CN114409559A - Preparation method and application of environment-friendly antifouling agent for marine coating - Google Patents
Preparation method and application of environment-friendly antifouling agent for marine coating Download PDFInfo
- Publication number
- CN114409559A CN114409559A CN202210015048.4A CN202210015048A CN114409559A CN 114409559 A CN114409559 A CN 114409559A CN 202210015048 A CN202210015048 A CN 202210015048A CN 114409559 A CN114409559 A CN 114409559A
- Authority
- CN
- China
- Prior art keywords
- agent
- parts
- antifouling
- reaction
- eleostearic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002519 antifouling agent Substances 0.000 title claims abstract description 35
- 238000000576 coating method Methods 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000011248 coating agent Substances 0.000 title claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- CUXYLFPMQMFGPL-UHFFFAOYSA-N (9Z,11E,13E)-9,11,13-Octadecatrienoic acid Natural products CCCCC=CC=CC=CCCCCCCCC(O)=O CUXYLFPMQMFGPL-UHFFFAOYSA-N 0.000 claims abstract description 32
- CUXYLFPMQMFGPL-SUTYWZMXSA-N all-trans-octadeca-9,11,13-trienoic acid Chemical compound CCCC\C=C\C=C\C=C\CCCCCCCC(O)=O CUXYLFPMQMFGPL-SUTYWZMXSA-N 0.000 claims abstract description 32
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 claims abstract description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 24
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000005406 washing Methods 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 12
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims description 66
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 45
- 239000003795 chemical substances by application Substances 0.000 claims description 36
- 230000003373 anti-fouling effect Effects 0.000 claims description 29
- 239000003085 diluting agent Substances 0.000 claims description 27
- 239000002383 tung oil Substances 0.000 claims description 25
- 239000003973 paint Substances 0.000 claims description 23
- 239000000945 filler Substances 0.000 claims description 18
- 239000004593 Epoxy Substances 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 16
- 238000001914 filtration Methods 0.000 claims description 15
- 229920005989 resin Polymers 0.000 claims description 14
- 239000011347 resin Substances 0.000 claims description 14
- 239000012535 impurity Substances 0.000 claims description 13
- 239000002244 precipitate Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 239000004952 Polyamide Substances 0.000 claims description 10
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 10
- 229920002647 polyamide Polymers 0.000 claims description 10
- 239000002270 dispersing agent Substances 0.000 claims description 9
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 8
- 230000003712 anti-aging effect Effects 0.000 claims description 8
- 229910052708 sodium Inorganic materials 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 239000012752 auxiliary agent Substances 0.000 claims description 3
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 claims description 3
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 claims description 2
- XTDYIOOONNVFMA-UHFFFAOYSA-N dimethyl pentanedioate Chemical compound COC(=O)CCCC(=O)OC XTDYIOOONNVFMA-UHFFFAOYSA-N 0.000 claims description 2
- 239000003921 oil Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 2
- 239000001301 oxygen Substances 0.000 abstract description 2
- 229910052760 oxygen Inorganic materials 0.000 abstract description 2
- 238000007348 radical reaction Methods 0.000 abstract description 2
- 150000003254 radicals Chemical class 0.000 abstract description 2
- 238000005119 centrifugation Methods 0.000 description 13
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 239000011148 porous material Substances 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 239000003963 antioxidant agent Substances 0.000 description 6
- 230000003078 antioxidant effect Effects 0.000 description 6
- 230000006378 damage Effects 0.000 description 6
- 239000004744 fabric Substances 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000011109 contamination Methods 0.000 description 4
- -1 imidazoline quaternary ammonium salt Chemical class 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229920003986 novolac Polymers 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 3
- 229940073608 benzyl chloride Drugs 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- 241001465754 Metazoa Species 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 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 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000005028 tinplate Substances 0.000 description 2
- PIILXFBHQILWPS-UHFFFAOYSA-N tributyltin Chemical compound CCCC[Sn](CCCC)CCCC PIILXFBHQILWPS-UHFFFAOYSA-N 0.000 description 2
- 239000012855 volatile organic compound Substances 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidine Chemical compound CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 241000238586 Cirripedia Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 241000237536 Mytilus edulis Species 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 241000237502 Ostreidae Species 0.000 description 1
- 235000010678 Paulownia tomentosa Nutrition 0.000 description 1
- 240000002834 Paulownia tomentosa Species 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- AGXUVMPSUKZYDT-UHFFFAOYSA-L barium(2+);octadecanoate Chemical compound [Ba+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AGXUVMPSUKZYDT-UHFFFAOYSA-L 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 239000003139 biocide Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- ZZTMMVAAULUFCS-UHFFFAOYSA-L disodium;methanedisulfonate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)CS([O-])(=O)=O ZZTMMVAAULUFCS-UHFFFAOYSA-L 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 235000020638 mussel Nutrition 0.000 description 1
- LCRMGUFGEDUSOG-UHFFFAOYSA-N naphthalen-1-ylsulfonyloxymethyl naphthalene-1-sulfonate;sodium Chemical compound [Na].C1=CC=C2C(S(=O)(OCOS(=O)(=O)C=3C4=CC=CC=C4C=CC=3)=O)=CC=CC2=C1 LCRMGUFGEDUSOG-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 125000005375 organosiloxane group Chemical group 0.000 description 1
- 235000020636 oyster Nutrition 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920000141 poly(maleic anhydride) Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229940037312 stearamide Drugs 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 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
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/12—Preparation of carboxylic acid amides by reactions not involving the formation of carboxamide groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
-
- 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
- C09D163/04—Epoxynovolacs
-
- 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
- C09D5/1625—Non-macromolecular compounds organic
Abstract
The invention relates to a preparation method of an environment-friendly antifouling agent for marine coatings, which comprises the following steps: eleostearic acid and diethylenetriamine are mixed according to the mass ratio (2-2.2): 1, adding trimethylbenzene into a reaction kettle, adding trimethylbenzene, continuously introducing nitrogen, keeping the nitrogen flow rate slow, heating to 140-150 ℃, reacting for 2-2.5h, heating to 210-22 ℃, continuing to react for 2-2.5h, cooling to 80-90 ℃, adding benzyl bromide accounting for 1-2% of the mass of eleostearic acid, reacting for 4-5h, washing the obtained product with dimethylbenzene, and drying. The invention adopts benzyl bromide with higher activity as raw material, which can effectively improve the final yield; because the intermediate reaction process in the preparation process is a free radical reaction and is easy to react with oxygen, the invention can remove air in the reaction kettle by introducing nitrogen, and can take out a part of generated water to promote the forward proceeding of the reaction process, further improve the yield, thereby being suitable for industrialized mass production and effectively reducing the production cost of the coating.
Description
Technical Field
The invention relates to the field of antifouling materials, and particularly relates to a preparation method and application of an environment-friendly antifouling agent for a marine coating.
Background
A large number of animals, plants and microorganisms live in the ocean. In general, undesirable deposits resulting from the attachment of marine organisms to the surface of marine solid facilities are referred to as marine biofouling. Many marine animals such as barnacles, oysters, mussels, limestates and the like often adhere to and grow on the surfaces of underwater facilities such as ship bottoms, buoys, seacoasts, pipelines and the like to cause undesirable deposition, thereby bringing harm to scientific research activities of marine production. If marine organisms are attached to and grow at the bottom of the ship, the speed is reduced, the sailing resistance is increased, the bottom of the ship is corroded, and the ship body is damaged; the coating is attached to the surface of a metal solid to damage the protective coating on the surface of the metal and accelerate the corrosion speed of the metal; attached to the inner surface of the marine pipeline to reduce the volume of the pipeline or to block the pipeline. The marine biofouling causes serious harm to coastal protection, marine transportation, fishery production and marine industrial production, and in the face of marine fouling, the coating of a layer of antifouling paint for preventing marine biofouling from growing is the simplest, convenient and feasible antifouling method at present, and the growth and propagation of marine fouling organisms are inhibited by active substances slowly and uniformly released from the paint. In order to prevent the adhesion of marine organisms and reduce the harm of the marine organisms, people begin to coat antifouling paint containing tin, copper and the like as biocides on the surfaces of ships as early as over a hundred years, and although toxic substances in the paint kill a large amount of organisms adhered to the bottom of the ship, the antifouling paint causes serious marine pollution. Tributyltin (TBT), a representative antifouling paint, was an excellent antifouling paint, widely used for the 20 th century, and banned by the International Maritime Organization (IMO) in 1 month in 2008 due to its harm to marine ecological environment and even influence on human health. With the increasing importance of environmental protection in China, China and other countries, toxic and harmful antifouling paints to marine environment and ecology are finally eliminated, and the research and development of nontoxic and pollution-free environment-friendly marine antifouling paints becomes the current research focus.
Patent CN 109053579a discloses an imidazoline quaternary ammonium salt corrosion inhibitor and a preparation method thereof, which prepares an environment-friendly quaternary ammonium salt corrosion inhibitor with an antifouling effect, but the preparation method adopts oleic acid or natural eleostearic acid and the like as raw materials, so that the raw material cost is high, and the yield of the corrosion inhibitor prepared by the method is not ideal, and the corrosion inhibitor is not suitable for industrial mass production.
Disclosure of Invention
Based on the technical problems, the invention provides a preparation method and application of an environment-friendly antifouling agent for marine coatings.
The technical scheme provided by the invention is as follows: a preparation method of an environment-friendly antifouling agent for marine coatings comprises the following steps:
eleostearic acid and diethylenetriamine are mixed according to the mass ratio (2-2.2): 1, adding trimethylbenzene into a reaction kettle, adding trimethylbenzene, continuously introducing nitrogen, keeping the nitrogen flow rate slow, heating to 140-150 ℃, reacting for 2-2.5h, heating to 210-22 ℃, continuing to react for 2-2.5h, cooling to 80-90 ℃, adding benzyl bromide accounting for 1-2% of the mass of eleostearic acid, reacting for 4-5h, washing the obtained product with dimethylbenzene, and drying.
Further, the dosage of the trimethylbenzene is 40-50% of the total mass of the eleostearic acid and the diethylenetriamine.
Further, stirring is continuously carried out in the reaction process, and the stirring speed is 300-400 r/min.
Further, the eleostearic acid is prepared by the following method:
s1, adding tung oil into a reaction kettle, adding a sodium hydroxide solution, and reacting under stirring;
s2, after the reaction is finished, standing and separating liquid, taking the lower layer liquid, and filtering to remove impurities to obtain a sodium eleostearate solution;
s3, titrating with acid until no white floccule is generated;
s4, filtering to obtain a precipitate eleostearic acid, and washing with water.
Further, in the step S1, the concentration of the sodium hydroxide solution (sodium hydroxide mass fraction) is 50-60%, the addition amount is 10-15% of the tung oil mass, the stirring speed in the reaction process is 500r/min, the reaction temperature is 60-70 ℃, and the reaction time is 1-2 h.
Further, in the step S2, a filter screen or a filter cloth with 400-mesh pores and 600-mesh pores is adopted for filtration, and then the centrifugation is carried out to further remove impurities, wherein the centrifugation rate is 20000-mesh 30000r/min, and the centrifugation time is 10-15min, so that the supernatant is the sodium eleostearate solution.
Further, in the step S3, 0.1-0.3mol/L HCl or 0.1-0.2mol/L H is used2SO4Titration was performed.
The invention also provides an antifouling paint which comprises the antifouling agent prepared by the preparation method.
Further, the antifouling paint comprises the following components in a mass ratio of 1: a, B of (5-7);
wherein the component A comprises the following raw materials in parts by weight:
30-55 parts of phenolic epoxy modified resin,
20-40 parts of a filler,
10-20 parts of an anti-fouling agent,
12-18 parts of a reactive diluent,
0.4-3.3 parts of an auxiliary agent;
the component B comprises the following raw materials in parts by weight: 60-80 parts of polyamide and 20-30 parts of organic solvent.
Further, the reactive diluent comprises one or more of benzyl alcohol, ethylene glycol, 1, 6-hexanediol diacrylate, tripropylene glycol diacrylate, preferably 1, 6-hexanediol diacrylate and benzyl alcohol, more preferably 1, 6-hexanediol diacrylate.
Further, the organic solvent comprises one or two of dearomatized diluent, diformate, dimethylformamide and dimethyl glutarate.
Further, the filler comprises the following components in the ratio of (1-2): 1 titanium dioxide and talcum powder; preferably, the titanium dioxide is alloy-grade titanium dioxide, and the talcum powder is 3500-mesh precipitated barium sulfate.
Further, the novolac epoxy modified resin contains an epoxy group with an epoxy equivalent of 100-400.
Further, the auxiliary agent comprises the following raw materials in parts by weight: 0.1-1 part of anti-settling agent, 0.1-1 part of anti-aging agent, 0.1-0.5 part of dispersing agent and 0.1-0.8 part of flatting agent.
Preferably, the anti-settling agent comprises one or more of fumed silica, organobentonite, polyolefin wax and polyamide wax.
Preferably, the aging-resistant agent comprises one or more of nano zinc oxide, 2, 6, 6-tetramethyl piperidine, benzophenone and benzotriazole.
Preferably, the dispersant comprises one or more of sodium methylene bis naphthalene sulfonate, vinyl bis stearamide, barium stearate, polyethylene wax and HPMA (hydrolyzed polymaleic anhydride), preferably sodium methylene bis sulfonate.
Preferably, the leveling agent includes one or more of silicone oil, polydimethylsiloxane, polyether polyester modified organosiloxane, and alkyl modified organosiloxane.
Preferably, the polyamide curing agent is an epoxy curing agent of an air chemical manufacturer.
The preparation method of the antifouling paint comprises the following steps:
adding 40-60% of novolac epoxy modified resin in a formula into a stirring kettle, sequentially adding a dispersing agent, a leveling agent, an anti-settling agent and an anti-aging agent, adding 10-30% of an active diluent in the formula, controlling the stirring rotation speed at 800r/min, slowly adding a filler into the stirring kettle after stirring for 3-5min, increasing the rotation speed to 1800 ion-resistant 2000r/min after the filler is completely added, continuously dispersing, reducing the rotation speed to 800 ion-resistant 1000r/min when the system fineness is not more than 30 mu m, adding the rest antifouling agent and the active diluent, uniformly stirring, reducing the rotation speed to 300 ion-resistant 500r/min, adding an antioxidant, and stirring for 20-30min to obtain the component A.
Adding the polyamide curing agent and the organic diluent into a stirring kettle, controlling the stirring speed at 800r/min, stirring for 15min to obtain the component B, and subpackaging.
Compared with the prior art, the invention has the following beneficial effects:
(1) benzyl bromide with higher activity is used as a raw material, so that the final yield can be effectively improved, and the method is suitable for industrial production;
because the intermediate reaction process in the preparation process is a free radical reaction and is easy to react with oxygen, the invention can remove air in the reaction kettle by introducing nitrogen, and can take out a part of generated water, thereby promoting the forward progress of the reaction process and further improving the yield.
(2) Tung oil can be used as a raw material to prepare the tung oil acid, the raw material source is wide, the cost for producing and preparing the antifouling agent is lower, and the toxicity to people is low.
(3) The component A of the coating adopts an active diluent which can participate in film forming reaction, thereby reducing the VOC (volatile organic compounds) release of the coating and reducing the environmental pollution and the injury of constructors;
the component B of the coating adopts an organic diluent which is a non-toxic diluent with high boiling point, so that the pungent smell of the coating is effectively reduced.
Detailed Description
The present invention will be further described with reference to the following specific examples, wherein the amounts of raw materials used for preparing the antifouling paint in the following examples and comparative examples are shown in table 1;
TABLE 1
When the component A and the component B are used, the ratio of 1: (5-7) in the mass ratio.
Example 1
A preparation method of an environment-friendly antifouling agent for marine coatings comprises the following steps:
s1, adding tung oil into a reaction kettle, adding a sodium hydroxide solution (the mass fraction of the sodium hydroxide is 60%) with the mass of 10% of the tung oil, and reacting under stirring at 300r/min, wherein the reaction temperature is 60 ℃ and the reaction time is 2 hours.
And S2, after the reaction is finished, standing and separating liquid, taking the lower layer liquid, filtering by using filter cloth with 400-mesh pores to remove impurities, centrifuging to further remove the impurities, wherein the centrifugation rate is 30000r/min, the centrifugation time is 10min, and separating to obtain the upper layer clear liquid which is a sodium eleostearate solution.
S3, titrating with 0.1mol/LHCl until no white floccule is generated;
s4, filtering the precipitate by using filter paper to obtain eleostearic acid, and washing the precipitate by using deionized water.
S5, mixing eleostearic acid and diethylenetriamine according to a mass ratio of 2: 1, adding the tung oil acid and trimethylbenzene accounting for 50 percent of the total mass of the diethylenetriamine into a reaction kettle, continuously and slowly introducing nitrogen, heating to 140 ℃, reacting for 2.5 hours, heating to 210 ℃, continuing to react for 2.5 hours, cooling to 80 ℃, adding benzyl bromide accounting for 1 percent of the mass of the tung oil acid, reacting for 5 hours, washing the obtained product with dimethylbenzene, and drying to obtain the tung oil modified quaternary ammonium salt.
The tung oil modified quaternary ammonium salt is used as an antifouling agent to prepare an antifouling coating, and the preparation method comprises the following steps:
(1) according to the formula, novolac epoxy modified resin with the formula amount of 60% is added into a stirring kettle, a dispersing agent, a leveling agent, an anti-settling agent and an anti-aging agent are sequentially added, an active diluent with the formula amount of 30% is added, the stirring speed is controlled at 800r/min, after stirring for 4min, a filler is slowly added into the stirring kettle, after the filler is completely added, the rotating speed is increased to 1900r/min, the dispersion is continued, when the system fineness is not more than 30 mu m, the rotating speed is reduced to 900r/min, the rest antifouling agent, active diluent and novolac epoxy modified resin are added, after the stirring is uniform, the rotating speed is reduced to 400r/min, an antioxidant is added, and the stirring is carried out for 25min, so that the component A is prepared.
(2) Adding polyamide curing agent and organic diluent into a stirring kettle, stirring at a stirring speed of 500r/min for 15min to obtain component B, and subpackaging.
The component A and the component B are prepared according to the following ratio of 1: 6 in a mass ratio.
Example 2
A preparation method of an environment-friendly antifouling agent for marine coatings comprises the following steps:
s1, adding tung oil into a reaction kettle, adding a sodium hydroxide solution (the mass fraction of the sodium hydroxide is 50%) accounting for 15% of the mass of the tung oil, and reacting under stirring at 300r/min, wherein the reaction temperature is 60 ℃ and the reaction time is 2 hours.
And S2, after the reaction is finished, standing and separating liquid, taking the lower layer liquid, filtering by using filter cloth with 400-mesh pores to remove impurities, centrifuging to further remove the impurities, wherein the centrifugation rate is 30000r/min, the centrifugation time is 10min, and separating to obtain the upper layer clear liquid which is a sodium eleostearate solution.
S3, titrating with 0.1mol/LHCl until no white floccule is generated;
s4, filtering the precipitate by using filter paper to obtain eleostearic acid, and washing the precipitate by using deionized water.
S5, mixing eleostearic acid and diethylenetriamine according to a mass ratio of 2.2: 1, adding the mixture into a reaction kettle, adding trimethylbenzene accounting for 50 percent of the total mass of eleostearic acid and diethylenetriamine, continuously and slowly introducing nitrogen, heating to 140 ℃, reacting for 2.5 hours, heating to 210 ℃, continuing to react for 2.5 hours, cooling to 80 ℃, adding benzyl bromide accounting for 1 percent of the mass of eleostearic acid, reacting for 5 hours, washing the obtained product with dimethylbenzene, and drying.
The tung oil modified quaternary ammonium salt is used as an antifouling agent to prepare an antifouling coating, and the preparation method comprises the following steps:
(1) according to the formula, phenolic epoxy modified resin with the formula amount of 50% is added into a stirring kettle, a dispersing agent, a leveling agent, an anti-settling agent and an anti-aging agent are sequentially added, an active diluent with the formula amount of 20% is added, the stirring speed is controlled at 600r/min, after stirring for 5min, a filler is slowly added into the stirring kettle, after the filler is completely added, the rotating speed is increased to 2000r/min, the dispersion is continued, when the system fineness is dispersed to be less than or equal to 30 mu m, the rotating speed is reduced to 1000r/min, the rest antifouling agent, active diluent and phenolic epoxy modified resin are added, after the uniform stirring, the rotating speed is reduced to 3500r/min, an antioxidant is added, and the stirring is carried out for 20min, so that the component A is prepared.
(2) Adding polyamide curing agent and organic diluent into a stirring kettle, stirring at a stirring speed of 500r/min for 15min to obtain component B, and subpackaging.
The component A and the component B are prepared according to the following ratio of 1: 6 in a mass ratio.
Example 3
A preparation method of an environment-friendly antifouling agent for marine coatings comprises the following steps:
s1, adding tung oil into a reaction kettle, adding a sodium hydroxide solution (the mass fraction of the sodium hydroxide is 55%) accounting for 15% of the mass of the tung oil, and reacting under stirring at 300r/min, wherein the reaction temperature is 60 ℃ and the reaction time is 2 hours.
S2, after the reaction is finished, standing and separating liquid, taking the lower layer liquid, filtering by using filter cloth with 600-mesh pores to remove impurities, centrifuging to further remove the impurities, wherein the centrifugation speed is 20000r/min, the centrifugation time is 10min, and separating to obtain the supernatant which is a sodium eleostearate solution.
S3, titrating with 0.3mol/LHCl until no white floccule is generated;
s4, filtering the precipitate by using filter paper to obtain eleostearic acid, and washing the precipitate by using deionized water.
S5, mixing eleostearic acid and diethylenetriamine according to a mass ratio of 2.1: 1, adding the mixture into a reaction kettle, adding trimethylbenzene accounting for 50 percent of the total mass of eleostearic acid and diethylenetriamine, continuously and slowly introducing nitrogen, heating to 140 ℃, reacting for 2.5 hours, heating to 210 ℃, continuing to react for 2.5 hours, cooling to 80 ℃, adding benzyl bromide accounting for 2 percent of the mass of eleostearic acid, reacting for 5 hours, washing the obtained product with dimethylbenzene, and drying.
The tung oil modified quaternary ammonium salt is used as an antifouling agent to prepare an antifouling coating, and the preparation method comprises the following steps:
(1) according to the formula, phenolic epoxy modified resin with the formula amount of 50% is added into a stirring kettle, a dispersing agent, a leveling agent, an anti-settling agent and an anti-aging agent are sequentially added, an active diluent with the formula amount of 20% is added, the stirring speed is controlled at 600r/min, after stirring for 3min, a filler is slowly added into the stirring kettle, after all the filler is added, the rotating speed is increased to 1800r/min, the filler is continuously dispersed, when the system fineness is not more than 30 mu m, the rotating speed is reduced to 800r/min, the rest antifouling agent, active diluent and phenolic epoxy modified resin are added, after uniform stirring, the rotating speed is reduced to 300r/min, an antioxidant is added, and the stirring is carried out for 30min, so that the component A is prepared.
(2) Adding polyamide curing agent and organic diluent into a stirring kettle, stirring at a stirring speed of 500r/min for 15min to obtain component B, and subpackaging.
The component A and the component B are prepared according to the following ratio of 1: 6 in a mass ratio.
Comparative example 1
A preparation method of an environment-friendly antifouling agent for marine coatings comprises the following steps:
s1, adding tung oil into a reaction kettle, adding a sodium hydroxide solution (the mass fraction of the sodium hydroxide is 55%) accounting for 15% of the mass of the tung oil, and reacting under stirring at 300r/min, wherein the reaction temperature is 60 ℃ and the reaction time is 2 hours.
S2, after the reaction is finished, standing and separating liquid, taking the lower layer liquid, filtering by using filter cloth with 600-mesh pores to remove impurities, centrifuging to further remove the impurities, wherein the centrifugation speed is 20000r/min, the centrifugation time is 10min, and separating to obtain the supernatant which is a sodium eleostearate solution.
S3, titrating with 0.3mol/LHCl until no white floccule is generated;
s4, filtering the precipitate by using filter paper to obtain eleostearic acid, and washing the precipitate by using deionized water.
S5, mixing eleostearic acid and diethylenetriamine according to a mass ratio of 2.1: 1 adding the mixture into a reaction kettle, simultaneously adding trimethylbenzene accounting for 50 percent of the total mass of eleostearic acid and diethylenetriamine, heating to 140 ℃, reacting for 2.5 hours, heating to 210 ℃, continuing to react for 2.5 hours, cooling to 80 ℃, adding benzyl bromide accounting for 2 percent of the mass of eleostearic acid, reacting for 5 hours, washing the obtained product with dimethylbenzene, and drying.
The tung oil modified quaternary ammonium salt is used as an antifouling agent to prepare an antifouling coating, and the preparation method comprises the following steps:
(1) according to the formula, phenolic epoxy modified resin with the formula amount of 50% is added into a stirring kettle, a dispersing agent, a leveling agent, an anti-settling agent and an anti-aging agent are sequentially added, an active diluent with the formula amount of 20% is added, the stirring speed is controlled at 600r/min, after stirring for 3min, a filler is slowly added into the stirring kettle, after all the filler is added, the rotating speed is increased to 1800r/min, the filler is continuously dispersed, when the system fineness is not more than 30 mu m, the rotating speed is reduced to 800r/min, the rest antifouling agent, active diluent and phenolic epoxy modified resin are added, after uniform stirring, the rotating speed is reduced to 300r/min, an antioxidant is added, and the stirring is carried out for 30min, so that the component A is prepared.
(2) Adding polyamide curing agent and organic diluent into a stirring kettle, stirring at a stirring speed of 500r/min for 15min to obtain component B, and subpackaging.
The component A and the component B are prepared according to the following ratio of 1: 6 in a mass ratio.
Comparative example 2
A preparation method of an environment-friendly antifouling agent for marine coatings comprises the following steps:
s1, adding tung oil into a reaction kettle, adding a sodium hydroxide solution (the mass fraction of the sodium hydroxide is 55%) accounting for 15% of the mass of the tung oil, and reacting under stirring at 300r/min, wherein the reaction temperature is 60 ℃ and the reaction time is 2 hours.
S2, after the reaction is finished, standing and separating liquid, taking the lower layer liquid, filtering by using filter cloth with 600-mesh pores to remove impurities, centrifuging to further remove the impurities, wherein the centrifugation speed is 20000r/min, the centrifugation time is 10min, and separating to obtain the supernatant which is a sodium eleostearate solution.
S3, titrating with 0.3mol/LHCl until no white floccule is generated;
s4, filtering the precipitate by using filter paper to obtain eleostearic acid, and washing the precipitate by using deionized water.
S5, mixing eleostearic acid and diethylenetriamine according to a mass ratio of 2.1: 1, adding the mixture into a reaction kettle, adding trimethylbenzene accounting for 50 percent of the total mass of eleostearic acid and diethylenetriamine, continuously and slowly introducing nitrogen, heating to 140 ℃, reacting for 2.5 hours, heating to 210 ℃, continuing to react for 2.5 hours, cooling to 80 ℃, adding benzyl chloride accounting for 2 percent of the mass of eleostearic acid, reacting for 5 hours, washing the obtained product with dimethylbenzene, and drying.
The tung oil modified quaternary ammonium salt is used as an antifouling agent to prepare an antifouling coating, and the preparation method comprises the following steps:
(1) according to the formula, phenolic epoxy modified resin with the formula amount of 50% is added into a stirring kettle, a dispersing agent, a leveling agent, an anti-settling agent and an anti-aging agent are sequentially added, an active diluent with the formula amount of 20% is added, the stirring speed is controlled at 600r/min, after stirring for 3min, a filler is slowly added into the stirring kettle, after all the filler is added, the rotating speed is increased to 1800r/min, the filler is continuously dispersed, when the system fineness is not more than 30 mu m, the rotating speed is reduced to 800r/min, the rest antifouling agent, active diluent and phenolic epoxy modified resin are added, after uniform stirring, the rotating speed is reduced to 300r/min, an antioxidant is added, and the stirring is carried out for 30min, so that the component A is prepared.
(2) Adding polyamide curing agent and organic diluent into a stirring kettle, stirring at a stirring speed of 500r/min for 15min to obtain component B, and subpackaging.
The component A and the component B are prepared according to the following ratio of 1: 6 in a mass ratio.
The yields of the tung oil-modified quaternary ammonium salts of examples 1-3 and comparative examples 1-2 are shown in table 2;
TABLE 2
The antifouling paints of examples 1 to 3 and comparative examples 1 to 2 were applied to tinplate to a thickness of 40 to 60 μm, and after 1 week of maintenance, the tinplate was placed in seawater for 6 months, and the surface was observed at intervals for contamination, and the contamination was measured according to GB/T5370-ion 2007 "method for testing shallow sea immersion of antifouling paint sample", and the results of contamination after 6 months are shown in Table 3:
TABLE 3
| Case(s) | Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 |
| Degree of contamination% | 6.5 | 8.3 | 7.8 | 7.8 | 7.7 |
As can be seen from Table 1, nitrogen is not introduced in the preparation process of the tung oil modified quaternary ammonium salt antifouling agent (comparative example 1), the yield of the antifouling agent is very low, but the yield of the preparation by using benzyl chloride is obviously lower than that of the preparation by using benzyl chloride in the invention, so that the preparation method improves the yield of the tung oil modified quaternary ammonium salt antifouling agent by improving the preparation process, is suitable for industrial mass production, and can effectively reduce the production cost of the coating.
As can be seen from Table 2, the ship antifouling paint prepared by the method has low pollution degree after being used for 6 months, and proves that the ship antifouling paint can effectively prevent pollution and has good long-term protection effect on ships.
Claims (10)
1. The preparation method of the environment-friendly antifouling agent for the marine coating is characterized by comprising the following steps of:
eleostearic acid and diethylenetriamine are mixed according to the mass ratio (2-2.2): 1, adding trimethylbenzene into a reaction kettle, continuously introducing nitrogen, heating to 140-150 ℃, reacting for 2-2.5h, heating to 210-22 ℃, continuing to react for 2-2.5h, cooling to 80-90 ℃, adding benzyl bromide accounting for 1-2% of the mass of eleostearic acid, reacting for 4-5h, washing the obtained product with dimethylbenzene, and drying.
2. The method for preparing the environment-friendly antifouling agent for marine coatings as claimed in claim 1, wherein the amount of trimethylbenzene is 40-50% of the total mass of eleostearic acid and diethylenetriamine.
3. The method for preparing an environmental-friendly antifouling agent for marine coatings as claimed in claim 1, wherein the stirring speed is 300-400r/min during the reaction process.
4. The method for preparing the environment-friendly antifouling agent for the marine coating according to claim 1, wherein the eleostearic acid is prepared by the following steps:
s1, adding tung oil into a reaction kettle, adding a sodium hydroxide solution, and reacting under stirring;
s2, after the reaction is finished, standing and separating liquid, taking the lower layer liquid, and filtering to remove impurities to obtain a sodium eleostearate solution;
s3, titrating with acid until no white floccule is generated;
s4, filtering to obtain a precipitate eleostearic acid, and washing with water.
5. The method for preparing the environment-friendly antifouling agent for marine coatings as claimed in claim 4, wherein in the method for preparing the eleostearic acid, the concentration of the sodium hydroxide solution is 50-60%, the addition amount is 10-15% of the mass of the eleostearic oil, the stirring speed in the reaction process is 300-500r/min, the reaction temperature is 60-70 ℃, and the reaction time is 1-2 h.
6. An antifouling paint comprising the antifouling agent produced by the production method according to any one of claims 1 to 5.
7. The antifouling paint according to claim 6, wherein the antifouling paint comprises the components in a mass ratio of 1: a, B of (5-7);
wherein the component A comprises the following raw materials in parts by weight:
30-55 parts of phenolic epoxy modified resin,
20-40 parts of a filler,
10-20 parts of an anti-fouling agent,
12-18 parts of a reactive diluent,
0.4-3.3 parts of an auxiliary agent;
the component B comprises the following raw materials in parts by weight: 60-80 parts of polyamide curing agent and 20-30 parts of organic solvent.
8. An antifouling paint according to claim 7, wherein the reactive diluent is one or more of benzyl alcohol, ethylene glycol, 1, 6-hexanediol diacrylate, and tripropylene glycol diacrylate.
9. An antifouling paint according to claim 7, wherein the organic solvent is one or two of a dearomatized diluent, a diformate, dimethylformamide and dimethyl glutarate.
10. The antifouling paint as claimed in claim 7, wherein the auxiliary comprises the following raw materials in parts by weight: 0.1-1 part of anti-settling agent, 0.1-1 part of anti-aging agent, 0.1-0.5 part of dispersing agent and 0.1-0.8 part of flatting agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210015048.4A CN114409559A (en) | 2022-01-07 | 2022-01-07 | Preparation method and application of environment-friendly antifouling agent for marine coating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210015048.4A CN114409559A (en) | 2022-01-07 | 2022-01-07 | Preparation method and application of environment-friendly antifouling agent for marine coating |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114409559A true CN114409559A (en) | 2022-04-29 |
Family
ID=81271916
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210015048.4A Pending CN114409559A (en) | 2022-01-07 | 2022-01-07 | Preparation method and application of environment-friendly antifouling agent for marine coating |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114409559A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105062175A (en) * | 2015-08-10 | 2015-11-18 | 广西经正科技开发有限责任公司 | Antifouling biological adhesive agent and antifouling biological adhesive coating |
| CN108251848A (en) * | 2016-12-28 | 2018-07-06 | 中国石油天然气股份有限公司 | A kind of corrosion inhibiter and preparation method thereof |
| CN109053579A (en) * | 2018-08-01 | 2018-12-21 | 延安大学 | A kind of Imidazoline Quatemary-ammonium-salt Corrosion Inhibitor and preparation method thereof |
| CN109280522A (en) * | 2018-10-17 | 2019-01-29 | 东莞市沅邦电子材料有限公司 | Fire resistant epoxy sealant |
| CN111138958A (en) * | 2020-01-10 | 2020-05-12 | 中国科学院海洋研究所 | Gel coat coating material with antifouling property and preparation method thereof |
| CN112680734A (en) * | 2020-12-09 | 2021-04-20 | 鞍钢集团矿业有限公司 | Corrosion inhibitor suitable for acidic medium and preparation method and application thereof |
-
2022
- 2022-01-07 CN CN202210015048.4A patent/CN114409559A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105062175A (en) * | 2015-08-10 | 2015-11-18 | 广西经正科技开发有限责任公司 | Antifouling biological adhesive agent and antifouling biological adhesive coating |
| CN108251848A (en) * | 2016-12-28 | 2018-07-06 | 中国石油天然气股份有限公司 | A kind of corrosion inhibiter and preparation method thereof |
| CN109053579A (en) * | 2018-08-01 | 2018-12-21 | 延安大学 | A kind of Imidazoline Quatemary-ammonium-salt Corrosion Inhibitor and preparation method thereof |
| CN109280522A (en) * | 2018-10-17 | 2019-01-29 | 东莞市沅邦电子材料有限公司 | Fire resistant epoxy sealant |
| CN111138958A (en) * | 2020-01-10 | 2020-05-12 | 中国科学院海洋研究所 | Gel coat coating material with antifouling property and preparation method thereof |
| CN112680734A (en) * | 2020-12-09 | 2021-04-20 | 鞍钢集团矿业有限公司 | Corrosion inhibitor suitable for acidic medium and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103254701B (en) | Novel anti-corrosion, anti-ultraviolet, anti-bacteria and wear-resistant paint and preparation method for same | |
| CN102807796B (en) | Novel environment-friendly anti-fouling coating paint for ocean | |
| US4675051A (en) | Marine anti-fouling paint | |
| CN104761991B (en) | Environmental-protection type multi-element collaborative marine anti-fouling coating | |
| CN111286273A (en) | Novel long-acting broad-spectrum antibacterial multifunctional water-based building coating and preparation method thereof | |
| CN111500130A (en) | Environment-friendly super-hydrophobic antifouling paint | |
| CN104403448A (en) | Nano cuprous oxide and nano silver compounded sea anti-fouling paint | |
| CN105837733A (en) | Capsaicin [(12-acryloyl-oxy)-dehydroabietate]-acrylic acid copolymer, and preparation and application thereof | |
| CN109651907A (en) | Novel tin-free self-polishing type antifouling paint | |
| CN112251141B (en) | Graphene modified nano silver-copper-zinc-aluminum composite coating and preparation method and application thereof | |
| CN112625586A (en) | Environment-friendly pollution-free ship antifouling finish paint and preparation method thereof | |
| CN106905780A (en) | A kind of capsicim environmental protection type anti-pollution paint and preparation method thereof | |
| CN112694833A (en) | Composite low-surface-energy antifouling paint containing basalt fiber powder and scale powder and preparation method thereof | |
| CN114409559A (en) | Preparation method and application of environment-friendly antifouling agent for marine coating | |
| CN108329783B (en) | Marine antifouling paint and preparation method thereof | |
| CN100341964C (en) | Antifouling paint for sea deep water net cage | |
| CN116179040A (en) | Tin-free low-surface-energy self-polishing environment-friendly thick-paste type anti-fouling paint and preparation method and application thereof | |
| CN110484139A (en) | A kind of capsaicine anti-fouling paint | |
| CN112745731B (en) | Hyperbranched polymer-containing waterborne antifouling composite coating and preparation method thereof | |
| CN110079170A (en) | A kind of ship pollution prevention coating of painting under water and preparation method thereof | |
| CN109266172B (en) | Marine antifouling paint and preparation method and application thereof | |
| AU2021105323A4 (en) | Capsaicin environmentally-friendly antifouling coating and preparation method thereof | |
| US4908061A (en) | Antifouling coating | |
| CN108997868A (en) | It is a kind of aqueous from polishing fishing antifouling paint and preparation method thereof | |
| CN111560207A (en) | Biological adhesion-preventing nontoxic nano coating and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |