CN116676011A - Sustained-release cellulose-cuprous oxide antifouling agent and preparation method and application thereof - Google Patents
Sustained-release cellulose-cuprous oxide antifouling agent and preparation method and application thereof Download PDFInfo
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- CN116676011A CN116676011A CN202310643185.7A CN202310643185A CN116676011A CN 116676011 A CN116676011 A CN 116676011A CN 202310643185 A CN202310643185 A CN 202310643185A CN 116676011 A CN116676011 A CN 116676011A
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- cellulose
- cuprous oxide
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- 239000002519 antifouling agent Substances 0.000 title claims abstract description 76
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 229940112669 cuprous oxide Drugs 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000013268 sustained release Methods 0.000 title claims description 10
- 239000012730 sustained-release form Substances 0.000 title claims description 10
- 230000003373 anti-fouling effect Effects 0.000 claims abstract description 67
- 239000003973 paint Substances 0.000 claims abstract description 59
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 30
- 238000003756 stirring Methods 0.000 claims abstract description 24
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims abstract description 20
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 18
- 229910000365 copper sulfate Inorganic materials 0.000 claims abstract description 16
- 239000001913 cellulose Substances 0.000 claims abstract description 15
- 229920002678 cellulose Polymers 0.000 claims abstract description 15
- 239000006185 dispersion Substances 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 239000012265 solid product Substances 0.000 claims abstract description 12
- 239000011668 ascorbic acid Substances 0.000 claims abstract description 10
- 229960005070 ascorbic acid Drugs 0.000 claims abstract description 10
- 235000010323 ascorbic acid Nutrition 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 10
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 10
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 10
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- 230000007935 neutral effect Effects 0.000 claims abstract description 5
- 238000000926 separation method Methods 0.000 claims abstract description 3
- 239000003822 epoxy resin Substances 0.000 claims description 19
- 229920000647 polyepoxide Polymers 0.000 claims description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 13
- 239000012752 auxiliary agent Substances 0.000 claims description 10
- 239000000945 filler Substances 0.000 claims description 10
- 239000000049 pigment Substances 0.000 claims description 10
- 239000010703 silicon Substances 0.000 claims description 10
- 229910052710 silicon Inorganic materials 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 9
- 239000004593 Epoxy Substances 0.000 claims description 8
- 239000011787 zinc oxide Substances 0.000 claims description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
- -1 glycidyl ester Chemical class 0.000 claims description 6
- 239000008096 xylene Substances 0.000 claims description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- 239000004952 Polyamide Substances 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 229920002647 polyamide Polymers 0.000 claims description 4
- NQBXSWAWVZHKBZ-UHFFFAOYSA-N 2-butoxyethyl acetate Chemical compound CCCCOCCOC(C)=O NQBXSWAWVZHKBZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- 229910000410 antimony oxide Inorganic materials 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 2
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 2
- 239000012948 isocyanate Substances 0.000 claims description 2
- 150000002513 isocyanates Chemical class 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 0.000 claims description 2
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 2
- 239000003921 oil Substances 0.000 claims description 2
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 239000001993 wax Substances 0.000 claims description 2
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 claims 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 abstract description 18
- 229910001431 copper ion Inorganic materials 0.000 abstract description 18
- 239000013535 sea water Substances 0.000 abstract description 9
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 7
- 230000006378 damage Effects 0.000 abstract description 5
- 230000009471 action Effects 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 229910001415 sodium ion Inorganic materials 0.000 abstract description 2
- 239000000047 product Substances 0.000 abstract 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical group [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 18
- 239000000243 solution Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 12
- 239000002131 composite material Substances 0.000 description 9
- 239000010949 copper Substances 0.000 description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- 229910052802 copper Inorganic materials 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 238000002386 leaching Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000004677 Nylon Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229920001778 nylon Polymers 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 3
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 3
- 239000002539 nanocarrier Substances 0.000 description 3
- 241000282414 Homo sapiens Species 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 150000004699 copper complex Chemical class 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 239000002574 poison Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 241000282412 Homo Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 238000011482 antibacterial activity assay Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000013270 controlled release Methods 0.000 description 1
- 229940116318 copper carbonate Drugs 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 229960004643 cupric oxide Drugs 0.000 description 1
- 238000005202 decontamination Methods 0.000 description 1
- 230000003588 decontaminative effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000004845 glycidylamine epoxy resin Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 229920013818 hydroxypropyl guar gum Polymers 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000010220 ion permeability Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000010446 mirabilite Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 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
- 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
- C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
- C09D5/1612—Non-macromolecular compounds
- C09D5/1618—Non-macromolecular compounds inorganic
-
- 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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2248—Oxides; Hydroxides of metals of copper
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Paints Or Removers (AREA)
Abstract
The invention discloses a slow-release cellulose-cuprous oxide antifouling agent, a preparation method and application thereof, wherein the preparation of the antifouling agent comprises the following steps: (1) Adding ascorbic acid and polyvinylpyrrolidone into a copper sulfate solution, and uniformly stirring to obtain a solution A; (2) Adding cellulose into the solution A, and oscillating to adsorb until the cellulose is balanced to obtain a dispersion liquid B; (3) Dropwise adding sodium hydroxide solution into the dispersion liquid B at a certain flow rate while stirring, and reacting until the solution is completely changed into red yellow; centrifugal separation is carried out to obtain a solid product; and (4) washing the solid product to be neutral, and drying to obtain the product. The anti-fouling agent can realize the exchange of copper ions and sodium ions under the action of seawater, thereby realizing the slow release of the copper ions; the copper ion release process is slow and stable, the antibacterial rate reaches 99.99%, the content of the anti-fouling agent in the anti-fouling paint can be reduced, and the anti-fouling paint has little harm to the environment and is more environment-friendly.
Description
Technical Field
The invention belongs to the technical field of marine antifouling paint, and particularly relates to a slow-release cellulose-cuprous oxide antifouling agent, and a preparation method and application thereof.
Background
There are many microorganisms, marine plants and marine animals in the ocean, of which there are up to 4000 marine organisms that are fouling. After the marine organisms are attached to the bottom of the ship, the resistance of the ship can be increased, the navigational speed of the ship can be reduced, the fuel consumption is increased, and the mechanical abrasion is increased; marine organisms can adhere to the steel sheet to damage the paint film, and accelerate corrosion of the steel sheet. The maintenance times and time of the ship are increased. With the continuous exploration of marine resources by humans and the explosive development of the marine industry, the marine biofouling problem is becoming more apparent.
The application of ship antifouling paint is the most economical and effective measure for reducing marine fouling to ships and has the widest application range. The antifouling paint is generally coated on the ship bottom antirust paint and is positioned at the outermost layer; the main function is to gradually release the poison materials through the seepage, diffusion or hydrolysis of the poison materials in the paint film, so as to achieve the purpose of preventing marine organisms from adhering to the ship bottom.
The antifouling agent is a main component of the antifouling coating layer which plays a role in antifouling. The currently widely used anti-fouling agent is cuprous oxide. The cuprous oxide antifouling mechanism is that after the antifouling coating is contacted with seawater, a copper complex is formed, the unstable copper complex is rapidly converted into stable bivalent copper ions by oxygen in the seawater, a toxic microlayer with the thickness of more than ten micrometers is formed on the surface of a coating film, and the copper ions in the microlayer can penetrate through biological cell membranes and enter cells to generate toxic effects, so that an antifouling effect is achieved. Copper ions react with organic matters or inorganic matters in the seawater and are continuously separated out from the water, so that the toxicity is obviously reduced, and the harm to non-target organisms is reduced.
The release rate of the anti-fouling agent in the anti-fouling paint has a direct effect on the effect of the marine anti-fouling paint. Many paints show good effects in the initial stage of use due to the relatively high initial release rate of the effective components of the anti-fouling agent, but little release of the anti-fouling agent in the later stage, so that the surface of the material is attached with fouling organisms by marine organisms. The cuprous oxide antifouling agent can achieve ideal antifouling effect only when the filling part of the cuprous oxide antifouling agent in a coating formula system is higher (generally 25-50 wt%); however, if the cuprous oxide is continuously used in a high amount, excessive copper ions are released into the marine environment and are continuously enriched in the marine ecosystem, and remain in organisms to be finally deposited into the human body, which poses a great threat to the safety of the marine ecosystem and the health of human beings.
In the long term, in order to protect the marine environment, the copper-containing anti-fouling agent should be slowly released, so that the addition amount of the cuprous oxide anti-fouling agent is reduced as much as possible while the anti-fouling performance is ensured. As patent document CN113402977a discloses a composite anti-fouling paint capable of controllably releasing cuprous oxide and a preparation method thereof, the cuprous oxide is coated on a composite nano-carrier, the tightness of the composite nano-carrier is controlled by pH, so that uniform and quantitative release of the cuprous oxide coated on the composite nano-carrier can be realized, and the cuprous oxide is released only when an anti-fouling agent contacts with seawater, i.e. the anti-fouling paint at the contact part of a ship body and the seawater can release the cuprous oxide for decontamination, thereby prolonging the service life of the paint. However, this document still has the problem that the release rate of cuprous oxide cannot be controlled for a long period of time after the hull is contacted with seawater.
Patent document CN112409026a discloses a method of coating a composite antifouling agent (Cu powder, cu 2 O、TiO 2 One or more than two of (a) are mixedThe compound) can lead the composite antifouling agent to be slowly released on the surface of the coating through the hydrolysis reaction of the functional group and the weak alkaline seawater. However, the antifouling coating in this document is required to be formed by sintering at 500 to 700 ℃, and is limited in construction and application.
Patent document CN108841171a discloses a nylon composite material capable of preventing marine organisms from fouling for a long time, which is prepared by uniformly mixing 0.5-10% of dried copper antifouling agent (copper oxide, cuprous oxide or copper carbonate) powder, 1-20% of sodium carboxymethyl cellulose powder, 0.1-1% of coupling agent and the balance of nylon powder in a high-speed mixer, and taking out the mixture to obtain the nylon copper composite powder. However, the nylon composite material for preventing adhesion of organisms injection molded in this document cannot be used in combination with a ship base material.
The patent document CN106987191A discloses a self-grinding nontoxic ship bottom antifouling paint and a preparation method thereof, wherein the self-grinding nontoxic ship bottom antifouling paint comprises, by weight, 26-31 parts of a modified resin composition, 10-13 parts of a solvent, 2.8-3.1 parts of nano cuprous oxide, 5-6 parts of hydroxyethyl cellulose, 0.3-0.8 part of hydroxypropyl guar gum, 2-3 parts of iron oxide red and 4-6 parts of mirabilite; the antifouling effect is as long as 24 months, and the later nanometer cuprous oxide has the slow release effect, thereby achieving the long-acting antifouling function. However, the hydroxyethyl cellulose in this document is mainly used as a thickener for a paint, and the problem of the ratio of the hydroxyethyl cellulose to the thickener in achieving a sustained release effect is not examined.
As the deposition of copper in water body can further cause harm to the environment, along with the continuous enhancement of environmental awareness, the development of the long-acting anti-fouling paint with low copper content and slow-release anti-fouling agent has important significance on the basis of not affecting the efficacy of the anti-fouling paint as much as possible.
Disclosure of Invention
Aiming at the problem of high content of the added cuprous oxide anti-fouling agent caused by ensuring long-term anti-fouling effect, the invention aims to provide a preparation method of the slow-release cellulose-cuprous oxide anti-fouling agent, and the prepared anti-fouling agent is applied to an anti-fouling paint, so that the content of the anti-fouling agent in the anti-fouling paint is reduced through the slow-release effect of copper ions, and the preparation method is simple, reduces the harm to the environment and is more environment-friendly.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the invention relates to a preparation method of a slow-release cellulose-cuprous oxide antifouling agent, which is characterized by comprising the following steps: (1) Adding ascorbic acid and polyvinylpyrrolidone into a copper sulfate solution, and uniformly stirring to obtain a solution A; (2) Adding cellulose into the solution A, and oscillating to adsorb until the cellulose is balanced to obtain a dispersion liquid B; (3) Dropwise adding sodium hydroxide solution into the dispersion liquid B at a certain flow rate while stirring, and reacting until the solution is completely changed into red yellow; centrifugal separation is carried out to obtain a solid product; (4) Washing the solid product to be neutral, and drying to obtain the slow-release cellulose-cuprous oxide antifouling agent;
the mass ratio of the ascorbic acid to the copper sulfate is 1 (2.5-3), and preferably the mass ratio of the ascorbic acid to the copper sulfate is 1:3, a step of;
the mass ratio of polyvinylpyrrolidone to copper sulfate is 1 (12.5-50), preferably the mass ratio of polyvinylpyrrolidone to copper sulfate is 1:12.5;
the diameter of the cellulose is 4-50 nm, and the length is 0.5-5 mu m;
the mass ratio of the cellulose to the copper sulfate is 1 (5-20);
the mass ratio of the sodium hydroxide to the copper sulfate is 1 (2.5-3).
Preferably, in the step (3), sodium hydroxide is added dropwise at a flow rate of 0.5-1 mL/min.
Preferably, the centrifugal speed in the step (3) is 4000-8000 r/min, and the centrifugal speed is 3-10 min.
The invention also provides the slow-release cellulose-cuprous oxide antifouling agent prepared by the preparation method of the slow-release cellulose-cuprous oxide antifouling agent.
The invention also provides application of the slow-release cellulose-cuprous oxide antifouling agent in preparation of antifouling paint; the invention relates to an antifouling paint containing a slow-release cellulose-cuprous oxide antifouling agent, which comprises a component A and a component B, and is characterized in that the component A contains 30-60% of epoxy resin, 20-30% of the slow-release cellulose-cuprous oxide antifouling agent, 1-5% of pigment and filler, 2-5% of auxiliary agent and 10-30% of solvent by mass percent; the component B is an epoxy curing agent; the mass ratio of the component A to the component B is 1 (0.4-1);
the epoxy resin is at least one of glycidyl ether epoxy resin, glycidyl amine epoxy resin and glycidyl ester epoxy resin; the pigment and filler is at least one of titanium dioxide, zinc oxide, iron oxide red, mica powder, talcum powder, calcium carbonate, montmorillonite, antimony oxide, kaolin and diatomite; the auxiliary agent is at least one of organic silicon, silicon dioxide, tower oil, polyamide wax, polyethylene glycol, ethylene glycol butyl ether acetate and fluorine-containing polysiloxane; the solvent is at least one of toluene, xylene, butyl acetate, ethyl acetate, methyl isobutyl ketone and n-butanol; the epoxy curing agent is at least one of isocyanate curing agent, polyamide curing agent and phenolic amine curing agent.
The preparation method of the antifouling paint containing the slow-release cellulose-cuprous oxide antifouling agent comprises the following steps: mixing epoxy resin, the slow-release cellulose-cuprous oxide antifouling agent, pigment and filler, an auxiliary agent and a solvent, and stirring for 2-4 hours at room temperature to prepare the component A; mixing the component A and the component B, and stirring for 0.2-0.5 h at room temperature.
Compared with the prior art, the invention has the beneficial effects that:
the invention reduces metallic copper on cellulose in situ to prepare the cellulose loaded metallic copper type antifouling agent powder, and the antifouling agent powder can realize the exchange of copper ions and sodium ions under the action of seawater, thereby realizing the slow release of copper ions; the anti-fouling paint is applied to the anti-fouling field to prepare the marine anti-fouling paint, the copper ion release process is stable, the antibacterial rate reaches 99.99%, the anti-fouling paint has the advantages of low copper content, long-acting copper ion release performance, high-efficiency anti-fouling performance and the like, the preparation method is simple, the content of an anti-fouling agent in the anti-fouling paint can be reduced, the environmental hazard is small, and the anti-fouling paint is more environment-friendly and can be applied to the marine ship anti-fouling field.
Drawings
FIG. 1 is a graph showing the copper ion permeability of the antifouling paint of the controlled-release cellulose-cuprous oxide antifouling agent of examples 3 to 4 and comparative example 2.
Detailed Description
It will be appreciated by persons skilled in the art that the present embodiment is provided for illustration only and not for limitation of the invention, and that modifications and variations may be made to the embodiment within the scope of the invention as defined in the appended claims.
Example 1
The preparation method of the slow-release cellulose-cuprous oxide antifouling agent comprises the following steps: (1) Dispersing 0.44g of ascorbic acid, 0.1g of polyvinylpyrrolidone and 1.25g of copper sulfate solution in 35mL of deionized water, and uniformly stirring at a rotating speed of 500r/min to obtain a solution A; (2) Adding 0.25g of cellulose into the solution A, and oscillating to adsorb to balance to obtain a dispersion liquid B; (3) Dropwise adding 20mL of sodium hydroxide solution with concentration of 0.5mol/L into the dispersion liquid B at a flow rate of 0.5mL/min under stirring, and reacting until the solution is completely red-yellow; centrifuging for 5min at 4000r/min, and separating to obtain a precipitated solid product; (4) And washing the solid product to be neutral, and drying to obtain the slow-release cellulose-cuprous oxide antifouling agent.
Example 2
The preparation method of the slow-release cellulose-cuprous oxide antifouling agent comprises the following steps: (1) Dispersing 1.0g of ascorbic acid, 0.1g of polyvinylpyrrolidone and 2.5g of copper sulfate solution in 40mL of deionized water, and uniformly stirring at a rotating speed of 500r/min to obtain a solution A; (2) Adding 0.5g of cellulose into the solution A, and oscillating to adsorb to balance to obtain a dispersion liquid B; (3) Dropwise adding 20mL of sodium hydroxide solution with the concentration of 1.0mol/L into the dispersion liquid B at the flow rate of 1.0mL/min under stirring, and reacting until the solution is completely red-yellow; centrifuging at 6000r/min for 5min, and separating to obtain a precipitated solid product; (4) And washing the solid product to be neutral, and drying to obtain the slow-release cellulose-cuprous oxide antifouling agent.
Example 3
An antifouling paint containing a slow-release cellulose-cuprous oxide antifouling agent comprises 4.0g of a component A and 4.0g of a component B; wherein the component A comprises the following components in percentage by mass: 45% of epoxy resin E51, 25% of the slow-release cellulose-cuprous oxide antifouling agent prepared in example 1, 4% of pigment and filler (2% of zinc oxide and 2% of diatomite), 2% of auxiliary agent (organic silicon) and 24% of solvent (xylene and toluene in a mass ratio of 3:2); the component B is an epoxy curing agent T31.
The preparation method of the antifouling paint comprises the following steps: (1) Mixing the epoxy resin in the component A, the antifouling agent, zinc oxide, diatomite, organic silicon and a solvent, and stirring for 2 hours at room temperature to prepare the resin containing the antifouling agent; (2) Mixing the component A and the component B according to the proportion of 1:1, and stirring for 0.2h at room temperature to obtain the antifouling paint containing the slow-release cellulose-cuprous oxide antifouling agent.
Example 4
An antifouling paint containing a slow-release cellulose-cuprous oxide antifouling agent comprises 10.0g of a component A and 10.0g of a component B; wherein the component A comprises the following components in percentage by mass: 55% of epoxy resin E51, 20% of the slow-release cellulose-cuprous oxide antifouling agent prepared in example 1, 3% of pigment and filler (2% of zinc oxide+1% of diatomite), 2% of auxiliary agent (organic silicon) and 20% of solvent (xylene and toluene in a mass ratio of 3:2); the component B is an epoxy curing agent T31.
The preparation method of the antifouling paint comprises the following steps: (1) Mixing the epoxy resin in the component A, the antifouling agent, zinc oxide, diatomite, organic silicon and a solvent, and stirring for 3 hours at room temperature to prepare the resin containing the antifouling agent; (2) Mixing the component A and the component B according to the proportion of 1:1, and stirring for 0.3h at room temperature to obtain the antifouling paint containing the slow-release cellulose-cuprous oxide antifouling agent.
Example 5
An antifouling paint containing a slow-release cellulose-cuprous oxide antifouling agent comprises 10.0g of a component A and 10.0g of a component B; wherein the component A comprises the following components in percentage by mass: 55% of epoxy resin E51, 20% of the slow-release cellulose-cuprous oxide antifouling agent prepared in example 2, 3% of pigment and filler (2% of zinc oxide+1% of diatomite), 2% of auxiliary agent (organic silicon) and 20% of solvent (xylene and toluene in a mass ratio of 3:2); the component B is an epoxy curing agent T31.
The preparation method of the antifouling paint comprises the following steps: (1) Mixing the epoxy resin in the component A, the antifouling agent, the diatomite, the organic silicon and the solvent, and stirring for 3 hours at room temperature to prepare the resin containing the antifouling agent; (2) Mixing the component A and the component B according to the proportion of 1:1, and stirring for 0.5h at room temperature to obtain the antifouling paint containing the slow-release cellulose-cuprous oxide antifouling agent.
Example 6
An antifouling paint containing a slow-release cellulose-cuprous oxide antifouling agent comprises 10.0g of a component A and 10.0g of a component B; wherein the component A comprises the following components in percentage by mass: 30% of epoxy resin E51, 30% of the slow-release cellulose-cuprous oxide antifouling agent prepared in example 2, 5% of pigment and filler (2% of zinc oxide+3% of diatomite), 5% of auxiliary agent (organic silicon) and 30% of solvent (xylene and toluene in a mass ratio of 3:2); the component B is an epoxy curing agent T31.
The preparation method of the antifouling paint comprises the following steps: (1) Mixing the epoxy resin in the component A, the antifouling agent, the diatomite, the organic silicon and the solvent, and stirring for 3 hours at room temperature to prepare the resin containing the antifouling agent; (2) Mixing the component A and the component B according to the proportion of 1:1, and stirring for 0.5h at room temperature to obtain the antifouling paint containing the slow-release cellulose-cuprous oxide antifouling agent.
Comparative example 1
Comparative example 1 is a comparative example of example 1, comprising the steps of: (1) Dispersing 0.1g of polyvinylpyrrolidone and 1.25g of copper sulfate in 35mL of deionized water, and uniformly stirring at a rotating speed of 500r/min to obtain a dispersion liquid; (2) Adding 20mL of sodium hydroxide solution with the concentration of 1mol/L to the dispersion liquid; (3) adding 0.44g of ascorbic acid to the dispersion; (4) adding 0.25g of cellulose into the dispersion liquid and uniformly stirring; centrifuging for 5min at 4000r/min, and separating to obtain a precipitated solid product; (5) Washing the solid product to neutrality and drying.
Comparative example 2
Comparative example 2 is a comparative example of example 3, and the formulation is the same as the preparation method except that the antifouling agent is replaced with the antifouling agent of comparative example 1.
Experimental example 1
Antibacterial performance tests were carried out on the antifouling paints prepared in examples 3 to 6 and comparative example 2 according to the methods of national Standard GB/T21866-2008 antibacterial paint (paint film) antibacterial assay and antibacterial Effect, respectively. The results shown in Table 1 indicate that the antibacterial rate of the antifouling paint prepared in examples 3 to 6 reaches 99.99%, indicating that the antifouling paint of the present invention has a high antifouling effect.
Table 1 results of detection of antibacterial properties of antifouling paints of examples 3 to 6 and comparative example 2
Experimental example 2
Copper ion leaching rate measurement was performed on the antifouling paints prepared in example 3, example 4 and comparative example 2 according to the method of national standard GB/T6824-2008, copper ion leaching rate measurement method of ship bottom antifouling paint.
The measurement results of fig. 1 show that the leaching rate of the example 3 is more stable in the antifouling paint of the example 3 and the comparative example 2 with the same cuprous oxide content; the relatively high leaching rate of copper ions in example 3, which has higher cuprous oxide content, in the antifouling paint of example 3 and example 4, shows that the copper ions in the antifouling paint prepared by the invention can be slowly and stably released. The copper ion leaching rate of the ship antifouling paint generally only reaches 20-30 mug/(cm) 2 D) only, the antifouling paint containing the slow-release cellulose-cuprous oxide antifouling agent prepared by the method can meet the surface antifouling use requirements of marine devices and facilities.
Claims (9)
1. The preparation method of the slow-release cellulose-cuprous oxide antifouling agent is characterized by comprising the following steps of: (1) Adding ascorbic acid and polyvinylpyrrolidone into a copper sulfate solution, and uniformly stirring to obtain a solution A; (2) Adding cellulose into the solution A, and oscillating to adsorb until the cellulose is balanced to obtain a dispersion liquid B; (3) Dropwise adding sodium hydroxide solution into the dispersion liquid B at a certain flow rate while stirring, and reacting until the solution is completely changed into red yellow; centrifugal separation is carried out to obtain a solid product; (4) And washing the solid product to be neutral, and drying to obtain the slow-release cellulose-cuprous oxide antifouling agent.
2. The method for preparing a sustained-release cellulose-cuprous oxide antifouling agent according to claim 1, wherein the mass ratio of ascorbic acid to cupric sulfate is 1 (2.5-3); the mass ratio of the polyvinylpyrrolidone to the copper sulfate is 1 (12.5-50); the mass ratio of the cellulose to the copper sulfate is 1 (5-20); the mass ratio of the sodium hydroxide to the copper sulfate is 1 (2.5-3).
3. The method for preparing the sustained-release cellulose-cuprous oxide antifouling agent according to claim 2, wherein the mass ratio of ascorbic acid to cupric sulfate is 1:3, a step of; the mass ratio of polyvinylpyrrolidone to copper sulfate is 1:12.5; the diameter of the cellulose is 4-50 nm, and the length is 0.5-5 mu m.
4. The method for preparing a sustained-release cellulose-cuprous oxide antifouling agent according to claim 1, wherein sodium hydroxide is added dropwise in step (3) at a flow rate of 0.5-1 mL/min; and (3) centrifuging for 3-10 min at the centrifugal speed of 4000-8000 r/min.
5. A sustained-release cellulose-cuprous oxide antifouling agent prepared by the method for preparing a sustained-release cellulose-cuprous oxide antifouling agent according to any one of claims 1 to 4.
6. Use of a slow release cellulose-cuprous oxide antifouling agent as claimed in claim 5 in the preparation of antifouling paint.
7. An antifouling paint containing the sustained-release cellulose-cuprous oxide antifouling agent according to claim 5, which comprises a component A and a component B, wherein the component A comprises 30-60% of epoxy resin, 20-30% of the sustained-release cellulose-cuprous oxide antifouling agent, 1-5% of pigment and filler, 2-5% of auxiliary agent and 10-30% of solvent by mass percent; the component B is an epoxy curing agent; the mass ratio of the component A to the component B is 1 (0.4-1).
8. The antifouling paint according to claim 7, wherein the epoxy resin is at least one of a glycidyl ether type epoxy resin, a glycidyl amine type epoxy resin and a glycidyl ester type epoxy resin; the pigment and filler is at least one of titanium dioxide, zinc oxide, iron oxide red, mica powder, talcum powder, calcium carbonate, montmorillonite, antimony oxide, kaolin and diatomite; the auxiliary agent is at least one of organic silicon, silicon dioxide, tower oil, polyamide wax, polyethylene glycol, ethylene glycol butyl ether acetate and fluorine-containing polysiloxane; the solvent is at least one of toluene, xylene, butyl acetate, ethyl acetate, methyl isobutyl ketone and n-butanol; the epoxy curing agent is at least one of isocyanate curing agent, polyamide curing agent and phenolic amine curing agent.
9. The method for producing an antifouling paint according to claim 7 or 8, comprising the steps of: mixing epoxy resin, the slow-release cellulose-cuprous oxide antifouling agent, pigment and filler, an auxiliary agent and a solvent, and stirring for 2-4 hours at room temperature to prepare the component A; mixing the component A and the component B, and stirring for 0.2-0.5 h at room temperature.
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