CN114891402A - Preparation method of vanadium and silver nano-optimized low-surface-energy antifouling paint - Google Patents
Preparation method of vanadium and silver nano-optimized low-surface-energy antifouling paint Download PDFInfo
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- 230000003373 anti-fouling effect Effects 0.000 title claims abstract description 37
- 239000003973 paint Substances 0.000 title claims abstract description 32
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 18
- 239000004332 silver Substances 0.000 title claims abstract description 18
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract 10
- 239000000243 solution Substances 0.000 claims abstract description 59
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 57
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 57
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 claims abstract description 54
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000011347 resin Substances 0.000 claims abstract description 28
- 229920005989 resin Polymers 0.000 claims abstract description 28
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims abstract description 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 22
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000002270 dispersing agent Substances 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000007788 liquid Substances 0.000 claims abstract description 18
- 239000008096 xylene Substances 0.000 claims abstract description 18
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 12
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 12
- 229940057995 liquid paraffin Drugs 0.000 claims abstract description 12
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 12
- 238000000926 separation method Methods 0.000 claims abstract description 12
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 11
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims abstract description 11
- 229930006000 Sucrose Natural products 0.000 claims abstract description 11
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 11
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims abstract description 11
- ZPIRTVJRHUMMOI-UHFFFAOYSA-N octoxybenzene Chemical compound CCCCCCCCOC1=CC=CC=C1 ZPIRTVJRHUMMOI-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 11
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 11
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 11
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 11
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 11
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 11
- 239000004094 surface-active agent Substances 0.000 claims abstract description 11
- 239000011259 mixed solution Substances 0.000 claims abstract description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 7
- 238000004321 preservation Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 239000005720 sucrose Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000000643 oven drying Methods 0.000 claims 1
- 229960004793 sucrose Drugs 0.000 abstract description 8
- 238000001035 drying Methods 0.000 abstract description 6
- 230000003385 bacteriostatic effect Effects 0.000 abstract description 4
- 239000006185 dispersion Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 description 14
- 239000011248 coating agent Substances 0.000 description 12
- 230000001699 photocatalysis Effects 0.000 description 9
- 229910010413 TiO 2 Inorganic materials 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 8
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 8
- 239000002519 antifouling agent Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 230000031700 light absorption Effects 0.000 description 5
- 230000001954 sterilising effect Effects 0.000 description 5
- 238000004659 sterilization and disinfection Methods 0.000 description 5
- 230000002195 synergetic effect Effects 0.000 description 5
- 238000007146 photocatalysis Methods 0.000 description 4
- 230000000844 anti-bacterial effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 3
- 241000588724 Escherichia coli Species 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 210000000170 cell membrane Anatomy 0.000 description 2
- 210000002421 cell wall Anatomy 0.000 description 2
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 2
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 2
- 229940112669 cuprous oxide Drugs 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- ZHPNWZCWUUJAJC-UHFFFAOYSA-N fluorosilicon Chemical compound [Si]F ZHPNWZCWUUJAJC-UHFFFAOYSA-N 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 230000003834 intracellular effect Effects 0.000 description 2
- 231100000956 nontoxicity Toxicity 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- 241000589517 Pseudomonas aeruginosa Species 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GCTFWCDSFPMHHS-UHFFFAOYSA-M Tributyltin chloride Chemical compound CCCC[Sn](Cl)(CCCC)CCCC GCTFWCDSFPMHHS-UHFFFAOYSA-M 0.000 description 1
- APQHKWPGGHMYKJ-UHFFFAOYSA-N Tributyltin oxide Chemical compound CCCC[Sn](CCCC)(CCCC)O[Sn](CCCC)(CCCC)CCCC APQHKWPGGHMYKJ-UHFFFAOYSA-N 0.000 description 1
- PBNWTHQQCFXWDF-UHFFFAOYSA-N [O-2].[V+5].[Bi+]=O.[O-2].[O-2] Chemical compound [O-2].[V+5].[Bi+]=O.[O-2].[O-2] PBNWTHQQCFXWDF-UHFFFAOYSA-N 0.000 description 1
- 239000010426 asphalt Substances 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
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004925 denaturation Methods 0.000 description 1
- 230000036425 denaturation Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910000474 mercury oxide Inorganic materials 0.000 description 1
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
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- 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
- C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
- C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
-
- 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
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
-
- 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
- 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
- C09D5/1687—Use of special additives
-
- 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
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0806—Silver
-
- 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
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Abstract
The invention provides a preparation method of a vanadium and silver nano-optimized low-surface-energy antifouling paint, belonging to the technical field of anticorrosive paints. The preparation method comprises the following steps: dispersing nano bismuth vanadate into water; adding silver nitrate and cane sugar into the nano bismuth vanadate solution, performing ultrasonic treatment and then preserving heat; centrifugal solid-liquid separation and drying are carried out to obtain silver-attached nano bismuth vanadate; dissolving polytetrafluoroethylene in xylene to prepare a solution A; dispersing silver-attached nano bismuth vanadate, silicon dioxide, nano titanium dioxide, a dispersing agent, polyethylene glycol octyl phenyl ether and a fluorosilicone surfactant in dimethylbenzene to form liquid B; dissolving fluorocarbon resin in a mixed solution of xylene and butyl acetate to obtain a fluorocarbon resin solution; pouring the solution A and the solution B into a fluorocarbon resin solution, and adding liquid paraffin, a hydrophobic auxiliary agent, a defoaming agent and a flatting agent for uniform dispersion; adding a curing agent to cure and form a film. The marine antifouling paint disclosed by the invention has the characteristics of good antifouling effect, good bacteriostatic effect, low surface energy and the like.
Description
Technical Field
The invention belongs to the technical field of anticorrosive coatings, and particularly relates to a preparation method of a vanadium and silver nano-optimized low-surface-energy antifouling coating.
Background
It is well known that the total area of the earth is about 5.1 hundred million square kilometers, and the ocean area is about 3.61 hundred million square kilometers, which accounts for about 71% of the total area of the earth. The ocean has wide area, and breeds abundant species, wherein the attached organisms are thousands of. These fouling organisms adhere to the surfaces of ships and ocean platforms, and cause problems in terms of safety of the ships, corrosion of equipment, and the like.
People have a very long history of using marine antifouling paints. As early as the 30 s of the 20 th century. Asphalt resin, vinyl resin and chlorinated rubber are used as resin, and cuprous oxide, mercury oxide and other metal oxides are used as antifouling agents to prepare the marine antifouling paint. The 20 th century, the 60 s. Organotin compounds (tributyltin oxide and tributyltin chloride) are beginning to find wide application in antifouling coatings. These antifouling paints rely on the slow release of antifouling agents in the ocean and on the toxicity to marine organisms to kill them. After the 80's of the 20 th century, self-polishing antifouling paints appeared and the exudation of the antifouling agent began to stabilize. Due to the increasing awareness of environmental protection, the use of organic tin antifouling agents is prohibited in the beginning of the 21 st century, and the use of cuprous oxide antifouling agents is gradually reduced.
BiVO 4 The semiconductor material has the advantages of no toxicity, stability, high light utilization rate, good sterilization effect and the like, is widely applied to photocatalysis and sterilization, but BiVO 4 Has the defects of higher photogenerated electron-hole recombination efficiency and the like, and needs to further improve the photocatalytic bactericidal activity and apply the photocatalytic bactericidal activity to the marine antifouling paint.
Disclosure of Invention
The invention solves the technical problems by providing a preparation method of the low surface energy antifouling paint with optimized vanadium and silver nanometer.
In order to achieve the purpose, the technical solution of the invention is as follows:
a preparation method of a vanadium and silver nano-optimized low-surface-energy antifouling paint comprises the following steps:
(1) dispersing nano bismuth vanadate into water, adding a dispersing agent, and uniformly dispersing to obtain a nano bismuth vanadate solution;
(2) adding silver nitrate and sucrose into the nano bismuth vanadate solution, uniformly stirring, heating the solution to 60-75 ℃, carrying out ultrasonic treatment for 0.5-1.5 hours while stirring, and then carrying out heat preservation and stirring for 8-10 hours;
(3) performing centrifugal solid-liquid separation, washing with clear water for three times, and drying the obtained solid at 80-85 ℃ to obtain silver-attached nano bismuth vanadate;
(4) dissolving polytetrafluoroethylene in xylene to prepare a solution A;
(5) dispersing silver-attached nano bismuth vanadate, silicon dioxide, nano titanium dioxide, a dispersing agent, polyethylene glycol octyl phenyl ether and a fluorosilicone surfactant in dimethylbenzene to form liquid B;
(6) dissolving fluorocarbon resin in a mixed solution of xylene and butyl acetate to obtain a fluorocarbon resin solution;
(7) pouring the solution A and the solution B into a fluorocarbon resin solution, adding liquid paraffin, a hydrophobic auxiliary agent, a defoaming agent and a flatting agent, and uniformly dispersing in a stirrer; finally, curing agent is added to form a film.
Preferably, the parts by weight of the nano bismuth vanadate, the water and the dispersant in the step (1) are respectively 15-20 parts of nano bismuth vanadate, 80-110 parts of water and 0.5-0.7 part of dispersant.
Preferably, the mass parts of the silver nitrate and the sucrose in the step (2) are 0.6-1.2 parts of silver nitrate and 1.5-3.0 parts of sucrose respectively.
Preferably, the temperature for heat preservation in the step (2) is 60-75 ℃, and the stirring time is 9 hours.
Preferably, in the step (4), the mass parts of the polytetrafluoroethylene and the xylene are 6-9 parts of polytetrafluoroethylene and 12-14 parts of xylene respectively.
Preferably, in the step (5), the mass parts of the silicon dioxide, the nano titanium dioxide, the dispersing agent, the polyethylene glycol octyl phenyl ether, the fluorine-silicon surfactant and the xylene are respectively 5 to 7 parts of the silicon dioxide, 4 to 6 parts of the nano titanium dioxide, 0.5 to 0.8 part of the dispersing agent, 1.2 to 1.6 parts of the polyethylene glycol octyl phenyl ether, 0.1 to 0.3 part of the fluorine-silicon surfactant and 15 to 18 parts of the xylene.
Preferably, the mass parts of the fluorocarbon resin, the xylene and the butyl acetate in the step (6) are 55-60 parts of the fluorocarbon resin, 1-4 parts of the xylene and 3-5 parts of the butyl acetate respectively.
Preferably, in the step (7), the liquid paraffin, the hydrophobic auxiliary agent, the defoaming agent, the leveling agent and the curing agent are respectively 3-4 parts by mass of the liquid paraffin, 1-2 parts by mass of the hydrophobic auxiliary agent, 0.2-0.7 part by mass of the defoaming agent, 0.1-0.2 part by mass of the leveling agent and 5-7 parts by mass of the curing agent.
The invention has the following action principle:
1. the forbidden band width of bismuth vanadate is about 2.4eV, the absorption peak wavelength is about 517nm, and the bismuth vanadate can have photocatalytic performance under the condition of visible light. The bismuth vanadate has strong visible light absorption capacity, strong chemical stability, strong oxidation-reduction capacity, strong sterilization capacity and no toxicity. Bismuth vanadate has very strong bactericidal effect on escherichia coli, pseudomonas aeruginosa and other strains, can effectively kill organisms attached to the surfaces of ships, ocean platforms and the like, and is a surface which marine organisms can not be effectively attached to the ships and the like for a long time.
Nano TiO 2 2 Has good photocatalysis effect under the condition of ultraviolet light, can supplement the sterilization capability of bismuth tungstate in an ultraviolet band, and ZnO has strong sterilization effect.
2. The forbidden band width of bismuth vanadate is 2.4eV, and the bismuth vanadate has better absorption on blue light with the wavelength of about 517 nm. The band absorption of the bismuth tungstate is a wider absorption peak, and the bismuth tungstate has better absorption from 500nm to 300 nm. TiO 2 2 The forbidden band width of the light absorption material is 3.2eV, the light absorption curve can be extended from 3.2eV to 4.5eV, and the light absorption material has stronger absorption to the ultraviolet light with 276-388nm wave band. The synergistic effect of the two nano materials can absorb light with stronger energy in the 500-276nm wave band, and the light absorption range is wider.
3. Bismuth vanadate and nano-silver have strong synergistic antifouling capability
The bismuth vanadate and the nano-silver have synergistic effect, the absorption band can be from 550 to 250nm, and the absorption band is wider. The bismuth vanadate and the nano-silver have strong synergistic antifouling capacity, and when the ultraviolet light excites Ag-BiVO 4 Then, electrons are transited from the valence band to the conduction band, at the moment, Ag particles or AgO on the surface of the catalyst are easy to capture the electrons, and the electrons are not easy to recombine under the action of an external electric field, so Ag-BiVO (bismuth oxide-vanadium oxide) under the photoelectric synergistic action 4 The photoelectrocatalysis performance of the bismuth vanadate exceeds that of single bismuth vanadate.
The photoelectrocatalysis process is as follows:
Ag-BiVO 4 +hν→[e - ]+[h+]
[h + ]+H 2 O→·OH+H +
O 2 +[e - ]→·O 2 -
therefore, the Ag-attached bismuth vanadate has good photocatalytic effect and can effectively prevent the attachment of marine organisms. At present, Ag-attached bismuth vanadate is applied to pollutant degradation and H is produced by photocatalysis 2 In the antifouling paint, the application of the antifouling agent is rarely reported.
4. Under certain conditions, the bismuth vanadate in the coating can form various types of photocatalytic materials with the nano titanium dioxide, including Z type, II type and the like. The material can effectively absorb visible light, form electrons in a conduction band and holes in a valence band of bismuth vanadate, and simultaneously form TiO 2 Ultraviolet light may be absorbed to form electrons in the conduction band and holes in the valence band. Then the following reactions will occur:
BiVO 4 +hν→BiVO 4 ([e – ]–[h + ])
TiO 2 [e – ]+BiVO 4 →TiO 2 +BiVO 4 [e – ]
meanwhile, on the conduction band of the nano titanium dioxide, oxygen reacts with electrons of the conduction band to form O – Free radical:
O 2 +[e – ]→[·O 2 ] –
[·O 2 ] – +H + →[HO 2 ·] –
[e – ]+[HO 2 ·] – +H + →H 2 O 2
H 2 O 2 +[e – ]→·OH+OH –
TiO 2 /BiVO 4 the formed heterojunction is mainly applied to pollutant degradation and H production by photocatalysis 2 And the like, the paint is rarely used for antifouling paint.
The invention has the beneficial effects that:
the invention combines the advantages of silver-attached nano bismuth vanadate and the low surface energy antifouling material, and the prepared marine antifouling paint has the characteristics of good antifouling effect, good bacteriostatic effect, low surface energy, contact angle with water of 120 degrees and the like.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In addition, the technical solutions in the embodiments of the present invention may be combined with each other, but it must be based on the realization of those skilled in the art, and when the technical solutions are contradictory or cannot be realized, such a combination of technical solutions should not be considered to exist, and is not within the protection scope of the present invention.
Example 1
A preparation method of a vanadium and silver nano-optimized low-surface-energy antifouling paint comprises the following steps:
(1) dispersing 20 parts of nano bismuth vanadate into 110 parts of water, adding 0.6 part of dispersing agent, and uniformly dispersing to obtain a nano bismuth vanadate solution;
(2) adding 0.6 part of silver nitrate and 2.0 parts of cane sugar into the nano bismuth vanadate solution, uniformly stirring, heating the solution to 75 ℃, carrying out ultrasonic treatment for 1.5 hours while stirring, and carrying out heat preservation and stirring for 9 hours at the temperature of 60 ℃;
(3) carrying out centrifugal solid-liquid separation, washing the solid-liquid separation with clear water for three times, and drying the obtained solid at 85 ℃ to obtain silver-attached nano bismuth vanadate;
(4) dissolving 6 parts of polytetrafluoroethylene in 14 parts of dimethylbenzene to prepare a solution A;
(5) dispersing 6 parts of silver-attached nano bismuth vanadate, 6 parts of silicon dioxide, 4-6 parts of nano titanium dioxide, 0.7 part of dispersing agent, 1.2 parts of polyethylene glycol octyl phenyl ether and 0.1 part of fluorosilicone surfactant in 16 parts of dimethylbenzene to form liquid B;
(6) dissolving 55 parts of fluorocarbon resin in a mixed solution of 1 part of dimethylbenzene and 3 parts of butyl acetate to obtain a fluorocarbon resin solution;
(7) pouring the solution A and the solution B into a fluorocarbon resin solution, adding 3 parts of liquid paraffin, 1 part of hydrophobic auxiliary agent, 0.5 part of defoaming agent and 0.2 part of flatting agent, and uniformly dispersing in a stirrer; and finally, 6 parts of curing agent is added to be cured into a film.
Example 2
A preparation method of a vanadium and silver nano-optimized low-surface-energy antifouling paint comprises the following steps:
(1) dispersing 15 parts of nano bismuth vanadate into 80 parts of water, adding 0.7 part of dispersing agent, and uniformly dispersing to obtain a nano bismuth vanadate solution;
(2) adding 1 part of silver nitrate and 3.0 parts of cane sugar into the nano bismuth vanadate solution, uniformly stirring, heating the solution to 60 ℃, carrying out ultrasonic treatment for 0.5 hour while stirring, and carrying out heat preservation and stirring for 10 hours at the temperature of 65 ℃;
(3) carrying out centrifugal solid-liquid separation, washing the solid-liquid separation with clear water for three times, and drying the obtained solid at 80 ℃ to obtain silver-attached nano bismuth vanadate;
(4) dissolving 7 parts of polytetrafluoroethylene in 12 parts of dimethylbenzene to prepare a solution A;
(5) dispersing 7 parts of silver-attached nano bismuth vanadate, 7 parts of silicon dioxide, 5 parts of nano titanium dioxide, 0.8 part of dispersing agent, 1.4 parts of polyethylene glycol octyl phenyl ether and 0.2 part of fluorosilicone surfactant in 18 parts of dimethylbenzene to form liquid B;
(6) dissolving 58 parts of fluorocarbon resin in a mixed solution of 2 parts of dimethylbenzene and 4 parts of butyl acetate to obtain a fluorocarbon resin solution;
(7) pouring the solution A and the solution B into a fluorocarbon resin solution, adding 3.5 parts of liquid paraffin, 1.5 parts of hydrophobic auxiliary agent, 0.7 part of defoaming agent and 0.1 part of flatting agent, and uniformly dispersing in a stirrer; and finally, 7 parts of curing agent is added to be cured into a film.
Example 3
A preparation method of a vanadium and silver nano-optimized low-surface-energy antifouling paint comprises the following steps:
(1) dispersing 18 parts of nano bismuth vanadate into 100 parts of water, adding 0.5 part of dispersing agent, and uniformly dispersing to obtain a nano bismuth vanadate solution;
(2) adding 1.2 parts of silver nitrate and 1.5 parts of cane sugar into the nano bismuth vanadate solution, uniformly stirring, heating the solution to 70 ℃, stirring while carrying out ultrasonic treatment for 1 hour, and then carrying out heat preservation and stirring for 8 hours at the temperature of 75 ℃;
(3) carrying out centrifugal solid-liquid separation, washing the solid-liquid separation with clear water for three times, and drying the obtained solid at 85 ℃ to obtain silver-attached nano bismuth vanadate;
(4) dissolving 9 parts of polytetrafluoroethylene in 13 parts of dimethylbenzene to prepare a solution A;
(5) dispersing 5 parts of silver-attached nano bismuth vanadate, 5 parts of silicon dioxide, 6 parts of nano titanium dioxide, 0.5 part of dispersing agent, 1.6 parts of polyethylene glycol octyl phenyl ether and 0.3 part of fluorosilicone surfactant in 15 parts of dimethylbenzene to form liquid B;
(6) dissolving 60 parts of fluorocarbon resin in a mixed solution of 3 parts of dimethylbenzene and 4.5 parts of butyl acetate to obtain a fluorocarbon resin solution;
(7) pouring the solution A and the solution B into a fluorocarbon resin solution, adding 4 parts of liquid paraffin, 2 parts of hydrophobic auxiliary agent, 0.2 part of defoaming agent and 0.1 part of flatting agent, and uniformly dispersing in a stirrer; and finally, adding 5 parts of curing agent and curing to form a film.
Example 4
A preparation method of a vanadium and silver nano-optimized low-surface-energy antifouling paint comprises the following steps:
(1) dispersing 19 parts of nano bismuth vanadate into 90 parts of water, adding 0.6 part of dispersing agent, and uniformly dispersing to obtain a nano bismuth vanadate solution;
(2) adding 1 part of silver nitrate and 2.5 parts of cane sugar into the nano bismuth vanadate solution, uniformly stirring, heating the solution to 70 ℃, stirring and ultrasonically treating for 0.8 hour, and then keeping the temperature and stirring for 9 hours at the temperature of 65 ℃;
(3) carrying out centrifugal solid-liquid separation, washing the solid-liquid separation with clear water for three times, and drying the obtained solid at 80 ℃ to obtain silver-attached nano bismuth vanadate;
(4) dissolving 7 parts of polytetrafluoroethylene in 13 parts of dimethylbenzene to prepare a solution A;
(5) dispersing 6 parts of silver-attached nano bismuth vanadate, 6 parts of silicon dioxide, 5 parts of nano titanium dioxide, 0.6 part of dispersing agent, 1.4 parts of polyethylene glycol octyl phenyl ether and 0.2 part of fluorosilicone surfactant in 17 parts of dimethylbenzene to form liquid B;
(6) dissolving 58 parts of fluorocarbon resin in a mixed solution of 4 parts of dimethylbenzene and 5 parts of butyl acetate to obtain a fluorocarbon resin solution;
(7) pouring the solution A and the solution B into a fluorocarbon resin solution, adding 3 parts of liquid paraffin, 1 part of hydrophobic auxiliary agent, 0.4 part of defoaming agent and 0.1 part of flatting agent, and uniformly dispersing in a stirrer; and finally, 6 parts of curing agent is added to be cured into a film.
Detection test
The coating contact angles of the antifouling paints obtained in examples 1 to 4 were measured in a water droplet manner.
Specifically, a certain amount of the antifouling paints obtained in examples 1 to 4 was dropped on an Escherichia coli culture dish, cultured at a constant temperature of 37 ℃ for 36 hours, and then taken out, photographed by a camera, and the size of the inhibition ring was determined by a vernier caliper. The quoted standards are: the detection and counting of staphylococcus aureus are realized according to the national standard GB/T4789.37-2008Baird-Parker plate counting, the bacteriostasis rate is calculated, and the result is shown in the following table.
Coating contact angle experiment result table of antifouling paint
| Examples | Contact angle | Bacteriostatic diameter | Rate of inhibition of bacteria |
| Example 1 | 121.2° | 12.7mm | 97.3％ |
| Example 2 | 123.1° | 14.6mm | 98.2％ |
| Example 3 | 125.7° | 15.8mm | 98.5％ |
| Example 4 | 128.5° | 17.9mm | 98.7％ |
From the above table, the coating contact angle of the antifouling paint of the invention is greater than 121.2 °, and the bacteriostasis rate is higher than 97.3%, because: large particle SiO 2 Can form tiny bulges on the surface of the coating by the interaction with the nano-filler, and the tiny bulges can play a role of being similar to lotus leaves, thereby effectively reducing the materialThe surface energy itself. In addition, the fluorocarbon coating has small surface energy, and the surface energy of the coating is further reduced and the contact angle is increased after the liquid paraffin and the hydrophobic auxiliary agent are added, so that the contact angle of the surface of the coating is more than 120 degrees, and the coating has good hydrophobicity. TiO 2 2 And BiVO 4 And part of TiO 2 /BiVO 4 The heterojunction generates photogeneration e under the illumination condition – Or h + And further with H 2 O or O 2 Oxidation-reduction reaction to produce OH and O with strong oxidizing property 2 And H 2 O 2 And the like. The photo-generated free radicals can react with cell walls, cell membranes or intracellular substances, so that the cell membranes and the cell walls are damaged, and the denaturation of intracellular functional molecules can well inhibit marine organisms and the like. On one hand, Ag can directly kill marine organisms, on the other hand, Ag can promote the separation of conduction band electrons and valence band holes and promote the good performance of the coating for preventing the marine organisms, so that the bacteriostatic rate of the coating is good and is more than 97.3 percent.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all equivalent modifications made by the present invention in the specification or other related fields directly or indirectly are included in the scope of the present invention.
Claims (8)
1. A preparation method of a vanadium and silver nano-optimized low-surface-energy antifouling paint is characterized by comprising the following steps:
(1) dispersing nano bismuth vanadate into water, adding a dispersing agent, and uniformly dispersing to obtain a nano bismuth vanadate solution;
(2) adding silver nitrate and sucrose into the nano bismuth vanadate solution, uniformly stirring, heating the solution to 60-75 ℃, carrying out ultrasonic treatment for 0.5-1.5 hours while stirring, and then carrying out heat preservation and stirring for 8-10 hours;
(3) centrifuging for solid-liquid separation, washing with clear water for three times, and oven drying the obtained solid at 80-85 deg.C to obtain silver-attached nano bismuth vanadate;
(4) dissolving polytetrafluoroethylene in xylene to prepare a solution A;
(5) dispersing silver-attached nano bismuth vanadate, silicon dioxide, nano titanium dioxide, a dispersing agent, polyethylene glycol octyl phenyl ether and a fluorosilicone surfactant in dimethylbenzene to form liquid B;
(6) dissolving fluorocarbon resin in a mixed solution of xylene and butyl acetate to obtain a fluorocarbon resin solution;
(7) pouring the solution A and the solution B into a fluorocarbon resin solution, adding liquid paraffin, a hydrophobic auxiliary agent, a defoaming agent and a flatting agent, and uniformly dispersing in a stirrer; finally, curing agent is added to form a film.
2. The method for preparing the vanadium and silver nano-optimized low surface energy antifouling paint according to claim 1, wherein the parts by weight of the nano bismuth vanadate, the water and the dispersant in the step (1) are respectively 15-20 parts of the nano bismuth vanadate, 80-110 parts of the water and 0.5-0.7 part of the dispersant.
3. The method for preparing the vanadium and silver nano optimized low surface energy antifouling paint according to the claim 1, wherein the mass parts of silver nitrate and sucrose in the step (2) are 0.6-1.2 parts of silver nitrate and 1.5-3.0 parts of sucrose, respectively.
4. The method for preparing the vanadium and silver nano-optimized low surface energy antifouling paint according to the claim 1, wherein the heat preservation temperature in the step (2) is 60-75 ℃, and the stirring time is 9 hours.
5. The method for preparing the vanadium and silver nano-optimized low-surface-energy antifouling paint according to the claim 1, wherein the mass parts of polytetrafluoroethylene and xylene in the step (4) are 6-9 parts of polytetrafluoroethylene and 12-14 parts of xylene respectively.
6. The method for preparing the vanadium and silver nano-optimized low-surface-energy antifouling paint as claimed in claim 1, wherein in the step (5), the mass parts of the silicon dioxide, the nano-titanium dioxide, the dispersing agent, the polyethylene glycol octyl phenyl ether, the fluorosilicone surfactant and the xylene are respectively 5-7 parts of the silicon dioxide, 4-6 parts of the nano-titanium dioxide, 0.5-0.8 part of the dispersing agent, 1.2-1.6 parts of the polyethylene glycol octyl phenyl ether, 0.1-0.3 part of the fluorosilicone surfactant and 15-18 parts of the xylene.
7. The method for preparing the vanadium and silver nano-optimized low-surface-energy antifouling paint as claimed in claim 1, wherein the mass parts of the fluorocarbon resin, the xylene and the butyl acetate in the step (6) are 55-60 parts of the fluorocarbon resin, 1-4 parts of the xylene and 3-5 parts of the butyl acetate respectively.
8. The preparation method of the vanadium and silver nano-optimized low-surface-energy antifouling paint as claimed in claim 1, wherein the liquid paraffin, the hydrophobic auxiliary agent, the defoaming agent, the leveling agent and the curing agent in the step (7) are respectively 3-4 parts by mass of the liquid paraffin, 1-2 parts by mass of the hydrophobic auxiliary agent, 0.2-0.7 part by mass of the defoaming agent, 0.1-0.2 part by mass of the leveling agent and 5-7 parts by mass of the curing agent.
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