CN114956155A - Composite anti-fouling agent and preparation method thereof - Google Patents
Composite anti-fouling agent and preparation method thereof Download PDFInfo
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- CN114956155A CN114956155A CN202210704527.7A CN202210704527A CN114956155A CN 114956155 A CN114956155 A CN 114956155A CN 202210704527 A CN202210704527 A CN 202210704527A CN 114956155 A CN114956155 A CN 114956155A
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- cuprous oxide
- oxide
- titanium
- antifouling agent
- composite
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- 239000002519 antifouling agent Substances 0.000 title claims abstract description 62
- 239000002131 composite material Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title abstract description 24
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical group [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims abstract description 162
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims abstract description 153
- 229940112669 cuprous oxide Drugs 0.000 claims abstract description 153
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 38
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000005260 corrosion Methods 0.000 claims abstract description 14
- 238000000576 coating method Methods 0.000 claims abstract description 13
- 239000011248 coating agent Substances 0.000 claims abstract description 12
- 230000007797 corrosion Effects 0.000 claims abstract description 12
- 239000011162 core material Substances 0.000 claims abstract description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000001301 oxygen Substances 0.000 claims abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 8
- 238000003860 storage Methods 0.000 claims abstract description 8
- 238000007539 photo-oxidation reaction Methods 0.000 claims abstract description 6
- 239000000969 carrier Substances 0.000 claims abstract description 5
- 230000003993 interaction Effects 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 37
- 239000010936 titanium Substances 0.000 claims description 32
- 229910052719 titanium Inorganic materials 0.000 claims description 32
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 31
- 239000000843 powder Substances 0.000 claims description 30
- 239000002243 precursor Substances 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 22
- 238000011065 in-situ storage Methods 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 19
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 18
- 238000005538 encapsulation Methods 0.000 claims description 16
- 150000003839 salts Chemical class 0.000 claims description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 238000000926 separation method Methods 0.000 claims description 14
- 239000003960 organic solvent Substances 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 12
- 238000000967 suction filtration Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- 150000003608 titanium Chemical class 0.000 claims description 10
- 238000006460 hydrolysis reaction Methods 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000001179 sorption measurement Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 230000036571 hydration Effects 0.000 claims description 6
- 238000006703 hydration reaction Methods 0.000 claims description 6
- 230000007062 hydrolysis Effects 0.000 claims description 6
- 230000001939 inductive effect Effects 0.000 claims description 6
- 238000003723 Smelting Methods 0.000 claims description 5
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 4
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 3
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 3
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 3
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 3
- 230000003373 anti-fouling effect Effects 0.000 abstract description 14
- 239000003973 paint Substances 0.000 abstract description 6
- 238000004806 packaging method and process Methods 0.000 abstract description 4
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 11
- 239000007788 liquid Substances 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 238000005286 illumination Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000012858 packaging process Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000004506 ultrasonic cleaning Methods 0.000 description 3
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 239000003899 bactericide agent Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 229960004643 cupric oxide Drugs 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 238000013341 scale-up Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical group NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 239000013148 Cu-BTC MOF Substances 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- XOJVVFBFDXDTEG-UHFFFAOYSA-N Norphytane Natural products CC(C)CCCC(C)CCCC(C)CCCC(C)C XOJVVFBFDXDTEG-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- ZYBWTEQKHIADDQ-UHFFFAOYSA-N ethanol;methanol Chemical compound OC.CCO ZYBWTEQKHIADDQ-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 238000006213 oxygenation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 230000000644 propagated effect Effects 0.000 description 1
- OVARTBFNCCXQKS-UHFFFAOYSA-N propan-2-one;hydrate Chemical compound O.CC(C)=O OVARTBFNCCXQKS-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- -1 titanium oxide compound Chemical class 0.000 description 1
- NOSIKKRVQUQXEJ-UHFFFAOYSA-H tricopper;benzene-1,3,5-tricarboxylate Chemical compound [Cu+2].[Cu+2].[Cu+2].[O-]C(=O)C1=CC(C([O-])=O)=CC(C([O-])=O)=C1.[O-]C(=O)C1=CC(C([O-])=O)=CC(C([O-])=O)=C1 NOSIKKRVQUQXEJ-UHFFFAOYSA-H 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/02—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
-
- 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
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
- C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
- C01P2004/84—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases one phase coated with the other
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- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The invention provides a composite antifouling agent and a preparation method thereof, wherein the composite antifouling agent is a cuprous oxide composite material with a titanium oxide packaging structure, and consists of a cuprous oxide core material and a titanium oxide packaging layer. By utilizing an oxide packaging structure, the contact between water, oxygen and the like in the environment and cuprous oxide is reduced, and the storage stability of the cuprous oxide is improved; meanwhile, by means of the energy band interaction between the cuprous oxide and the titanium oxide, the photogenerated carriers generated on the surface of the cuprous oxide are enhanced and separated, the photooxidation corrosion of the cuprous oxide is inhibited, and the use stability is improved; the composite antifouling agent disclosed by the invention has the advantages of high stability, controllable structure, simple preparation process, suitability for large-scale production and the like, and can be applied to marine antifouling paint to improve the antifouling period of a coating.
Description
Technical Field
The invention relates to the technical field of marine antifouling, and particularly relates to a composite antifouling agent and a preparation method thereof.
Background
Marine organisms, plants, animals and the like, which are inevitable for any marine industry and marine activity, are adsorbed, grown and propagated on the surface of a ship body or a facility submerged in seawater to form biofouling, which increases fuel consumption and aggravates substrate corrosion. The most effective solution to the above fouling problem is to coat antifouling paint on the surface of ships and facilities, and currently, cuprous oxide with broad-spectrum biocidal property is the most widely used main antifouling agent in the field of antifouling paint. However, cuprous oxide is relatively active in chemical properties and is susceptible to environmental conditions (such as temperature, humidity, oxygen, light, etc.) to cause oxidative corrosion failure.
Specifically, in the storage process of raw materials and coatings, cuprous oxide reacts with water and oxygen in the air to cause oxidation failure; during the preparation process of the coating, the heat accumulated by stirring or grinding dispersion can aggravate the oxidation degree; in the practical application process, cuprous oxide exposed on the surface of the coating is easily oxidized by self photon-generated carriers in the environment of simultaneously contacting with light, water and oxygen, and photooxidation self-corrosion occurs. In other words, the chemical stability of the cuprous oxide antifouling agent is a key factor affecting the service performance and the lifetime of the antifouling coating.
In the prior art, the stability of the cuprous oxide is improved mainly by coating a protective layer on the surface of the cuprous oxide. Patent CN107022043A discloses a cuprous oxide composite bactericide and a preparation method thereof, wherein the method couples physical and chemical processes of soluble copper salt adsorption-reduction, acrylamide monomer copolymerization and the like, and a high polymer gel/cuprous oxide composite material is prepared by a one-pot method and is used as a long-acting stable bactericide for marine antifouling paint. The paper Angew. chem. int. Ed.2021,60,8455 proposes a catalyst cuprous oxide @ copper-based organometallic framework compound (Cu) 2 O @ Cu-BTC) and a preparation method thereof, the method adopts a dipping deposition strategy, and utilizes strong complexation between copper ions on the surface of the cuprous oxide and organic ligand molecules to form atoms on the surface of the cuprous oxide nanowireThe copper-based organic metal framework compound is deposited, and the formed Cu-BTC coating layer obviously improves the stability of the cuprous oxide substrate in the catalytic cycle process. However, in order to ensure the stability of the cuprous oxide in the above synthesis and preparation processes, the existing modification strategies either require the simultaneous processes of cuprous oxide synthesis and protective layer coating, or require the use of specific reagents (organic ligand small molecules, etc.) and fine preparation means (such as electrochemical deposition, monatomic deposition, etc.), which greatly limits the synthesis efficiency of the cuprous oxide composite antifouling agent material, greatly increases the preparation process cost, and is not conducive to scale-up production and popularization of coating application.
In view of the high filling proportion (generally up to 25-50 wt%) of the cuprous oxide antifouling agent in the coating formula system, the antifouling coating is generally prepared by an electrolysis method capable of mass production or smelting cuprous oxide in the industry. Cuprous oxide manufacturers introduce specific measures in the process flow to improve the stability of cuprous oxide: patent CN102089392A proposes adding antioxidant such as glycerol and glucose into electrolyte; patent CN104497679A proposes depositing a hydrophobic carbon layer during high temperature sintering. However, these protective measures do not regulate the intrinsic structure-performance of the cuprous oxide, so that it is difficult to fundamentally inhibit the oxidative corrosion of the cuprous oxide during storage and use, especially the photo-oxidative self-corrosion during the antifouling process, and thus the technical bottlenecks of poor stability and short service life of the existing cuprous oxide antifouling agent cannot be overcome.
Disclosure of Invention
In view of the above, the invention aims to provide a composite antifouling agent and a preparation method thereof, which solve the problems of poor storage resistance and poor antifouling use stability of the existing cuprous oxide antifouling agent, so as to meet the application requirement of long-term stability of an antifouling coating, effectively improve the structural controllability of the composite antifouling agent, simplify the preparation process of the antifouling agent, reduce the cost, facilitate large-scale production, and are suitable for popularization and application in the technical field of marine antifouling paints.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
the invention relates to a composite antifouling agent and a preparation method thereof, wherein the composite antifouling agent is a titanium oxide-encapsulated cuprous oxide composite material and consists of a cuprous oxide core material and a titanium oxide encapsulating layer, and the titanium oxide encapsulating layer is coated on the outer surface of cuprous oxide and is used for reducing the contact of water, oxygen and the like with the cuprous oxide in the environment and improving the storage stability by utilizing an oxide encapsulating structure; meanwhile, by means of the energy band interaction between the cuprous oxide and the titanium oxide, the photogenerated carriers generated on the surface of the cuprous oxide are enhanced and separated, the photooxidation corrosion of the cuprous oxide is inhibited, and the use stability is improved.
Further, the titanium oxide encapsulating layer has a porous structure formed by stacking oxide particles, the coating thickness is 50-200nm, and the crystal form of the titanium oxide encapsulating layer is at least one of amorphous, anatase and rutile.
Further, the composite antifouling agent is prepared by in-situ adsorption-hydrolysis of titanium precursor salt on the surface of cuprous oxide.
Further, the preparation method of the composite anti-fouling agent comprises the following steps:
1) and (3) cuprous oxide surface hydration pretreatment: adding cuprous oxide powder into an organic solvent for ultrasonic dispersion to remove residual oil stains and other assistants on the surfaces of the particles; then, adding the cleaned cuprous oxide powder into deionized water, stirring at a constant speed for 1-4 hours, and performing suction filtration separation to obtain hydrated cuprous oxide core material powder;
2) in-situ hydrolysis-encapsulation of the titanium oxide: adding the hydrated cuprous oxide powder, titanium precursor salt and acetylacetone into an ethanol solution; stirring at a constant speed, carrying out adsorption reaction for 12-36 hours, and then using deionized water-organic solvent mixed washing liquor; and washing and separating the cuprous oxide composite antifouling agent material, placing the cuprous oxide composite antifouling agent material in an environment of room temperature of 25-30 ℃ for drying for 12-24 hours, and inducing the titanium precursor adsorbed on the surface of the cuprous oxide to generate in-situ hydrolysis by virtue of water vapor in the air to obtain the titanium oxide-encapsulated cuprous oxide composite antifouling agent material.
Further, the cuprous oxide comprises industrial-grade electrolytic cuprous oxide, smelting cuprous oxide or laboratory-made cuprous oxide.
Further, the titanium precursor salt is an organic or inorganic titanium salt, the organic titanium salt comprises at least one of tetrabutyl titanate and isopropyl titanate, and the inorganic titanium salt comprises at least one of titanium trichloride and titanium sulfate.
Furthermore, in the hydration pretreatment process, the mass ratio of the cuprous oxide to the deionized water is 1 (10-20).
Further, in the in-situ hydrolysis-packaging process, the mass ratio of the cuprous oxide to the ethanol is 1 (80-150).
Furthermore, in the in-situ hydrolysis-packaging process, the molar ratio of the cuprous oxide to the titanium precursor salt is 1 (1.2-2.5), and the molar ratio of the acetylacetone to the titanium precursor salt is 0.02-0.05) to 1.
Further, in the in-situ hydrolysis-packaging process, the volume ratio of deionized water and an organic solvent of the mixed washing liquid is (0.11-1):1, wherein the organic solvent comprises one or more of methanol, ethanol, isopropanol and acetone, and the separation mode comprises centrifugation or suction filtration.
Compared with the prior art, the composite antifouling agent and the preparation method thereof have the following beneficial effects:
the cuprous oxide composite antifouling agent has a typical titanium oxide packaging structure, can exert a physical protection effect, isolates the corrosion of water, oxygen and the like in the environment to a cuprous oxide core material, and improves the storage stability of the cuprous oxide composite antifouling agent; meanwhile, the titanium oxide has an energy band structure matched with cuprous oxide, and a surface photon-generated carrier can be rapidly separated, so that the photo-oxidation corrosion of the cuprous oxide in the antifouling process is fundamentally inhibited, and the use stability of the titanium oxide is improved. The preparation method has the advantages of clear route, simple reaction conditions and high repeatability, can directly modify the existing industrial cuprous oxide powder, is favorable for scale-up production, and enables the composite antifouling agent to be effectively applied to the application field of marine antifouling paint.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention, illustrate embodiments of the invention and together with the description serve to explain the invention and are not to limit the invention. In the drawings:
FIG. 1 is a schematic drawing of an electron scanning microscope photograph of pristine cuprous oxide;
FIG. 2 is a schematic view of an electron scanning microscope photograph of a titanium oxide-encapsulated cuprous oxide;
FIG. 3 is a schematic diagram of the X-ray diffraction patterns of cuprous oxide encapsulated by titanium oxide and raw cuprous oxide;
FIG. 4 is a graphical representation of the X-ray photoelectron spectroscopy spectrum of titanium oxide-encapsulated cuprous oxide;
FIG. 5 is a schematic diagram of an X-ray diffraction spectrum of cuprous oxide encapsulated by titanium oxide before and after a stability evaluation test;
FIG. 6 is a schematic diagram of an X-ray diffraction spectrum of original cuprous oxide before and after a stability evaluation test;
FIG. 7 is a schematic drawing of a scanning electron microscope photograph of a titanyl compound-encapsulated cuprous oxide after a stability evaluation test;
fig. 8 is a schematic view of a scanning electron microscope photograph of raw cuprous oxide after a stability evaluation test.
Detailed Description
The inventive concepts of the present disclosure will be described hereinafter using terms commonly employed by those skilled in the art to convey the substance of their work to others skilled in the art. These inventive concepts may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.
It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings.
This example provides a composite anti-fouling agent and a method for preparing the same. The composite antifouling agent is a titanium oxide-encapsulated cuprous oxide composite material and consists of a cuprous oxide core material and a titanium oxide encapsulation layer, wherein the titanium oxide encapsulation layer is wrapped on the outer surface of cuprous oxide and used for reducing the contact between water, oxygen and the like in the environment and the cuprous oxide by utilizing an oxide encapsulation structure and improving the storage stability of the composite antifouling agent; meanwhile, by means of the energy band interaction between the cuprous oxide and the titanium oxide, the photogenerated carriers generated on the surface of the cuprous oxide are enhanced and separated, the photooxidation corrosion of the cuprous oxide is inhibited, and the use stability is improved. The titanium oxide layer on the surface of the cuprous oxide core material has a porous structure formed by stacking oxide nanoparticles, and the coating thickness of the titanium oxide layer is 50-200nm (shown in figures 1 and 2). The composite antifouling agent is prepared by in-situ adsorption-hydrolysis of titanium precursor salt on the surface of cuprous oxide, the preparation conditions are mild, and a reducing agent, a precipitator, an etching agent and the like are not needed in the preparation reaction process.
The titanium precursor salt is adsorbed and hydrolyzed in situ on the surface of cuprous oxide, so that the structure of the cuprous oxide can be effectively protected, the stability of the cuprous oxide is improved, the integral corrosion resistance of the antifouling agent is enhanced, the preparation method is simplified, the production scale of the antifouling agent can be effectively improved, and the preparation yield can be increased to a certain extent.
The preparation method of the composite antifouling agent comprises two steps:
1) and (3) cuprous oxide surface hydration pretreatment: adding a certain amount of cuprous oxide powder into an organic solvent for ultrasonic dispersion, removing residual oil stains and other assistants on the surfaces of the particles, then adding the cleaned cuprous oxide powder into a certain amount of deionized water, stirring at a constant speed for 1-4 hours, and performing suction filtration separation to obtain hydrated cuprous oxide powder.
Wherein the mass ratio of the cuprous oxide to the deionized water is 1 (10-20), the cuprous oxide powder comprises industrial electrolysis or smelting cuprous oxide (micron scale) or laboratory self-made cuprous oxide (nano scale), and the pretreatment washing organic solvent comprises one or more of methanol, ethanol, isopropanol and acetone.
The method has the advantages that the hydration pretreatment of the cuprous oxide surface is beneficial to removing other compounds on the cuprous oxide surface, the purity of the cuprous oxide surface is kept, and the hydrated cuprous oxide powder is obtained by using the suction filtration and separation of deionized water, so that the adsorption capacity of the cuprous oxide surface to the titanium oxide compound is enhanced.
2) In-situ hydrolysis-encapsulation of the titanium oxide: adding the hydrated cuprous oxide powder, titanium precursor salt and acetylacetone into an ethanol solution, stirring at a constant speed, carrying out adsorption reaction for 12-36 hours, then using a certain amount of deionized water-organic solvent mixed washing liquid, washing and separating the washing liquid, placing the washing liquid in an environment with room temperature of 25-30 ℃ for drying for 12-24 hours, and inducing the titanium precursor adsorbed on the surface of cuprous oxide to carry out in-situ hydrolysis by virtue of water vapor in the air to obtain the cuprous oxide composite antifouling agent material with the titanium oxide encapsulation structure.
Wherein the mass ratio of the cuprous oxide to the ethanol is 1 (80-150), the molar ratio of the cuprous oxide to the titanium precursor salt is 1 (1.2-2.5), the molar ratio of the acetylacetone to the titanium precursor salt is (0.02-0.05):1, and the volume ratio of the deionized water to the organic solvent of the mixed lotion is (0.11-1): 1; in addition, the in-situ hydrolysis-encapsulation organic solvent comprises one or more of methanol, ethanol, isopropanol and acetone, and the separation mode comprises centrifugation or suction filtration; the titanium precursor salt is organic or inorganic titanium salt, the organic titanium salt comprises at least one of tetrabutyl titanate and isopropyl titanate, and the inorganic titanium salt comprises at least one of titanium trichloride and titanium sulfate. The cuprous oxide composite antifouling agent is subjected to calcination post-treatment (300-650 ℃) at different temperatures according to different types of the selected titanium salt precursors, and the crystalline phase structure of the titanium oxide encapsulation layer can be further regulated and controlled. In this embodiment, the crystal form of the titanium oxide encapsulation layer on the surface of the cuprous oxide core material is a single or mixed crystal phase such as amorphous, anatase, and rutile, and has an energy band structure matched with the cuprous oxide core material.
As shown in fig. 3, the titanyl compound-encapsulated cuprous oxide composite antifouling agent shows characteristic diffraction peaks attributed to cuprous oxide and titanyl compound, respectively, and no characteristic diffraction peak of cupric oxide appears, as characterized by X-ray diffraction. As shown in FIG. 4, the titanyl compound-encapsulated cuprous oxide composite antifouling agent shows Cu attributed to cuprous oxide as characterized by X-ray photoelectron spectroscopy 2 p and Ti of titanyl compound 2 p characteristic signal peak.
As shown in fig. 5 to 8, the stability evaluation test was performed on the raw cuprous oxide and the titanyl compound-encapsulated cuprous oxide composite antifouling agent under the following test conditions: the cuprous oxide material is immersed in deionized water and placed in a constant-temperature illumination incubator, wherein the environmental temperature and the illumination intensity are respectively 25 ℃ and 2000 lux. By comparing the X-ray diffraction spectra and scanning electron microscope photographs of the original cuprous oxide and titanium oxide encapsulated cuprous oxide composite antifouling agent before and after the stability evaluation test, the cuprous oxide composite antifouling agent can be found to have better chemical stability, and the composition-structure of the cuprous oxide composite antifouling agent still remains unchanged after the illumination and immersion tests. In contrast, the unmodified original cuprous oxide shows an obvious oxidation corrosion trend after illumination and soaking tests, characteristic diffraction peaks belonging to the copper oxide and positioned at 35.3 degrees and 38.6 degrees appear, and the surface of a cuprous oxide particle shows obvious corrosion and disintegration appearance.
Example 1
Firstly weighing 100g of industrial-grade electrolytic cuprous oxide powder, dispersing the electrolytic cuprous oxide powder in methanol, carrying out ultrasonic cleaning to remove oil stains and other auxiliary agents attached to the surfaces of particles, then, adding the cleaned cuprous oxide powder into 1.5L of deionized water, stirring at a constant speed for 2 hours, performing suction filtration and separation to obtain hydrated cuprous oxide powder, then 100g of hydrated cuprous oxide powder, 370g of tetrabutyl titanate and 3.0g of acetylacetone are added into 12L of ethanol solution and stirred at a constant speed for adsorption reaction for 24 hours, then, deionized water-ethanol (200mL:1800mL) mixed washing liquor is adopted for suction filtration washing and separation, placing the titanium precursor in a room temperature environment at 25 ℃, inducing the titanium precursor adsorbed on the surface of the cuprous oxide to generate in-situ hydrolysis by virtue of water vapor in the air, drying for 24 hours, and finally, calcining for 5 hours at the temperature of 450 ℃ by using nitrogen to obtain the titanium oxide-encapsulated cuprous oxide composite antifouling agent material.
Example 2
Firstly weighing 50g of industrial smelting cuprous oxide powder, dispersing the powder in acetone, carrying out ultrasonic cleaning to remove oil stains and other auxiliary agents attached to the surfaces of particles, then adding the cleaned cuprous oxide powder into 1L of deionized water, stirring at a constant speed for 3.5 hours, carrying out suction filtration and separation to obtain hydrated cuprous oxide powder, then adding 50g of the hydrated cuprous oxide powder, 125g of isopropyl titanate and 1.5g of acetylacetone into 5L of ethanol solution, stirring at a constant speed, carrying out adsorption reaction for 30 hours, then adopting deionized water-methanol (300mL:700mL) mixed washing liquid, carrying out suction filtration, washing and separation, placing the mixed washing liquid in a room temperature environment at 30 ℃, inducing a titanium precursor adsorbed on the cuprous oxide surface to generate in-situ hydrolysis by means of water vapor in the air, drying for 24 hours, and finally calcining for 3 hours at 650 ℃ under nitrogen, and obtaining the titanium oxide encapsulated cuprous oxide composite antifouling agent material.
Example 3
Firstly, 1g of self-made cuprous oxide powder in a laboratory is weighed, the cuprous oxide powder is dispersed in methanol-ethanol mixed solution for ultrasonic cleaning to remove oil stains and other auxiliary agents attached to the surfaces of particles, and then, adding the cleaned cuprous oxide powder into 15mL of deionized water, stirring at a constant speed for 1 hour, performing suction filtration and separation to obtain hydrated cuprous oxide powder, then, 1g of hydrated cuprous oxide powder, 2.2g of titanium trichloride and 0.06g of acetylacetone are added into 150mL of ethanol solution and stirred at a constant speed, and the mixture is subjected to adsorption reaction for 12 hours, then deionized water-acetone (10mL:10mL) mixed washing liquid is adopted for centrifugal washing and separation, placing the cuprous oxide precursor in a room temperature environment of 25 ℃, inducing the titanium precursor adsorbed on the surface of the cuprous oxide to generate in-situ hydrolysis by virtue of water vapor in the air, drying for 12 hours, the titanium oxide encapsulated cuprous oxide composite antifouling agent material can be obtained without calcination post-treatment.
In the present invention, any composite antifouling agent may include the cuprous oxide component described in this embodiment, and the preparation method of the composite antifouling agent further includes conventional preparation methods such as washing and separation methods on the basis of the relevant components of cuprous oxide provided in this embodiment, which are not described herein again in view of the fact that they are all the prior art.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. The composite antifouling agent is characterized in that the composite antifouling agent is a titanium oxide-encapsulated cuprous oxide composite material and consists of a cuprous oxide core material and a titanium oxide encapsulation layer, and the titanium oxide encapsulation layer is coated on the outer surface of cuprous oxide and used for reducing the contact of water, oxygen and the like in the environment with the cuprous oxide by utilizing an oxide encapsulation structure and improving the storage stability of the composite antifouling agent; meanwhile, by means of the energy band interaction between the cuprous oxide and the titanium oxide, the photogenerated carriers generated on the surface of the cuprous oxide are enhanced and separated, the photooxidation corrosion of the cuprous oxide is inhibited, and the use stability is improved.
2. The composite antifouling agent as claimed in claim 1, wherein the titanium oxide encapsulating layer has a porous structure formed by stacking oxide particles, the coating thickness is 50-200nm, and the crystal form of the titanium oxide encapsulating layer is at least one of amorphous, anatase and rutile.
3. The composite antifouling agent of claim 1, wherein the composite antifouling agent is prepared by in-situ adsorption-hydrolysis of a titanium precursor salt on a cuprous oxide surface.
4. A method for preparing a composite anti-fouling agent, which is capable of preparing the composite anti-fouling agent according to any one of claims 1 to 3, the method comprising the steps of:
1) and (3) cuprous oxide surface hydration pretreatment: adding cuprous oxide powder into an organic solvent for ultrasonic dispersion to remove residual oil stains and other assistants on the surfaces of the particles; then, adding the cleaned cuprous oxide powder into deionized water, stirring at a constant speed for 1-4 hours, and performing suction filtration and separation to obtain hydrated cuprous oxide core powder;
2) in-situ hydrolysis-encapsulation of the titanium oxide: adding the hydrated cuprous oxide powder, titanium precursor salt and acetylacetone into an ethanol solution; stirring at a constant speed, carrying out adsorption reaction for 12-36 hours, and then using deionized water-organic solvent mixed washing liquor; and washing and separating the cuprous oxide composite antifouling agent material, placing the cuprous oxide composite antifouling agent material in an environment of room temperature of 25-30 ℃ for drying for 12-24 hours, and inducing the titanium precursor adsorbed on the surface of the cuprous oxide to generate in-situ hydrolysis by virtue of water vapor in the air to obtain the titanium oxide-encapsulated cuprous oxide composite antifouling agent material.
5. The method for preparing a composite antifouling agent according to claim 4, wherein the cuprous oxide comprises technical-grade electrolytic cuprous oxide, smelting cuprous oxide or laboratory-made cuprous oxide.
6. The method of claim 4, wherein the titanium precursor salt is an organic or inorganic titanium salt, the organic titanium salt comprises at least one of tetrabutyl titanate and isopropyl titanate, and the inorganic titanium salt comprises at least one of titanium trichloride and titanium sulfate.
7. The method for preparing a composite antifouling agent according to claim 4, wherein the mass ratio of cuprous oxide to deionized water in the hydration pretreatment process is 1 (10-20).
8. The composite antifouling agent as claimed in claim 4, wherein the weight ratio of cuprous oxide to ethanol in the in-situ hydrolysis-encapsulation process is 1 (80-150).
9. The composite antifouling agent as claimed in claim 4, wherein the molar ratio of cuprous oxide to titanium precursor salt in the in-situ hydrolysis-encapsulation process is 1 (1.2-2.5), and the molar ratio of acetylacetone to titanium precursor salt is (0.02-0.05): 1.
10. The composite antifouling agent as claimed in claim 4, wherein the volume ratio of deionized water to organic solvent in the mixed washing solution in the in-situ hydrolysis-encapsulation process is (0.11-1):1, wherein the organic solvent comprises one or more of methanol, ethanol, isopropanol and acetone, and the separation method comprises centrifugation or suction filtration.
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