CN115353789A - Bionic non-toxic marine antifouling paint and preparation method thereof - Google Patents
Bionic non-toxic marine antifouling paint and preparation method thereof Download PDFInfo
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- CN115353789A CN115353789A CN202211015985.6A CN202211015985A CN115353789A CN 115353789 A CN115353789 A CN 115353789A CN 202211015985 A CN202211015985 A CN 202211015985A CN 115353789 A CN115353789 A CN 115353789A
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- zinc
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- antifouling paint
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Images
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
- C09D133/00—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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
- C09D133/16—Homopolymers or copolymers of esters containing halogen atoms
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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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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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
- 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
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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
- 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
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
- C09D5/1675—Polyorganosiloxane-containing compositions
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T70/00—Maritime or waterways transport
- Y02T70/10—Measures concerning design or construction of watercraft hulls
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Abstract
The invention discloses a bionic nontoxic marine antifouling paint and a preparation method thereof, and the paint is a brand-new bionic nontoxic environment-friendly ship and a marine antifouling preparation which are used for marine facilities and ship antifouling and have no pollution hazard.
Description
[ technical field ] A
The invention relates to the technical field of corrosion prevention and pollution prevention of marine equipment, marine ship industry, marine fishery and the like, in particular to a bionic non-toxic marine antifouling paint and a preparation method thereof.
[ background ] A method for producing a semiconductor device
The attachment and growth of marine organisms on the surfaces of marine equipment, marine facilities, ships and the like is called marine organism fouling, and the marine organism fouling brings great harm to the marine facilities, the ships and the like. On one hand, the self weight of marine facilities, ships and the like is increased due to marine organism fouling, and the frictional resistance of ship navigation is increased, so that the ship navigation speed is reduced, and the fuel consumption is increased; on the other hand, the corrosion of the ship body and the marine facility is accelerated, the normal service life of the ship and the marine facility is shortened, for example, a sonar instrument is distorted, a pipeline and a breeding net are blocked, the danger of a marine oil drilling platform is increased, and the military facility and military activities are also greatly threatened. According to incomplete statistics, the economic loss caused by marine biofouling is huge worldwide, the direct economic loss is about $ 500-800 million each year, the frictional resistance of a ship in navigation is more than 80% from the surface of a ship body, the resistance depends on the fouling condition of marine organisms, when the marine biofouling rate is 5%, the navigation resistance of the ship is increased to 3-5 times that of the ship in navigation on the net surface, the fuel consumption is increased by 30%, and therefore, the prevention of the marine biofouling becomes one of the main subjects of scientific and technological attack research in the aspect worldwide.
At present, people usually deal with marine organisms such as marine facilities, ships and the like by using a mechanical cleaning method, an electrochemical method, an ultrasonic method, a radiation method, a low-surface-energy material method, a coating method and the like. Among the methods, the coating method is most economical and effective and has the widest application range. However, most of the antifouling products sold on the market throughout the market contain a large amount of heavy metals (such as copper, mercury, tin, lead, silver and the like) or highly toxic organic compounds, and the application of the antifouling products inevitably causes huge pollution to the marine ecological environment.
Since the development of marine antifouling paints in the early 20 th century, the problem of marine organism adhesion was basically solved, but most of the antifouling paints are toxic products, and in the later 20 th century, with various heavy metal compounds being banned, such as antifouling agents having main antifouling effects of mercury, arsenic and the like, being completely removed and banned, the organotin compound "TBT" becomes a representative antifouling preparation at that time, and is widely used in antifouling paints for ships and marine facilities. In the 80 s, more and more people are aware that most of the existing antifouling preparations are mainly organic tin compounds, which accumulate and remain in the bodies of fishes and shellfishes to cause various pathological changes and genetic variations of marine organisms, so that the maritime organizations of various countries and the world start to make legislation, and the production and use of antifouling paints containing organic tin compounds are required to be prohibited gradually.
There are still organotin-containing antifouling paint products on the market today, but the sales volume has been on the decline. 80% -95% of the marine antifouling paint on the market is used as an antifouling agent, but cuprous oxide has good hydrophilicity and can be precipitated in seawater or partially dissociated in a water body, so that a great amount of algae die. After being enriched, a large amount of metal ions are fused into a food chain through marine organisms, and cuprous oxide deserts the submarine pasture after the precipitation, and the cuprous oxide is believed to be completely forbidden in the near future.
[ summary of the invention ]
The invention aims to effectively control and prohibit the use of an organotin compound antifouling preparation, effectively inhibit fouling of marine organisms on marine equipment, ships and the like, and reduce pollution and harm to marine ecological environment. The invention provides a bionic nontoxic marine antifouling paint and a preparation method thereof, and the paint is a brand-new bionic nontoxic environment-friendly ship and marine facility antifouling paint which is used for marine facilities and ships, is antifouling and has no pollution hazard.
The purpose of the invention is realized by the following technical scheme:
a bionic nontoxic marine antifouling paint is prepared from the following raw materials in parts by weight:
100 parts of base material, 5.0-15.0 parts of hydrolysable tannic acid, 5.0-12.0 parts of zinc disulfide carbamate and zinc pyrithione, 5.1-13.0 parts of N-di (substituted phenyl) methylene dithioacetamide, 5.0-15.0 parts of isothiazolinone, 20.0-35.0 parts of silicon-based polymer, 7.0-14.0 parts of rosin resin, 10.0-22.0 parts of zinc oxide, 1.0-8.0 parts of iron red powder, 1.0-5.0 parts of organic silicone grease, 5.0-13.0 parts of dimethylbenzene, 1.0-6.0 parts of butanol and 3.0-9.0 parts of ethylene oxide-propylene oxide block copolymer; wherein the mass ratio of the zinc disulfide carbamate to the zinc pyrithione is 15;
the preparation method of the base material comprises the following steps:
1) Taking 2.5g of ethanolamine and 10ml of tetrahydrofuran, placing the mixture in a flask, carrying out ice bath to 5 ℃, slowly dropwise adding 7.0g of heptafluorobutyryl chloride, completing dropwise adding, slowly heating to 24 ℃, and shaking for 3 hours to obtain a product, namely a yellow brown pasty substance;
2) Removing excessive tetrahydrofuran at 66-68 deg.C by rotary evaporation, adjusting pH to 7.0-8.0 with hydrochloric acid, washing with 50 deg.C hot water once, removing excessive water by rotary evaporation, and repeatedly crystallizing with chloroform for 3 times to obtain brown crystal-N-hydroxyethyl heptafluoro butyramide;
3) Adding 0.8g of 2, 4-toluene diisocyanate and 0.10ml of zinc isooctanoate into a flask, introducing 99.99% pure nitrogen as a protective gas, heating to 55-60 ℃, slowly dropwise adding 3.8g of N-hydroxyethyl heptafluorobutanamide and 8.6ml of dehydrated 4-methyl-2-pentanone, reacting for 6 hours under the condition, wherein after 3 hours, heating to 82-85 ℃, dropwise adding 6.0ml of phenoxyethyl acrylate, and continuously reacting for 3 hours to obtain a modified product, namely a fluorocarbon monomer;
4) The flask was charged with dehydrated 4-methyl-2-pentanone and 1: diacyl peroxide with the mass of 3.2, raising the temperature to 70-76 ℃, keeping the temperature for reaction for 1h, adding the fluorocarbon monomer, slowly dropwise adding 3.0ml of ethyl methacrylate, keeping the temperature at 75 ℃, reacting for 10h, and adding 6 mass percent of KH-550 to obtain the fluorocarbon resin copolymer.
Further, the bionic non-toxic marine antifouling paint is prepared from the following raw materials in parts by weight:
100 parts of base material, 8.4-12.7 parts of hydrolysable tannic acid, 9.1-11.2 parts of zinc disulfide carbamate compound and zinc pyrithione, 9.8-11.6 parts of N-bis (substituted phenyl) methylene bis (thioacetamide), 8.0-11.3 parts of isothiazolinone compound, 24.6-27.5 parts of silicon-based polymer, 9.3-12.1 parts of rosin resin, 14.7-18.4 parts of zinc oxide, 4.2-5.7 parts of iron red powder, 2.8-3.9 parts of organic silicone grease, 7.6-11.1 parts of dimethylbenzene, 3.8-5.2 parts of butanol and 5.2-4.9 parts of ethylene oxide-propylene oxide block copolymer; wherein the mass ratio of the zinc disulfide carbamate to the zinc pyrithione is 15.
Furthermore, the bionic nontoxic marine antifouling paint is prepared from the following raw materials in parts by weight:
100 parts of base material, 10.2 parts of hydrolysable tannic acid, 10.7 parts of zinc disulfide carbamate and zinc pyrithione, 11.4 parts of N-di (substituted phenyl) methylene dithioacetamide, 10.6 parts of isothiazolinone compound, 25.7 parts of silicon-based polymer, 10.0 parts of rosin resin, 15.9 parts of zinc oxide, 5.0 parts of iron oxide red powder, 3.2 parts of organic silicone grease, 10.0 parts of xylene, 4.1 parts of butanol and 5.7 parts of ethylene oxide-propylene oxide block copolymer; wherein the mass ratio of the zinc disulfide carbamate to the zinc pyrithione is 15.
The bionic non-toxic marine antifouling paint disclosed by the invention comprises the following components:
base material: the selection of the base material must ensure that the base material meets the original purpose of the 'environment-friendly and non-toxic' invention of the patent, and also ensures the required physical properties and the conventional mechanical index; the bionic nontoxic marine antifouling paint can only be coated on a hydrophobic base material to release the protein of the effective component acting on the aquatic attachment, so that the invention is of great significance by selecting a hydrophobic base material. The inventor screens a part of base materials aiming at hydrophobicity, innocuity and easy modification, and finally selects fluorocarbon resin copolymer with low surface energy as the component of the base materials, the fluorocarbon resin copolymer has stable structure and extremely strong hydrophobicity and elasticity, the inventor arranges fluorocarbon side chains on a linear siloxane main chain to ensure that the side chains are arranged in a coating film according to a certain orientation relation, namely, the fluorocarbon resin copolymer has the characteristics of high elasticity and low surface energy, and is matched with the main effective components of the coating, so as to achieve the purpose of preventing marine organisms from attaching and have the excellent performances of fluorine and silicon.
Hydrolyzable tannic acid: organisms with tannin components are spread over the sea and the biology monitoring of oceans with the largest global area shows that mangrove forest is not parasitized by barnacles, the bark is cut open by a knife, the wounds are oxidized into blood red for a short time, and researches show that the tannin plays a great role in the organisms, has bitter taste, generates p-benzoquinone after oxidation, has an irritant effect, can act on more than 540 families of the order 8 of the barnacles, and is expelled to ships before the metamorphosis development or in the stage of the primary metamorphosis development, namely in the larval stage (reversible stage); the hydrolysable tannin can also react with various alkaloids and heavy metal ions to generate a complex, and the chemical structure of the hydrolysable tannin has the structural characteristics of polyphenol, so that the hydrolysable tannin also has the antioxidant and bactericidal properties and effects of the polyphenol. When the hydrolysable tannic acid encounters protein molecules, strong interactions occur, destroying the expression of the protein. Therefore, when marine organisms dilute the protein adhesions towards the surface of the marine equipment, the hydrolyzable tannic acid which is slowly released in the coating on the surface of the equipment can respond to destroy the protein adhesions, thereby expelling the marine organisms. The present invention applies a bionic method to destroy the synthetic expression of protein on the surface of equipment, and is very obvious to prevent the adhesion of marine organisms and to be used as a sterilization promoter.
Zinc dithiocarbamates, zinc pyrithione: the combination of zinc disulfide compound and zinc pyrithione has broad spectrum anticorrosion mechanism effect, wherein, the zinc disulfide carbamate can perform ester exchange reaction with C1-C4 alcohols (polyol as far as possible) in the components to obtain the polyol carbamate compound, in order to improve the compatibility of the patent, the inventor selects another method with low cost and higher product rate: in the molecular formula, R1 and R2 are the same or different hydrogen atoms, alkyl, cycloalkyl, aryl, macromolecules, heterocyclic rings and other groups, and a substituent R3 is selected as Zn ions and synthesized into zinc disulfide carbamate, so that the synthesized polyurethane does not contain residual toxic isocyanate groups. The bactericide selects zinc pyrithione with broad spectrum effect to expel most spinal cord animals similar to ascidians in water and reduce the attachment rate of marine organisms, and the chelating agent zinc pyrithione with weak lipophilicity is used as an ionophore and acts on fertilized eggs of the spinal cord animals which are attached and fixed to transport protons into the fertilized eggs and carry potassium ions away, so that the shuttle back and forth breaks the ion gradient of cell membranes, the process is not lost, the action mechanism is that ions of cell sap in the fertilized eggs are unbalanced through ion exchange to play a role in sterilization and expulsion, and the toxicity mechanism is not utilized, because the bactericide meets the original purpose of the invention and cannot generate drug resistance.
N-N, -di (substituted phenyl) methylene bisthioacetamide is used as an algaecide which is used for inhibiting the adhesion performance of seaweed, so that the inventor selects a bisthioacetamide compound to achieve the aim. In order to reduce the hydrolysis toxicity of the product and integrate expelling and long acting, the inventor does not adopt dithiocyano methane and diiodomethyl antihistaminic substances commonly used by most pesticides, so that the possibility of high toxicity of the hydrolysate to marine organisms is reduced, in order to better meet the original design purpose of 'non-toxicity and environment-friendliness' of the invention, the inventor selects N-di (substituted phenyl) methylene dithioacetamide as an algaecide, the effect of the algaecide is achieved by inhibiting the activity of a compound algal fructose-1, 6-/sedoheptulose-1, 7-diphosphatase for controlling the growth of algae, the excellent inhibition rate is far higher than that of a copper sulfate inhibitor added into most of the prior coatings, the condition that heavy metal ions are free and enriched in marine organism chains does not exist, and the characteristics of hydrolysis, non-toxicity, high inhibition rate, wide action range and the like are realized while the inhibition effect is exerted.
Isothiazolinone: isothiazolinone is a repellent for aquatic organisms and can repel marine organisms. Isothiazolinone consists mainly of 5-chloro-2-methyl-4-isothiazolin-3-one (CIT) and 2-methyl-4-isothiazolin-3-one (MIT). Isothiazolinones are anti-attachment by breaking the bonds of bacterial or algal proteins. The marine microorganisms are mainly attached to the surface of equipment by virtue of protein mucus eruption and then grow and multiply, and when isothiazolinone released by a coating is contacted with the proteins, the continuous expression of the proteins can be rapidly and irreversibly inhibited, and the information expression is cut off, so that microbial cells are killed, and therefore, the marine microorganisms have a strong anti-attachment effect on common bacteria, fungi, algae and the like. The bionic nontoxic environment-friendly antifouling preparation is mainly characterized in that a hydrolyzable tannin substance degradable by a land and sea symbiotic plant is used as a first effective component of the preparation, and other three substances are used as a second effective component of the preparation. The chemical names and molecular structural formulas of the substances are as follows:
rosin resin: the paint integrates excellent performances of oxidation resistance, impact resistance, corrosion resistance, aging resistance and the like; the addition of the rosin resin can greatly improve the toughness of the product, and the excellent environmental protection performance of the rosin resin can also make the rosin resin be evaluated as a solvent-free environment-friendly coating raw material "
Silicon-based polymer: it contains both "organic groups" and "inorganic structures" with different functions, and has organic and inorganic functions due to the special structure. The polymer used in the method is polyethylene silicone resin, the proportion of ethyl connected with silicon atoms in a siloxane chain is adjusted, the proportion of the number of the ethyl and the silicon atoms in the polymer is adjusted to be 0.8-1.2, and the flexibility and the saline-alkali resistance of a condensation product are effectively improved; when the ratio is about 1.0, the product has good elasticity and can form a paint film having high adhesion.
Ethylene oxide-propylene oxide block copolymer: because the ethylene oxide-propylene oxide segmented copolymer has no dissociation and charge and extremely weak adsorption force to pigment, the ethylene oxide-propylene oxide segmented copolymer serving as the stabilizer of the water-based paint has the functions of emulsification stability, strengthening the corrosion resistance of the paint and endowing a surface of a metal substrate with a layer of involucra, so that the water-based paint is easy to paint and is not easy to fall off.
Alcohols: C1-C4 saturated alcohols, such as butanol, are selected as product dispersants. By adjusting the concentration, the release speed and the time effect of the antifouling agent are controlled.
Other fillers: inorganic pigments, dispersion solvents, and the like.
In the invention, the hydrolysable tannic acid has good antibacterial ability, algae-preventing activity, antiviral effect and other effects, but the antifouling effect is weaker in durability, after the zinc disulfide carbamate, the zinc pyrithione, N-N, -bis (substituted phenyl) methylene bisthioacetamide and isothiazolinone are added, the antifouling effect is excellent, the hydrolysable tannic acid can hydrolyze in seawater and has no residue, the four compounds are compounded and prepared into the bionic nontoxic environment-friendly antifouling paint, the antifouling performance, the efficacy energy and the biological activity of the antifouling paint are greatly improved, the antifouling effect is obviously enhanced, the antifouling paint has good stability and excellent antifouling effect, is nontoxic and does not harm marine ecological environment.
The invention also relates to a preparation method of the bionic nontoxic marine antifouling paint, which comprises the following steps:
1) Extracting hydrolyzable tannic acid by an organic solvent extraction method: crushing 100 parts by weight of an extract to be extracted, soaking in 155 parts by weight of a methanol aqueous solution in a mass ratio of 9;
2) Adding 45 parts by weight of n-hexane at 30 ℃, mixing and soaking for 2.5 hours, and then further purifying;
3) And (3) reduced pressure distillation I: the pressure is 133.30Pa-133.33Pa; putting the liquid obtained in the previous step into a round-bottom flask, and adding two stirrers; assembling a reduced pressure distillation glass device, and smearing a small amount of vacuum grease on all joints to achieve a sealing effect; the Weigler distillation column is wrapped by absorbent cotton to achieve the heat preservation effect, reduce the distillation time and reduce the heat dissipation; a condensation pipe is connected with a water pipe, a tap is opened for leak detection, the flask is slowly vacuumized under the condition of excellent sealing effect and no leakage, and when the flask is vacuumized, foam in the flask is gradually reduced until the foam disappears, and the flask is heated to 155-157 ℃; monitoring the temperature rise process at any moment, wherein the temperature rise process cannot be carried out too quickly until the product liquid in the previous step starts to reflux, after the reflux is finished, the temperature starts to drop, introducing nitrogen into the device, removing a heat source, and after the temperature of the device is reduced to room temperature, obtaining a reduced pressure distillation product, soaking the reduced pressure distillation product solution by using 125 parts by weight of methanol aqueous solution with the mass ratio of 8;
4) And (3) reduced pressure distillation II: the method is the same as the above steps, the pressure is unchanged, the heating temperature is 170-175 ℃, the reduced pressure distillation product solution in the above steps is soaked by 105 parts by weight of methanol water solution with the mass ratio of 6;
5) And (3) reduced pressure distillation III: the method is the same as the above steps, the pressure is unchanged, the heating temperature is 142-145 ℃, water is added to dilute the redundant solvent, and the finished product of the hydrolysable tannin extract is obtained after vacuum drying; the specific process of vacuum drying is as follows: keeping the normal operation of the equipment, switching on a water source, a power supply and a gas source, putting a product diluted by adding water in the previous step into a drying tray, pushing the product into a drying box, closing a box door, tightening a screw, opening a vacuum pump, closing an exhaust valve, opening an air pump, opening a steam valve when the air pressure is stabilized at-0.08 MPa, opening a drain valve, closing the drain valve after draining condensed water in a heating pipe, starting heating, setting the temperature at 72-74 ℃, observing the condition of the object to be dried every 15min, and warely preventing overhigh drying; after 80min, when the dried matter is completely dried, closing the steam valve and the air extraction valve, opening the evacuation valve, returning the air pressure in the drying oven, closing the vacuum pump, and when the air pressure returns to normal, obtaining the product, namely the hydrolyzed tannin extract;
6) Sequentially adding the following components into a reaction kettle: the preparation method comprises the following steps of (1) setting an initial temperature to be 25-28 ℃, gradually increasing the temperature to 75-80 ℃ within 3 hours, and maintaining stirring for 8 hours to obtain a crude product, wherein the initial temperature is set to be 25-28 ℃, the reaction solvent (silicon-based polymer, rosin resin, organic silicone grease, xylene and butanol), the pigment (iron oxide red powder), the effective components of the antifouling paint (hydrolyzable tannic acid, zinc disulfide carbamate + zinc pyrithione, N-N, -di (substituted phenyl) methylene bis (thioacetamide) and isothiazolinone), the base material (fluorocarbon resin copolymer) and the auxiliary agent (zinc oxide and ethylene oxide-propylene oxide block copolymer);
7) And (3) finely grinding the crude product for 2 times in a high-speed grinding disperser, and finely grinding for 4 times to obtain the product.
The raw materials of the extract to be extracted in the step 1) are selected from seaweed, pomegranate, immature persimmon or tea.
The bionic nontoxic marine antifouling paint disclosed by the invention can be selected according to the use design requirements of the antifouling paint, the hydrolyzable tannic acid of the effective component of the antifouling agent and the mixture of zinc disulfide carbamate and zinc pyrithione with the mass ratio of 15, the effective component of the antifouling agent is N-N, any two or three of di (substituted phenyl) methylene bisthioacetamide and the effective component of the antifouling agent is completely combined together, and the total mixing amount is the main component of the paint.
The bionic nontoxic marine antifouling paint disclosed by the invention is disclosed in detail in the description of preparation and use of the antifouling paint, so that the bionic nontoxic marine antifouling paint disclosed by the invention can be better prepared. The compounding process includes dissolving and mixing the compounds as effective antifouling components in common organic solvent, or mixing the compounds in powder state in a grinding machine, mixing the solution or powder of the effective antifouling preparation compounds, adding the liquid and powder antifouling preparation compounds into the paint, and mixing the liquid and powder antifouling preparation compounds with the organic solvent, paint, surface active material and other required components via scattering, stirring and grinding.
In order to completely replace heavy metal ions with high toxicity, such as Cu, sn and the like, the inventor extracts tannic acid from marine organisms, crudely extracts active substances in marine animals, plants and microbial protomers by utilizing the existing technologies of extraction, separation, detection and the like, and separates and extracts hydrolyzable tannic acid which can strongly act with biological protein and destroy protein adhesive substances through the processes of polarity increase, activity detection and the like. The extraction and separation of the crude extract and the secondary metabolite are carried out in a closed reaction kettle, no harmful substances are discharged, and the clean manufacturing process is realized.
The solvents used for preparing the bionic nontoxic marine antifouling paint comprise alcohols: methanol, ethanol, propanol, butanol, etc., or polyhydric saturated alcohols; aromatic hydrocarbon compound: toluene, xylene, mixed benzene, etc., and also ketones, lipids, amines, etc.
Compared with the prior art, the invention has the following advantages:
1. the bionic nontoxic marine antifouling paint disclosed by the invention is characterized in that two substances with good compatibility are simultaneously developed, namely an environment-friendly antifouling component and a resin matrix with controllable degradation, the main component of the preparation is biological hydrolyzable tannic acid extracted from marine and terrestrial symbiotic plants, and the biological hydrolyzable tannic acid is taken as one of the effective components of the bionic nontoxic marine antifouling paint, so that the bionic nontoxic marine antifouling paint has the main effects of antifouling, mildew proofing and antibiosis.
2. According to the bionic nontoxic marine antifouling paint, according to the adhesion mechanism of marine fouling substances, an organic or inorganic antibacterial substance is introduced as one of effective components of the bionic nontoxic environment-friendly antifouling preparation through a bionic principle, the organic or inorganic antibacterial substance is introduced, does not contain heavy metal ions, and can be hydrolyzed in seawater without residues, such as zinc disulfide, zinc pyrithione \8230 \\ 8230
3. The bionic nontoxic marine antifouling paint disclosed by the invention can be well mixed with film-forming resin of the paint in the process of preparing the antifouling paint, and can be mixed and used with various common resins, such as epoxy resin, chlorinated rubber resin, chlorinated polypropylene resin, petroleum resin, alkyd resin, acrylic resin, silicon resin and the like.
[ description of the drawings ]
FIG. 1 is a flow chart of a production process of the bionic nontoxic marine antifouling paint;
FIG. 2 is a schematic diagram of a simple preparation scheme of the bionic nontoxic marine antifouling paint;
FIG. 3 is a process diagram of the extraction of hydrolysable tannic acid of the bionic nontoxic marine antifouling paint.
[ detailed description ] embodiments
The following examples are provided to further illustrate the embodiments of the present invention.
Example 1:
a bionic nontoxic marine antifouling paint is prepared from the following raw materials in parts by weight:
the preparation method of the base material comprises the following steps:
1) Taking 2.5g of ethanolamine and 10ml of tetrahydrofuran, placing the mixture in a flask, carrying out ice bath to 5 ℃, slowly dropwise adding 7.0g of heptafluorobutyryl chloride, completing dropwise adding, slowly heating to 24 ℃, and shaking for 3 hours to obtain a product, namely a yellow brown pasty substance;
2) Removing excessive tetrahydrofuran at 66-68 deg.C by rotary evaporation, adjusting pH to 7.0-8.0 with hydrochloric acid, washing with 50 deg.C hot water once, removing excessive water by rotary evaporation, and repeatedly crystallizing with chloroform for 3 times to obtain brown crystal-N-hydroxyethyl heptafluoro butyramide;
3) Adding 0.8g of 2, 4-toluene diisocyanate and 0.10ml of zinc isooctanoate into a flask, introducing 99.99% pure nitrogen as a protective gas, heating to 55-60 ℃, slowly dropwise adding 3.8g of N-hydroxyethyl heptafluorobutanamide and 8.6ml of dehydrated 4-methyl-2-pentanone, reacting for 6 hours under the condition, wherein after 3 hours, heating to 82-85 ℃, dropwise adding 6.0ml of phenoxyethyl acrylate, and continuously reacting for 3 hours to obtain a modified product, namely a fluorocarbon monomer;
4) The flask was charged with 4-methyl-2-pentanone which had been dehydrated and 1:3.2 mass percent of diacyl peroxide, raising the temperature to 70-76 ℃, keeping the reaction for 1h, adding the fluorocarbon monomer, slowly dropwise adding 3.0ml of ethyl methacrylate, keeping the temperature at 75 ℃, reacting for 10h, and adding 6 mass percent of KH-550 to obtain the fluorocarbon resin copolymer.
The preparation method of the bionic nontoxic marine antifouling paint comprises the following steps:
1) Extracting hydrolyzable tannic acid by an organic solvent extraction method: crushing 100 parts by weight of an extract to be extracted, soaking in 155 parts by weight of a methanol aqueous solution in a mass ratio of 9;
2) Adding 45 parts by weight of n-hexane at 30 ℃, mixing and soaking for 2.5 hours, and then further purifying;
3) And (3) reduced pressure distillation I: the pressure is 133.30Pa to 133.33Pa; putting the liquid obtained in the previous step into a round-bottom flask, and adding two stirrers; assembling a reduced pressure distillation glass device, and smearing a small amount of vacuum grease on all joints to achieve a sealing effect; the Weigler distillation column is wrapped by absorbent cotton to achieve the heat preservation effect, reduce the distillation time and reduce the heat dissipation; a condensation pipe is connected with a water pipe, a tap is opened for leak detection, the flask is slowly vacuumized under the condition of excellent sealing effect and no leakage, and when the flask is vacuumized, foam in the flask is gradually reduced until the foam disappears, and the flask is heated to 155-157 ℃; monitoring the temperature rise process at any moment, wherein the temperature rise process cannot be carried out too quickly until the product liquid in the previous step starts to reflux, after the reflux is finished, the temperature starts to drop, introducing nitrogen into the device, removing a heat source, and after the temperature of the device is reduced to room temperature, obtaining a reduced pressure distillation product, soaking the reduced pressure distillation product solution by using 125 parts by weight of methanol aqueous solution with the mass ratio of 8;
4) And (3) reduced pressure distillation II: the method is the same as the above steps, the pressure is unchanged, the heating temperature is 170-175 ℃, the reduced pressure distillation product solution in the above steps is soaked by 105 parts by weight of methanol water solution with the mass ratio of 6;
5) And (3) reduced pressure distillation III: the method is the same as the above steps, the pressure is unchanged, the heating temperature is 142-145 ℃, water is added to dilute the redundant solvent, and the finished product of the hydrolysable tannin extract is obtained after vacuum drying; the specific process of vacuum drying is as follows: keeping the normal operation of the equipment, switching on a water source, a power supply and a gas source, putting a product diluted by adding water in the previous step into a drying tray, pushing the product into a drying box, closing a box door, tightening a screw, opening a vacuum pump, closing an exhaust valve, opening an air pump, opening a steam valve when the air pressure is stabilized at-0.08 MPa, opening a drain valve, closing the drain valve after draining condensed water in a heating pipe, starting heating, setting the temperature at 72-74 ℃, observing the condition of the object to be dried every 15min, and warely preventing overhigh drying; after 80min, when the dried matter is completely dried, closing the steam valve and the air extraction valve, opening the evacuation valve, returning the air pressure in the drying oven, closing the vacuum pump, and when the air pressure returns to normal, obtaining the product, namely the hydrolyzed tannin extract;
6) Sequentially adding the following components into a reaction kettle: the preparation method comprises the following steps of (1) setting an initial temperature to be 25-28 ℃, gradually increasing the temperature to 75-80 ℃ within 3 hours, and maintaining stirring for 8 hours to obtain a crude product, wherein the initial temperature is set to be 25-28 ℃, the reaction solvent (silicon-based polymer, rosin resin, organic silicone grease, xylene and butanol), the pigment (iron oxide red powder), the effective components of the antifouling paint (hydrolyzable tannic acid, zinc disulfide carbamate + zinc pyrithione, N-N, -di (substituted phenyl) methylene bis (thioacetamide) and isothiazolinone), the base material (fluorocarbon resin copolymer) and the auxiliary agent (zinc oxide and ethylene oxide-propylene oxide block copolymer);
7) And (3) finely grinding the crude product for 2 times in a high-speed grinding disperser, and finely grinding for 4 times to obtain the product.
Example 2:
a bionic non-toxic marine antifouling paint is prepared from the following raw materials in parts by weight:
the preparation methods of the base material and the coating are the same as the example 1.
Example 3:
a bionic nontoxic marine antifouling paint is prepared from the following raw materials in parts by weight:
| base material | 100g、 |
| Hydrolysable tannic acid | 15.0、 |
| Zinc dithiocarbamate + Zinc pyrithione | 12.0g、 |
| N-di (substituted phenyl) methylene bisthioacetamide | 13.0g、 |
| Isothiazolinone | 15.0g、 |
| Silicon-based polymers | 35.0g、 |
| Rosin resin | 14.0g、 |
| Zinc oxide | 18.4g、 |
| Iron oxide red powder | 8.0g、 |
| Organic silicone grease | 5.0g、 |
| Xylene | 13.0g、 |
| Butanol | 5.2g、 |
| Ethylene oxide-propylene oxide block copolymers | 9.0g。 |
The preparation methods of the base material and the coating are the same as the example 1.
Example 4:
a bionic nontoxic marine antifouling paint is prepared from the following raw materials in parts by weight:
the preparation methods of the base material and the coating are the same as the example 1.
Example 5:
a bionic non-toxic marine antifouling paint is prepared from the following raw materials in parts by weight:
| base material | 100g、 |
| Hydrolysable tannic acid | 10.2g、 |
| Zinc disulfide carbamate + Zinc pyrithione | 10.7g、 |
| N-di (substituted phenyl) methylene bisthioacetamide | 11.4g、 |
| Isothiazolinone | 10.6g、 |
| Silicon-based polymers | 25.7g、 |
| Rosin resin | 10.0g、 |
| Zinc oxide | 15.9g、 |
| Iron oxide red powder | 5.0g、 |
| Organic silicone grease | 3.2g、 |
| Xylene | 10.0g、 |
| Butanol | 4.1g、 |
| Ethylene oxide-propylene oxide block copolymers | 5.7g。 |
The preparation methods of the base material and the coating are the same as the example 1.
The preparation method of the bionic nontoxic marine antifouling paint in the embodiment 1-5 comprises the following steps:
1) The bionic nontoxic marine antifouling paint disclosed by the invention is disclosed in detail in the description of preparation and use of antifouling paint, so that the excellent modern bionic nontoxic marine antifouling paint can be prepared by better using the components of the bionic nontoxic marine antifouling paint disclosed by the invention. The compounding process includes dissolving and mixing the compounds as effective antifouling components in organic solvent, grinding and mixing the compounds in powder state in a mixing grinder, mixing the solution or powder of the effective antifouling preparation compounds, adding the liquid and powder antifouling preparation compounds into the paint, and spraying, stirring and grinding the mixture with the organic solvent, paint, surface active material and other required components to produce the bionic non-toxic antifouling paint.
Comparative example 1:
a bionic nontoxic marine antifouling paint is prepared from the following raw materials in parts by weight (compared with example 5, the paint lacks hydrolyzable tannic acid):
| base material | 100g、 |
| Zinc disulfide carbamate + Zinc pyrithione | 10.7g、 |
| N-di (substituted phenyl) methylene bisthioacetamide | 11.4g、 |
| Isothiazolinone | 10.6g、 |
| Silicon-based polymers | 25.7g、 |
| Rosin resin | 10.0g、 |
| Zinc oxide | 15.9g、 |
| Iron oxide red powder | 5.0g、 |
| Organic silicone grease | 3.2g、 |
| Xylene | 10.0g、 |
| Butanol | 4.1g、 |
| Ethylene oxide-propylene oxide block copolymers | 5.7g。 |
Comparative example 2:
a bionic nontoxic marine antifouling paint is prepared from the following raw materials in parts by weight (in comparison with example 5, lacking zinc disulfide carbamate and zinc pyrithione):
comparative example 3:
a bionic nontoxic marine antifouling paint is prepared from the following raw materials in parts by weight (compared with example 5, N-N, -di (substituted phenyl) methylene dithioacetamide is absent):
| base material | 100g、 |
| Hydrolyzable tannic acid | 10.2g、 |
| Zinc dithiocarbamate + Zinc pyrithione | 10.7g、 |
| Isothiazolinone | 10.6g、 |
| Silicon-based polymers | 25.7g、 |
| Rosin resin | 10.0g、 |
| Zinc oxide | 15.9g、 |
| Iron oxide red powder | 5.0g、 |
| Organic silicone grease | 3.2g、 |
| Xylene | 10.0g、 |
| Butanol | 4.1g、 |
| Ethylene oxide-propylene oxide block copolymers | 5.7g。 |
Comparative example 4:
a bionic nontoxic marine antifouling paint is prepared from the following raw materials in parts by weight (compared with example 5, the paint lacks isothiazolinone):
| base material | 100g、 |
| Hydrolysable tannic acid | 10.2g、 |
| Zinc dithiocarbamate + Zinc pyrithione | 10.7g、 |
| N-di (substituted phenyl) methylene bisthioacetamide | 11.4g、 |
| Silicon-based polymers | 25.7g、 |
| Rosin resin | 10.0g、 |
| Zinc oxide | 15.9g、 |
| Iron oxide red powder | 5.0g、 |
| Organic silicone grease | 3.2g、 |
| Xylene | 10.0g、 |
| Butanol | 4.1g、 |
| Ethylene oxide-propylene oxide block copolymers | 5.7g。 |
Comparative example 5:
a bionic nontoxic marine antifouling paint is prepared from the following raw materials in parts by weight (compared with example 5, silicon-based polymer is lacked):
experimental example:
according to the mixing proportion, various components are mixed to prepare the bionic nontoxic antifouling paint, the plate hanging real sea experiment test and the real ship ocean detection are carried out, the antifouling paint in the experimental example is respectively coated on an experimental plate and a real ship to carry out various technical parameter comparison, the optimal assembly mode and the optimal proportion coefficient are found out, and the bionic nontoxic marine antifouling paint with the optimal antifouling effect is obtained.
The rust preventive paint for ship was coated on the steel plate subjected to sand blasting, and the antifouling paint prepared according to the formulation of each example and comparative example was applied to a test steel plate (150 mmx300 mm) by a brush and a spray gun on the dried coating film, and it was required that the means of coating the steel plate with each formulation paint was as the same as possible. And the dry film thickness of the anti-fouling coating on the sample plate is about 100 μm; then placing the coated experimental plate in a Bohai sea old iron mountain Bay of China, soaking the experimental plate in water in a real sea with the depth of 2-3m for 24 months, measuring the attaching area of aquatic organisms every 6 months, calculating the percentage of antifouling effect of each component by using a calculation formula of an antifouling effect theory, and obtaining the calculation result by the formula: antifouling effect (%) = (1-marine organism adhesion area/total area of coating of experimental coating) x100%.
Table 1: antifouling effect of various formulas of antifouling paint in different periods of actual sea tests
Table 2: sensory expression of antifouling effect of each formula antifouling paint at 24 months of sea test
And (4) analyzing results:
it is clear from the results shown in tables 1 and 2 that with this invention, a mixture of hydrolyzable tannic acid and zinc disulfide carbamate, zinc pyrithione in a mass ratio of 15; the bionic nontoxic marine antifouling paint prepared from N-N, -di (substituted phenyl) methylene bisthioacetamide and isothiazolinone has the advantages that the ratio of antifouling effect after soaking in different sea areas for 18 months is still maintained at 94.5-98.6%, most of the house area after soaking for 24 months is maintained at 91.8-97.4%, and the embodiment 5 can reach 97.4%, the antifouling effect with extremely high stability greatly improves the accuracy and reliability of the bionic nontoxic marine antifouling paint prepared by the bionic nontoxic marine antifouling paint, and has more remarkable antifouling effect compared with the antifouling paint prepared by using a single compound and commonly used cuprous oxide as main active ingredients in the past, meanwhile, the bionic nontoxic marine antifouling paint prepared by the bionic nontoxic marine antifouling paint disclosed by the invention is used on a real ship for coating detection, particularly used on an offshore fishing boat, has excellent antifouling effect in the sailing operation of 6 months, 12 months, 18 months and 24 months, and has excellent antifouling effect on a Liaoning boat 178, 167, yellow sea fishing boat, yellow fishing boat, 59, 5% fishing boat, 5-76% fishing boat, 5% fishing boat, and 5.4% fishing boat, and 5% fishing boat. Most of the antifouling effects reach more than 95 percent, and the examples detect and verify that the bionic nontoxic marine antifouling paint disclosed by the invention is advanced in technology and reliable in performance.
The invention has the following effects:
the invention is a bionic nontoxic marine antifouling paint prepared by the antifouling preparation, and the paint is coated on the parts below the waterline of a ship and the surfaces of structures of various marine facilities, and can be soaked in seawater for a long time to prevent marine organisms such as: the antifouling paint has the advantages that the antifouling paint prepared from the antifouling preparation has stable antifouling effect and long duration, and does not harm the marine ecological environment in the test of real sea. The antifouling paint of the present invention has antifouling effect far superior to that of available antifouling paint, and the antifouling effective components of all the effective components have no toxicity to human, animal, fish and marine plant and this avoids most pyrethrins poisoning aquatic organism. Therefore, the bionic nontoxic marine antifouling paint prepared from the fouling preparation can be safely used, can play a greater role in the development and utilization of marine ecological environment and marine facilities, and enables the marine ecological environment to be more friendly and marine organisms to be effectively protected.
The above embodiments are only for illustrating the technical concept and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention accordingly, and not to limit the protection scope of the present invention accordingly. All equivalent changes or modifications made in accordance with the spirit of the present disclosure are intended to be covered by the scope of the present disclosure.
Claims (5)
1. A bionic nontoxic marine antifouling paint is characterized in that: the feed is prepared from the following raw materials in parts by weight:
100 parts of base material, 5.0-15.0 parts of hydrolysable tannic acid, 5.0-12.0 parts of zinc disulfide carbamate and zinc pyrithione, 5.1-13.0 parts of N-di (substituted phenyl) methylene dithioacetamide, 5.0-15.0 parts of isothiazolinone, 20.0-35.0 parts of silicon-based polymer, 7.0-14.0 parts of rosin resin, 10.0-22.0 parts of zinc oxide, 1.0-8.0 parts of iron red powder, 1.0-5.0 parts of organic silicone grease, 5.0-13.0 parts of dimethylbenzene, 1.0-6.0 parts of butanol and 3.0-9.0 parts of ethylene oxide-propylene oxide block copolymer; wherein the mass ratio of the zinc disulfide carbamate to the zinc pyrithione is 15;
the preparation method of the base material comprises the following steps:
1) Taking 2.5g of ethanolamine and 10ml of tetrahydrofuran, placing the mixture in a flask, carrying out ice bath to 5 ℃, slowly dropwise adding 7.0g of heptafluorobutyryl chloride, completing dropwise adding, slowly heating to 24 ℃, and shaking for 3 hours to obtain a product, namely a yellow brown pasty substance;
2) Removing excessive tetrahydrofuran at 66-68 deg.C by rotary evaporation, adjusting pH to 7.0-8.0 with hydrochloric acid, washing with 50 deg.C hot water once, removing excessive water by rotary evaporation, and repeatedly crystallizing with chloroform for 3 times to obtain brown crystal-N-hydroxyethyl heptafluoro butyramide;
3) Adding 0.8g of 2, 4-toluene diisocyanate and 0.10ml of zinc isooctanoate into a flask, introducing 99.99% pure nitrogen as a protective gas, heating to 55-60 ℃, slowly dropwise adding 3.8g of N-hydroxyethyl heptafluorobutanamide and 8.6ml of dehydrated 4-methyl-2-pentanone, reacting for 6 hours under the condition, heating to 82-85 ℃ after 3 hours, dropwise adding 6.0ml of phenoxyethyl acrylate, and continuously reacting for 3 hours to obtain a modified product, namely a fluorocarbon monomer;
4) The flask was charged with dehydrated 4-methyl-2-pentanone and 1:3.2 mass percent of diacyl peroxide, raising the temperature to 70-76 ℃, keeping the reaction for 1h, adding the fluorocarbon monomer, slowly dropwise adding 3.0ml of ethyl methacrylate, keeping the temperature at 75 ℃, reacting for 10h, and adding 6 mass percent of KH-550 to obtain the fluorocarbon resin copolymer.
2. The biomimetic non-toxic marine antifouling paint according to claim 1, characterized in that: the feed is prepared from the following raw materials in parts by weight:
100 parts of base material, 8.4-12.7 parts of hydrolysable tannic acid, 9.1-11.2 parts of zinc disulfide carbamate compound and zinc pyrithione, 9.8-11.6 parts of N-bis (substituted phenyl) methylene bis (thioacetamide), 8.0-11.3 parts of isothiazolinone compound, 24.6-27.5 parts of silicon-based polymer, 9.3-12.1 parts of rosin resin, 14.7-18.4 parts of zinc oxide, 4.2-5.7 parts of iron red powder, 2.8-3.9 parts of organic silicone grease, 7.6-11.1 parts of dimethylbenzene, 3.8-5.2 parts of butanol and 5.2-4.9 parts of ethylene oxide-propylene oxide block copolymer; wherein the mass ratio of the zinc disulfide carbamate to the zinc pyrithione is 15.
3. The biomimetic non-toxic marine antifouling paint according to claim 1, characterized in that: the feed is prepared from the following raw materials in parts by weight:
100 parts of base material, 10.2 parts of hydrolysable tannic acid, 10.7 parts of zinc disulfide carbamate and zinc pyrithione, 11.4 parts of N-di (substituted phenyl) methylene dithioacetamide, 10.6 parts of isothiazolinone compound, 25.7 parts of silicon-based polymer, 10.0 parts of rosin resin, 15.9 parts of zinc oxide, 5.0 parts of iron red powder, 3.2 parts of organic silicone grease, 10.0 parts of xylene, 4.1 parts of butanol and 5.7 parts of ethylene oxide-propylene oxide block copolymer; wherein the mass ratio of the zinc disulfide carbamate to the zinc pyrithione is 15.
4. The method for preparing a bionic nontoxic marine antifouling paint as claimed in any one of claims 1 to 3, which is characterized in that: the method comprises the following steps:
1) Extracting hydrolyzable tannic acid by an organic solvent extraction method: crushing 100 parts by weight of an extract to be extracted, soaking in 155 parts by weight of a methanol aqueous solution in a mass ratio of 9;
2) Adding 45 parts by weight of n-hexane at 30 ℃, mixing and soaking for 2.5 hours, and then further purifying;
3) And (3) reduced pressure distillation I: the pressure is 133.30Pa to 133.33Pa; putting the liquid obtained in the previous step into a round-bottom flask, adding two stirrers, and heating to 155-157 ℃; until the product liquid in the last step starts to flow back, when the flow back is finished, the temperature starts to drop, nitrogen is introduced into the device, a heat source is removed, when the temperature of the device drops to room temperature, a reduced pressure distillation product is obtained, the reduced pressure distillation product solution is soaked by 125 parts by weight of methanol water solution with the mass ratio of 8, and is further purified after being soaked for 2 hours by adding 45 parts by weight of carbon tetrachloride solution;
4) And (3) reduced pressure distillation II: the method is the same as the above steps, the pressure is unchanged, the heating temperature is 170-175 ℃, the reduced pressure distillation product solution in the above steps is soaked by 105 parts by weight of methanol water solution with the mass ratio of 6;
5) And (3) reduced pressure distillation III: the method is the same as the above steps, the pressure is unchanged, the heating temperature is 142-145 ℃, water is added to dilute the redundant solvent, and the finished product of the hydrolysable tannin extract is obtained after vacuum drying;
6) Sequentially adding the following components into a reaction kettle: silicon-based polymer, rosin resin, organic silicone grease, xylene and butanol, iron oxide red powder, hydrolysable tannic acid, zinc disulfide carbamate + zinc pyrithione, N-N, -di (substituted phenyl) methylene bis (thioacetamide) and isothiazolinone, base material, zinc oxide and ethylene oxide-propylene oxide block copolymer, setting the initial temperature to be 25-28 ℃, gradually increasing to 75-80 ℃ within 3 hours, and maintaining stirring for 8 hours to produce a crude product;
7) And (3) finely grinding the crude product for 2 times in a high-speed grinding disperser, and finely grinding for 4 times to obtain the product.
5. The preparation method of the bionic nontoxic marine antifouling paint as claimed in claim 4, which is characterized in that: the raw materials of the extract to be extracted in the step 1) are selected from seaweed, pomegranate, immature persimmon or tea.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1392208A (en) * | 2002-06-28 | 2003-01-22 | 王钧宇 | Bionic poisonless anti-pollution paint for ship and its preducing method |
| CN103740163A (en) * | 2013-12-27 | 2014-04-23 | 王钧宇 | Bionic nontoxic environment-friendly antifouling preparation |
| CN108164572A (en) * | 2018-02-06 | 2018-06-15 | 黔西南州成章农业发展有限公司 | A kind of method using stem of noble dendrobium extraction tannic acid |
| CN111925696A (en) * | 2020-07-31 | 2020-11-13 | 江苏华夏制漆科技有限公司 | Long-acting heavy-duty anticorrosive coating |
-
2022
- 2022-08-24 CN CN202211015985.6A patent/CN115353789A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1392208A (en) * | 2002-06-28 | 2003-01-22 | 王钧宇 | Bionic poisonless anti-pollution paint for ship and its preducing method |
| CN103740163A (en) * | 2013-12-27 | 2014-04-23 | 王钧宇 | Bionic nontoxic environment-friendly antifouling preparation |
| CN108164572A (en) * | 2018-02-06 | 2018-06-15 | 黔西南州成章农业发展有限公司 | A kind of method using stem of noble dendrobium extraction tannic acid |
| CN111925696A (en) * | 2020-07-31 | 2020-11-13 | 江苏华夏制漆科技有限公司 | Long-acting heavy-duty anticorrosive coating |
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Application publication date: 20221118 |