CN117965073A - Marine antifouling coating and preparation method thereof - Google Patents
Marine antifouling coating and preparation method thereof Download PDFInfo
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- CN117965073A CN117965073A CN202410194784.XA CN202410194784A CN117965073A CN 117965073 A CN117965073 A CN 117965073A CN 202410194784 A CN202410194784 A CN 202410194784A CN 117965073 A CN117965073 A CN 117965073A
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- 239000011248 coating agent Substances 0.000 title claims abstract description 61
- 238000000576 coating method Methods 0.000 title claims abstract description 61
- 230000003373 anti-fouling effect Effects 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000002904 solvent Substances 0.000 claims abstract description 48
- 229920000587 hyperbranched polymer Polymers 0.000 claims abstract description 25
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 23
- -1 ethyl 2-ethoxythiocarbon Chemical compound 0.000 claims abstract description 19
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- 239000000126 substance Substances 0.000 claims abstract description 13
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims abstract description 12
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims abstract description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- ARFLASKVLJTEJD-UHFFFAOYSA-N ethyl 2-bromopropanoate Chemical compound CCOC(=O)C(C)Br ARFLASKVLJTEJD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 244000028419 Styrax benzoin Species 0.000 claims abstract description 6
- 235000000126 Styrax benzoin Nutrition 0.000 claims abstract description 6
- 235000008411 Sumatra benzointree Nutrition 0.000 claims abstract description 6
- 229960002130 benzoin Drugs 0.000 claims abstract description 6
- 235000019382 gum benzoic Nutrition 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 238000005303 weighing Methods 0.000 claims abstract description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 30
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 21
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 15
- AVUFZLGLMCACRE-UHFFFAOYSA-N 2-methylidene-1,3-dioxepane Chemical compound C=C1OCCCCO1 AVUFZLGLMCACRE-UHFFFAOYSA-N 0.000 claims description 12
- SAMJGBVVQUEMGC-UHFFFAOYSA-N 1-ethenoxy-2-(2-ethenoxyethoxy)ethane Chemical compound C=COCCOCCOC=C SAMJGBVVQUEMGC-UHFFFAOYSA-N 0.000 claims description 11
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 11
- 238000001704 evaporation Methods 0.000 claims description 9
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 7
- 230000002829 reductive effect Effects 0.000 claims description 6
- 239000013557 residual solvent Substances 0.000 claims description 6
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical group C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- XOAMURIABKEBKW-UHFFFAOYSA-N 2-sulfonylpropanoic acid Chemical compound OC(=O)C(C)=S(=O)=O XOAMURIABKEBKW-UHFFFAOYSA-N 0.000 claims description 4
- 239000002274 desiccant Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 125000003147 glycosyl group Chemical group 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 238000005086 pumping Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 6
- 239000002244 precipitate Substances 0.000 claims 1
- 230000001376 precipitating effect Effects 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 10
- PSGAAPLEWMOORI-PEINSRQWSA-N medroxyprogesterone acetate Chemical compound C([C@@]12C)CC(=O)C=C1[C@@H](C)C[C@@H]1[C@@H]2CC[C@]2(C)[C@@](OC(C)=O)(C(C)=O)CC[C@H]21 PSGAAPLEWMOORI-PEINSRQWSA-N 0.000 abstract description 6
- 239000003973 paint Substances 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 abstract 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 abstract 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 abstract 1
- 229910052700 potassium Inorganic materials 0.000 abstract 1
- 239000011591 potassium Substances 0.000 abstract 1
- VRZJGNXBSRQZGM-UHFFFAOYSA-N xanthine-8-carboxylic acid Chemical compound N1C(=O)NC(=O)C2=C1N=C(C(=O)O)N2 VRZJGNXBSRQZGM-UHFFFAOYSA-N 0.000 abstract 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 14
- 229910052710 silicon Inorganic materials 0.000 description 14
- 239000010703 silicon Substances 0.000 description 14
- 239000000523 sample Substances 0.000 description 9
- 239000013068 control sample Substances 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- 239000013535 sea water Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 230000001580 bacterial effect Effects 0.000 description 6
- 239000012496 blank sample Substances 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 241000894006 Bacteria Species 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- 241000206761 Bacillariophyta Species 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000012712 reversible addition−fragmentation chain-transfer polymerization Methods 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 241000195493 Cryptophyta Species 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 241000589516 Pseudomonas Species 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000010065 bacterial adhesion Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000000799 fluorescence microscopy Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 235000015170 shellfish Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 241000556533 uncultured marine bacterium Species 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D153/00—Coating compositions based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
- C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2438/00—Living radical polymerisation
- C08F2438/03—Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Paints Or Removers (AREA)
Abstract
The invention aims to provide a marine antifouling paint with excellent antifouling performance and a preparation method thereof, and solves the problems of environmental pollution and low antifouling efficiency caused by the traditional antifouling material. The method comprises the following steps: step S1, dissolving ethyl 2-bromopropionate and potassium ethyl xanthinate in a first solvent for reaction to obtain ethyl 2-ethoxythiocarbon glycosylsulfonyl-propionate (EXEP). And S2, weighing MDO, VAc, DEGDVE, EXEP and AIBN according to the proportion, dissolving in a third solvent, heating in an oil bath, cooling to room temperature, and removing unreacted chemical substances and the third solvent to obtain the hyperbranched polymer. And S3, dissolving the hyperbranched polymer in Tetrahydrofuran (THF), adding benzoin dimethyl ether (DMPA) as an ultraviolet catalyst, mixing to obtain a precursor, coating the precursor on the surface of an object, heating the surface of the object, and emitting ultraviolet rays to irradiate the surface of the object to obtain the marine antifouling coating.
Description
Technical Field
The invention relates to the technical field of paint preparation, in particular to a marine antifouling coating and a preparation method thereof.
Background
The ship running in the ocean is easy to be adhered by marine organisms such as algae, shellfish and the like to form biological scale, and the adhesion of the marine organisms can cause the great increase of the weight of the ship, so that the running of the ship can be influenced, the running cost of the ship is increased, and the service life of the ship can be reduced.
The application of an antifouling coating on the surface of a ship is the most convenient and common method for preventing marine organism from adhering, and the traditional antifouling material, such as organic tin, contains heavy metal components, so that the marine environment can be polluted and the ecology of the sea can be destroyed after long-term use, and therefore, the development of efficient and environment-friendly antifouling materials is an urgent need in the field of marine antifouling.
Disclosure of Invention
The invention aims to provide a marine antifouling paint with excellent antifouling performance and a preparation method thereof, and solves the problems of environmental pollution and low antifouling efficiency caused by the traditional antifouling material.
The first aspect of the invention provides a preparation method of the marine antifouling coating, comprising the following steps:
Step S1, dissolving ethyl 2-bromopropionate and potassium ethylene xanthinate in a first solvent, reacting in an environment lower than room temperature, further reacting in the room temperature environment to obtain a first solution, filtering and evaporating the first solution under reduced pressure, dissolving in a second solvent to obtain a second solution, washing the second solution with water, adding a drying agent, decompressing, evaporating and concentrating to obtain the ethyl 2-ethoxythiocarbon glycosyl sulfonyl-propionate (EXEP).
Step S2, weighing 2-methylene-1, 3-dioxepane (MDO), vinyl acetate (VAc), diethylene glycol divinyl ether (DEGDVE), ethyl 2-ethoxythiocarbon sulfonyl-propionate (EXEP) and Azodiisobutyronitrile (AIBN) according to the proportion, dissolving in a third solvent, pumping and circulating by a freeze pump, heating in an oil bath in an inert gas environment, completing the reaction, cooling to room temperature, adding the reacted substance into a fourth solvent, collecting a mixture precipitated in the fourth solvent, and removing residual solvent in the mixture to obtain the hyperbranched polymer.
And S3, dissolving the hyperbranched polymer in Tetrahydrofuran (THF), adding benzoin dimethyl ether (DMPA) as an ultraviolet catalyst, mixing to obtain a precursor, coating the precursor on the surface of an object, heating the surface of the object, and emitting ultraviolet rays to irradiate the surface of the object to obtain the marine antifouling coating.
As a preferable technical scheme of the invention, the first solvent is anhydrous acetonitrile, the second solvent is dichloromethane, and the third solvent is 1, 4-dioxane.
As a preferred technical scheme of the invention, in the step S1, ethyl 2-bromopropionate and potassium ethylene xanthinate are dissolved in anhydrous acetonitrile, and are reacted for 2-5 hours in a temperature environment of-10-0 ℃ and then are further reacted for 24-48 hours in a room temperature environment to obtain a first solution.
As a preferred embodiment of the present invention, in step S2, the concentration of 2-methylene-1, 3-dioxepane (MDO) in the third solvent is 15-50mg/mL; the concentration of vinyl acetate (VAc) in the third solvent is 7.5-20mg/mL; diethylene glycol divinyl ether (degve) in the third solvent at a concentration of 25-100mg/mL; the concentration of the ethyl 2-ethoxythiocarbon sulfonyl-propionate (EXEP) in the third solvent is 50-200mg/mL; the concentration of Azobisisobutyronitrile (AIBN) in the third solvent is 0.75-2mg/mL.
As a preferable technical scheme of the invention, in the step S2, the refrigerating pump is circulated for 3-5 times, the heating temperature of the oil bath is 70-90 ℃, and the reaction time is 24-48 hours.
In the step S2, the fourth solvent is n-hexane, the reacted substance is added into n-hexane, the unreacted substance is dissolved in n-hexane, the reacted substance is precipitated in n-hexane, the precipitated mixture in n-hexane is collected, and the mixture is placed in a vacuum environment at 60-80 ℃ for 7-15 hours, and the residual solvent is removed to obtain the hyperbranched polymer.
As a preferable technical scheme of the invention, in the step S3, the mass ratio of benzoin dimethyl ether (DMPA) to the hyperbranched polymer is 1% -3%.
As a preferable technical scheme of the invention, the tail end of the main chain of the hyperbranched polymer obtained in the step S2 is provided with vinyl, and in the step S3, the vinyl at the tail end among the hyperbranched polymers is reacted and connected to form a coating structure.
In the preferred technical scheme of the invention, in the step S3, after the precursor is coated on the surface of the object, the surface of the object is heated by using an oven, the temperature of the oven is set to be 60-80 ℃, and the heating time is 3-5 hours.
The invention also provides a marine antifouling coating, which is prepared by the preparation method of the marine antifouling coating in any technical scheme.
Experiments prove that in the marine antifouling coating prepared by the preparation method of the marine antifouling coating, in the step S2, 2-ethoxythiocarbon glycosyl sulfonyl-ethyl propionate (EXEP) is used as a chain transfer agent (RAFT reagent for controlled free radical polymerization), azobisisobutyronitrile (AIBN) is used as a free radical polymerization initiator, 2-methylene-1, 3-dioxepane (MDO), vinyl acetate (VAc) and diethylene glycol divinyl ether (DEGDVE) are subjected to reversible addition-fragmentation chain transfer polymerization (RAFT) in a third solvent to obtain a hyperbranched polymer with terminal vinyl groups, and in the step S3, the terminal vinyl groups of the hyperbranched polymer react under the catalysis of an ultraviolet catalyst and the irradiation of ultraviolet rays to form a coating structure, so that the marine antifouling coating has excellent marine antifouling properties of preventing marine bacteria from entering the coating surface, inhibiting algae adhesion and the like, and is rapidly degraded and environment-friendly.
Drawings
FIG. 1 is a flow chart of a method for preparing a marine antifouling coating according to an embodiment of the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; the reagents, materials, etc. used in the examples described below are commercially available unless otherwise specified.
1. Material preparation
Fig. 1 is a flowchart of a method for preparing an antifouling coating for sea according to the present embodiment. As shown in FIG. 1, the preparation method of the marine antifouling coating comprises the following steps:
Step S1, dissolving ethyl 2-bromopropionate and potassium ethylene xanthinate in a first solvent, reacting in an environment lower than room temperature, further reacting in the room temperature environment to obtain a first solution, filtering and evaporating the first solution under reduced pressure, dissolving in a second solvent to obtain a second solution, washing the second solution with water, adding a drying agent, decompressing, evaporating and concentrating to obtain the ethyl 2-ethoxythiocarbon glycosyl sulfonyl-propionate (EXEP).
Among them, in this embodiment, anhydrous acetonitrile is selected as the first solvent. The reaction temperature of ethyl 2-bromopropionate and potassium ethylene xanthinate in the first solvent is selected as follows: the reaction is carried out for 2 to 5 hours under the temperature environment of-5 ℃ and then the reaction is carried out for 24 to 48 hours under the room temperature (20 to 25 ℃). Dichloromethane was chosen as the second solvent and magnesium sulfate as the desiccant.
The preparation process of the specific ethyl 2-ethoxythiocarbon sulfonyl-propionate (EXEP) is as follows:
Dissolving ethyl 2-bromopropionate and potassium ethylene xanthinate in anhydrous acetonitrile, adding the anhydrous acetonitrile into a single-neck round-bottom flask with a magneton, carrying out reaction at-5 ℃ for 2-5 hours, then further reacting at room temperature for 24-48 hours, filtering and evaporating the first solution after the reaction under reduced pressure, dissolving the first solution in dichloromethane to obtain a second solution, washing the second solution with water for five times, drying the second solution with magnesium sulfate, and finally evaporating and concentrating under reduced pressure to obtain yellow liquid, namely ethyl 2-ethoxythiocarbon glycosyl sulfonyl-propionate (EXEP).
Step S2, weighing 2-methylene-1, 3-dioxepane (MDO), vinyl acetate (VAc), diethylene glycol divinyl ether (DEGDVE), ethyl 2-ethoxythiocarbon sulfonyl-propionate (EXEP) and Azodiisobutyronitrile (AIBN) according to the proportion, dissolving in a third solvent, pumping and circulating by a freeze pump, heating in an oil bath in an inert gas environment, completing the reaction, cooling to room temperature, adding the reacted substance into a fourth solvent, collecting a mixture precipitated in the fourth solvent, and removing residual solvent in the mixture to obtain the hyperbranched polymer.
In this embodiment, 1, 4-dioxane is selected as the third solvent, n-hexane is selected as the fourth solvent, nitrogen is selected as the inert gas, the oil bath temperature in the oil bath heating process is selected to be 70-90 ℃, the oil bath time is 24-48 hours, and two ways are specifically provided for removing unreacted chemical substances and residual solvents respectively.
The specific hyperbranched polymer (DHP) copolymerization process is as follows:
0.3-0.5g MDO,0.15-0.20g VAc,0.5-1g DEGDVE,0.1-0.2gEXEP and 15-20mgAIBN were weighed into 10-20mL 1, 4-dioxane and then added to a Schlenk flask with a magnetic stirring bar. After 3-5 freeze pump cycles, the flask was filled with nitrogen and placed in an oil bath at 70-90 ℃ for 24-48 hours, after cooling to room temperature, a mixture was obtained, which contained unreacted chemicals (i.e., MDO, vac, DEGDVE, EXEP and AIBN), a third solvent (1, 4-dioxane) and a hyperbranched polymer, the mixture was added to a fourth solvent (n-hexane), the unreacted materials were dissolved in n-hexane, the reacted materials were precipitated in n-hexane to remove the unreacted chemicals, then the precipitated mixture in n-hexane was collected, and the mixture was kept under vacuum at 60-80 ℃ for 7-15 hours to remove the remaining solvent, to obtain the hyperbranched polymer.
And S3, dissolving the hyperbranched polymer obtained in the step S2 in Tetrahydrofuran (THF), adding benzoin dimethyl ether (DMPA) as an ultraviolet catalyst, mixing to obtain a precursor, coating the precursor on the surface of an object, heating the surface of the object, and radiating ultraviolet rays to irradiate the surface of the object to obtain the marine antifouling coating.
Wherein, in the present embodiment, the mass of the ultraviolet catalyst DMPA is preferably made to be 2wt% with respect to the hyperbranched polymer, and after the precursor is coated on the surface of the object, heating is selected using an oven, and THF is completely removed from the coating by controlling the temperature and time of the oven.
The preparation process of the specific marine antifouling coating comprises the following steps:
the preparation method comprises the steps of taking DMPA (dimethyl formamide) accounting for 2wt% of hyperbranched polymer as an ultraviolet catalyst and THF (tetrahydrofuran) as a solvent, forming a coating structure through reaction and connection between terminal vinyl groups of a hyperbranched polymer main chain, coating a coating precursor on a silicon glass slide, putting the silicon glass slide in an oven at 60-80 ℃ for 3-5 hours, completely removing the THF, and then carrying out ultraviolet irradiation on the silicon glass slide for 20-30min to obtain the marine antifouling coating.
It should be noted that, in order to facilitate understanding of the preparation method and performance of the marine antifouling coating provided by the present invention by those skilled in the art, the inventor selects specific reagents and parameters for experiments, but this does not constitute a limitation on the selection of the reagents and parameters in the preparation method of the present invention, and the technical scheme obtained by simply adjusting or replacing the reagents and parameters in the preparation method of the present invention also falls within the scope of protection of the present invention.
2. Detail anti-adhesion Performance test
The antibacterial performance of the marine antifouling coating prepared in this embodiment was tested using the marine bacterium pseudomonas.
The marine antifouling coating in this embodiment was prepared on a silicon slide (1×1cm 2) as an experimental sample, a conventional antifouling material was set on the silicon slide (1×1cm 2) as a control sample, and an untreated silicon slide (1×1cm 2) as a blank sample.
The bacterial concentration of the artificial seawater (ARTIFICIAL SEAWATER, ASW) bacterial suspension was adjusted spectrophotometrically to 1 x 10 7 cells per ml, each sample was immersed in the artificial seawater bacterial suspension for 5 hours, gently washed with fresh Artificial Seawater (ASW), stained with LIVE/DEAD BacLight bacterial activity kit, and the adhered bacterial cells were observed with fluorescence microscopy (Scope A1, zeiss) and analyzed for relative bacterial adsorption with ImageJ software.
Many green spots were observed on the silicon slide surface of the blank sample, indicating that a large amount of marine bacteria were adhered to the silicon surface, and the same phenomenon was observed on the control sample coating surface, indicating that the control sample coating surface was unable to inhibit bacterial adhesion.
And by observing that almost no bacteria adhere to the surface of the marine antifouling coating prepared in this embodiment, it can be confirmed that the marine antifouling coating prepared in this embodiment can effectively prevent marine bacteria from entering the surface.
3. Anti-algae adhesion Property test
The marine antifouling coating in this embodiment was prepared on a silicon slide (1×1cm 2) as an experimental sample, a conventional antifouling material was set on the silicon slide (1×1cm 2) as a control sample, and an untreated silicon slide (1×1cm 2) as a blank sample.
Each sample was immersed in the diatom suspension, illuminated for 12 hours and darkened for 12 hours. Then, the unattached diatoms were removed by gently washing with fresh Artificial Seawater (ASW), and observed with a microscope, and an average value of the diatom densities was obtained by observing 10 random fields of view of each sample.
For the silicon slide surface of the blank sample and the control sample coating surface, 12 diatoms were observed on the silicon slide surface of the blank sample in the photograph, and 11 diatoms were observed on the control sample coating surface. The surface density of the silicon slide of the blank sample is 295 cells per square millimeter; the control sample coating surface density was not 273 cells per square millimeter, indicating that the ordinary coating surface did not affect the adhesion of diatom.
Whereas for the marine antifouling coating prepared in this embodiment a very clean surface was observed, indicating that the coating has remarkable properties of inhibiting diatom adhesion.
4. Degradation Performance test
Hyperbranched polymer (20 mg) was dissolved in 10mL of THF and mixed with the same volume of potassium hydroxide/methanol (0.02M). The mixture was stirred at 30℃and the stirred solution (1 mL) was taken and then neutralized with hydrochloric acid, followed by evaporation to remove the solvent. The resulting solid was dissolved in dichloromethane and filtered, and the final product was dissolved in THF as the solvent evaporated for GPC measurement.
Samples were prepared on epoxy panels and then cured under uv irradiation for 20min, after which the initial weight of each dried sample and epoxy panel was recorded. Then, the sample was immersed in artificial seawater at 25 ℃ and taken out of the artificial seawater at regular time intervals, rinsed with deionized water, freeze-dried for 2 days, and then the dry weight thereof was recorded to calculate mass loss.
In a 0.01M potassium hydroxide/methanol solution, the mass loss value of the conventional antifouling coating after 14 days is 0.3mg cm -2, and the mass loss value of the marine antifouling coating provided by the embodiment is 0.9mg cm -2. The marine antifouling coating provided by the embodiment can be degraded into small fragments with Mn less than 650gmol -1, and the mass loss and the immersion time are in a first-order linear relationship, and the gradient is greater than that of a traditional antifouling coating sample, so that the degradation rate is higher than that of the traditional antifouling coating sample.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention. The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (10)
1. The preparation method of the marine antifouling coating is characterized by comprising the following steps of:
Step S1, dissolving ethyl 2-bromopropionate and potassium ethylene xanthinate in a first solvent, reacting in an environment lower than room temperature, further reacting in the room temperature environment to obtain a first solution, filtering and evaporating the first solution under reduced pressure, dissolving the first solution in a second solvent to obtain a second solution, washing the second solution with water, adding a drying agent, decompressing, evaporating and concentrating to obtain 2-ethoxythiocarbon glycosylsulfonyl-ethyl propionate;
s2, weighing 2-methylene-1, 3-dioxepane, vinyl acetate, diethylene glycol divinyl ether, ethyl 2-ethoxythiocarbon glycosyl sulfonyl-propionate and azodiisobutyronitrile according to a proportion, dissolving in a third solvent, pumping and circulating by a freeze pump, heating in an oil bath in an inert gas environment, cooling to room temperature after the reaction is completed, adding the reacted substance into a fourth solvent, collecting a mixture precipitated in the fourth solvent, and removing residual solvent in the mixture precipitate to obtain a hyperbranched polymer;
and S3, dissolving the hyperbranched polymer in tetrahydrofuran, adding benzoin dimethyl ether as an ultraviolet catalyst, mixing to obtain a precursor, coating the precursor on the surface of an object, heating the surface of the object, and emitting ultraviolet rays to irradiate the surface of the object to obtain the marine antifouling coating.
2. The method for producing a marine antifouling coating according to claim 1, wherein the first solvent is anhydrous acetonitrile, the second solvent is dichloromethane, and the third solvent is 1, 4-dioxane.
3. The method for preparing a marine antifouling coating according to claim 2, wherein in said step S1, said ethyl 2-bromopropionate and said Huang Piaosuan ethylpotassium acetate are dissolved in said anhydrous acetonitrile, reacted for 2 to 5 hours in a temperature environment of-10 to 0 ℃ and then further reacted for 24 to 48 hours in a room temperature environment to obtain a first solution.
4. A method for producing a marine antifouling coating according to claim 1, wherein in said step S2,
The concentration of the 2-methylene-1, 3-dioxepane in the third solvent is 15-50mg/mL;
The concentration of the vinyl acetate in the third solvent is 7.5-20mg/mL;
The concentration of the diethylene glycol divinyl ether in the third solvent is 25-100mg/mL;
The concentration of the ethyl 2-ethoxythiocarbon glycosylsulfonyl-propionate in the third solvent is 50-200mg/mL;
The concentration of the azodiisobutyronitrile in the third solvent is 0.75-2mg/mL.
5. The method for producing marine antifouling coating according to claim 4, wherein in said step S2, said cryopump is circulated 3 to 5 times, the heating temperature of the oil bath is 70 to 90 ℃ and the reaction time is 24 to 48 hours.
6. A method for producing a marine antifouling coating according to claim 5, wherein in said step S2, said fourth solvent is n-hexane,
Adding the reacted substance into the n-hexane, dissolving unreacted substance in the n-hexane, precipitating the reacted substance in the n-hexane, collecting the precipitated mixture in the n-hexane, then placing the mixture in a vacuum environment of 60-80 ℃ for 7-15 hours, and removing the residual solvent to obtain the hyperbranched polymer.
7. The method of producing a marine antifouling coating according to claim 1, wherein in step S3, the mass ratio of benzoin dimethyl ether to the hyperbranched polymer is 1% -3%.
8. The method for producing a marine antifouling coating according to claim 3, wherein the terminal of the hyperbranched polymer backbone obtained in step S2 has a vinyl group, and in step S3, the terminal vinyl groups between the hyperbranched polymers react and bond to form a coating structure.
9. The method for producing a marine antifouling coating according to claim 8, wherein in said step S3, after said precursor is applied to the surface of said object, the surface of said object is heated by an oven, the temperature of said oven is set to 60 to 80 ℃ and the heating time is set to 3 to 5 hours.
10. A marine antifouling coating prepared by the method of preparing a marine antifouling coating according to any of claims 1 to 9.
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