylene adipate), isophorone diisocyanate, dibutyltin dilaurate (DBTDL), and 2,5-furandicarboxaldehyde oxime;

[0101] (2) 0.5 g of isophorone diisocyanate and 0.05 g of dibutyltin dilaurate (DBTDL) were dissolved in a solvent and added to 6.5 g of poly(ethylene adipate), and the mixture was stirred at 70° C. for 5 h to synthesize a prepolymer.

[0102] (3) Dissolve 0.2 g of furan dioxime in a solvent and add the mixture to the prepolymer. Stir the mixture at 70° C. for 5 h to obtain the target product.

[0103] (4) The target product is dried under vacuum at 90° C. for more than 24 hours to obtain a deep-sea intrinsic antifouling polyoxime urethane, the structural formula of which is shown in FIG. (6):

[0104] Formula (6)

[0105] Comparative Example 1

[0106] Preparation of furan dioxime-free polyoxime urethanes:

[0107] (1) Prepare the following reactants: isophorone diisocyanate, dibutyltin dilaurate (DBTDL), and 2,5-furandicarboxaldehyde oxime;

[0108] (2) 0.5 g of isophorone diisocyanate, 2 g of furan dioxime and 0.05 g of dibutyltin dilaurate (DBTDL) were dissolved in a solvent and stirred at 70° C. for 5 h to obtain the target product.

[0109] (3) The target product is dried under vacuum at 90° C. for more than 24 hours to obtain a polyoxime urethane without a soft segment, the structural formula of which is shown in FIG. (7):

[0110]

[0111] Comparative Example 2

[0112] Preparation of polyoxime urethane based on furan dioxime with hydroxy silicone oil as soft segment:

[0113] (1) Prepare the following reactants: hydroxy silicone oil, isophorone diisocyanate, dibutyltin dilaurate (DBTDL), and 2,5-furandicarboxaldehyde oxime.

[0114] (2) 0.5 g of isophorone diisocyanate and 0.05 g of dibutyltin dilaurate (DBTDL) were dissolved in a solvent and added to 6 g of hydroxy silicone oil. The mixture was stirred at 70° C. for 5 h to synthesize a prepolymer.

[0115] (3) Dissolve 0.2 g of furan dioxime in a solvent and add the mixture to the prepolymer. Stir the mixture at 70° C. for 5 h to obtain the target product.

[0116] (4) The target product is dried under vacuum at 90° C. for more than 24 hours to obtain a furan dioxime-based polyoxime urethane with a soft segment of hydroxy silicone oil, the structural formula of which is shown in Formula (8):

[0117] Formula (8)

[0118] Comparative Example 3

[0119] The preparation method of the polyoxime urethane without antibacterial hard segment is the same as that of Example 1, except that the antibacterial hard segment is missing;

[0120] (1) Prepare the following reactants: polytetramethyl ether glycol, isophorone diisocyanate, and dibutyltin dilaurate (DBTDL).

[0121] (2) 0.5 g of isophorone diisocyanate and 0.05 g of dibutyltin dilaurate (DBTDL) were dissolved in a solvent and added to 6 g of polytetrakis dimethyl ether glycol, and stirred at 70° C. for 5 h to synthesize the target product.

[0122] (3) The target product is dried under vacuum at 90° C. for more than 24 hours to obtain a polyoxime urethane resin, the structural formula of which is shown in FIG. (9):

[0123]

[0124] Comparative Example 4

[0125] The method is the same as that of Example 1, except that the antibacterial hard segment is replaced by a similar structure without the furandioxime structure.

[0126] Preparation of polyoxime urethane based on dimethylglyoxime:

[0127] (1) Prepare the following reactants: polytetramethyl ether glycol, isophorone diisocyanate, dibutyltin dilaurate (DBTDL), dimethylglyoxime, the molecular structure of which is shown in the following formula;

[0128]

[0129] (2) 0.5 g of isophorone diisocyanate and 0.05 g of dibutyltin dilaurate (DBTDL) were dissolved in a solvent and added to 6 g of polytetrakis dimethyl ether glycol. The mixture was stirred at 70° C. for 5 h to synthesize a prepolymer.

[0130] (3) Dissolve 0.2 g of furan dioxime in a solvent and add the mixture to the prepolymer. Stir the mixture at 70° C. for 5 h to obtain the target product.

[0131] (4) The target product is dried under vacuum at 90° C. for more than 24 hours to obtain a polyoxime urethane resin, the structural formula of which is shown in FIG. (10):

[0132]

[0133] Performance characterization:

[0134] The samples of Examples 1-6 and Comparative Examples 1-4 were prepared into coatings, and the antibacterial properties of the coating surfaces were tested using the GB / T31402-2015 method to verify the intrinsic bactericidal properties of the coatings. Figure 2a-2k As shown, the coatings prepared from the samples of Examples 1-6 sterilize (E. coli) the epoxy board, as well as Comparative Example 1 and Comparative Examples 3-4 by 100%, and can achieve effective sterilization.

[0135] The samples of Examples 1-6 and Comparative Examples 1-4 were prepared into strips, and the strips were stretched according to the GB / T 1040.2-2022 method to verify the strength and mechanical properties of the samples. Figure 3a-Figure 3b As shown. Figure 3a As shown, the fracture strengths of Examples 1-6 are all greater than 20 MPa, indicating that they have relatively high strength and can withstand the deep-sea high-pressure environment, while the sample of Comparative Example 1 has no strength, and the strengths of Comparative Examples 2 and 4 are both very low.

[0136] The samples of Examples 1-6 and Comparative Examples 1-4 were immersed in 3.5 wt% NaCl, and the penetration resistance of the samples was tested using the GB / T 173-1993 method. Figure 4a-4b As shown, the swelling ratios of Examples 1-6 are all less than 5%, indicating that the coating has excellent anti-penetration performance.

[0137] In addition, the inventors of this case also referred to the aforementioned embodiments and conducted experiments with other raw materials, process operations, and process conditions described in this specification, and obtained relatively ideal results.

[0138] It should be understood that the technical solution of the present invention is not limited to the above-mentioned specific implementation cases. Any technical deformation made according to the technical solution of the present invention without departing from the scope of protection of the purpose of the present invention and the claims shall fall within the protection scope of the present invention.

Claims

1. A deep-sea intrinsic antifouling polyoxime urethane with pressure resistance and anti-permeability, characterized in that: include: A polymer soft segment, an antibacterial hard segment and a polyisocyanate segment, wherein the polymer soft segment, the antibacterial hard segment and the polyisocyanate segment are alternately distributed; wherein the antibacterial hard segment comprises a furanyl dioxime unit.

2. The deep-sea intrinsic antifouling polyoxime urethane according to claim 1, characterized in that: The polymer soft segment is derived from a soft segment polymer, and the soft segment polymer includes any one or more polymers selected from tetrakis dimethyl ether glycol, polycaprolactone alcohol, poly(ethylene adipate), polyhydroxyalkanoate, and bisphenol A polyoxypropylene ether.

3. The deep-sea intrinsic antifouling polyoxime urethane according to claim 2, characterized in that: The molecular weight of the soft segment polymer is 500 to 20000 g / mol.

4. The deep-sea intrinsic antifouling polyoxime urethane according to claim 1, characterized in that: The source of the furanyl dioxime unit includes any one of the following compounds or a combination of two or more thereof: Wherein, the values ​​of x and y are 0 to 5, and M is selected from Cu, Zn or Ag.

5. The deep-sea intrinsic antifouling polyoxime urethane according to claim 1, characterized in that: The polyisocyanate chain segment is derived from a polyisocyanate, and the polyisocyanate includes any one or more combinations of diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, naphthalene 1,5-diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, meta-xylylene diisocyanate, tetramethyl meta-xylylene diisocyanate, 1,4-cyclohexane diisocyanate, methylcyclohexane diisocyanate, 1,4-phenylene diisocyanate, norbornane dimethylene isocyanate, and L-lysine diisocyanate.

6. The deep-sea intrinsic antifouling polyoxime urethane according to claim 1, characterized in that: The molar ratio of the polymer soft segment, the antibacterial hard segment and the polyisocyanate segment in the deep-sea intrinsic antifouling polyoxime urethane is 1:0.5:1 to 1:2:

4.

7. The method for preparing the pressure-resistant and anti-permeability deep-sea intrinsic antifouling polyoxime urethane according to any one of claims 1 to 6, characterized in that: include: Conducting a prepolymerization reaction of a prepolymerization system comprising polyisocyanate, a soft segment polymer, a catalyst and a solvent to obtain a prepolymer; And, the compound used to form the antibacterial hard segment is dissolved in a solvent and mixed with the prepolymer to carry out polymerization reaction to prepare the deep-sea intrinsic antifouling polyoxime urethane.

8. The preparation method according to claim 7, characterized in that: The catalyst includes any one of dibutyltin dilaurate, stannous octoate, dibutyltin didodecylsulfide, and dibutyltin diacetate, or a combination of two or more thereof; And / or, the solvent includes any one or a combination of two or more of ethanol, methanol, isopropanol, toluene, xylene, n-hexane, cyclohexane, ether, petroleum ether, dichloromethane, chloroform, carbon tetrachloride, ethyl acetate, tetrahydrofuran, acetonitrile, N,N-dimethylformamide, and N,N-dimethylacetamide; And / or, the compound used to form the antibacterial hard segment is selected from any one of the following compounds or a combination of two or more thereof: Wherein, the values ​​of x and y are 0 to 5, and M is selected from Cu, Zn or Ag; and / or, the molar ratio of the polyisocyanate, the soft segment polymer and the catalyst is 1 to 4:1:0.2; And / or, the molar ratio of the compound for forming the antibacterial hard segment to the prepolymer is 0.5-2:2-5.

9. The preparation method according to claim 7, characterized in that: The prepolymerization reaction temperature is 50°C to 90°C; and / or the prepolymerization reaction time is 3h to 12h; and / or, the polymerization reaction temperature is 50° C. to 90° C.; and / or, the polymerization reaction time is 3 h to 12 h; And / or, the preparation method further comprises: after the polymerization reaction is completed, vacuum drying the obtained product; preferably, the temperature of the vacuum drying is 90° C. to 150° C., and the time is 24 h to 96 h.

10. Use of the pressure-resistant and permeation-resistant deep-sea intrinsic antifouling polyoxime urethane according to any one of claims 1 to 6 in the preparation of high-pressure-resistant, permeation-resistant and antifouling paint or coating for the surface of deep-sea environment equipment.

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