CN113462241A - Copper powder-based self-polishing antifouling paint containing copper and copper alloy powder and preparation method thereof - Google Patents

Copper powder-based self-polishing antifouling paint containing copper and copper alloy powder and preparation method thereof Download PDF

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Publication number
CN113462241A
CN113462241A CN202010239092.4A CN202010239092A CN113462241A CN 113462241 A CN113462241 A CN 113462241A CN 202010239092 A CN202010239092 A CN 202010239092A CN 113462241 A CN113462241 A CN 113462241A
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copper
powder
antifouling paint
resin
copper powder
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CN202010239092.4A
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Chinese (zh)
Inventor
王邦建
王炳程
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Central Haihua Xiamen Marine Intelligent Coating Co ltd
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Central Haihua Xiamen Marine Intelligent Coating Co ltd
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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
    • C09D133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • 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
    • C09D143/00—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 containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
    • C09D143/04—Homopolymers or copolymers of monomers containing silicon
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
    • C09D5/1662—Synthetic film-forming substance
    • C09D5/1668—Vinyl-type polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1687—Use of special additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/085—Copper
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2265—Oxides; Hydroxides of metals of iron
    • C08K2003/2272—Ferric oxide (Fe2O3)
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter

Abstract

The copper powder-based self-polishing antifouling paint containing copper and copper alloy powder is prepared by adopting hydrolysis type acrylate resin as a main film forming material, adding copper powder and copper alloy powder as main antifouling active substance release sources and adding iron oxide red, titanium dioxide, talcum powder, a film forming aid and related aids in an auxiliary manner. The copper powder-based self-polishing antifouling paint is mainly applied to parts below a waterline of ships, docks, piers, offshore platforms and the like, the adhesion force of the coating is 2MPa, the coating is continuously updated under the hydrolysis action of resin, the surface is always full of copper powder and copper alloy powder, and Cu can be slowly released in seawater+And Cu2+Can ensure the effectiveness of antifouling, and the antifoulingThe performance is not influenced by the hydrolysis performance of the resin, and the antifouling effect lasts for 3-5 years.

Description

Copper powder-based self-polishing antifouling paint containing copper and copper alloy powder and preparation method thereof
Technical Field
The invention belongs to the technical field of chemical materials, and particularly relates to a copper powder-based self-polishing antifouling paint containing copper and copper alloy powder and a preparation method thereof.
Background
In the service process of the ship, marine fouling organisms are attached to the ship body, the roughness of the surface of the ship body can be increased, the weight and the navigation resistance of the ship are greatly increased, the navigation speed is reduced, and the fuel consumption is increased. People do not invent antifouling paint in the middle of the 18 th century, and antifouling is carried out on a wooden ship by adopting a copper sheet coating method. However, the method is used on a steel substrate ship body, so that the serious galvanic corrosion problem occurs, and the strict and careful insulation measures are required. Antifouling paints did not start to appear until the 1860 s began and were gradually applied on ships. The antifouling paint in the beginning of 20 th century is mainly soluble base material type and contact exudation type 2, which adopts soluble resin and insoluble resin as base material, copper powder and copper compound as main antifouling agent, mercury oxide, lead, mercury, arsenic, zinc, tin and other basic metal organic compound as auxiliary antifouling agent, and can reach the antifouling aim through the exudation of the antifouling agent.
Vender Kerk and Luijten discovered in 1954 that a class of toxic materials based on tributyltin has a broad spectrum of marine biofouling killing capabilities, which are 10 to 20 times stronger in antifouling capabilities than cuprous oxide. Later researchers grafted tributyltin to acrylic resin side chains, slowly released organotin through hydrolysis, and kept the surface of the coating smooth and flat in the using process, thereby achieving the purpose of excellent resistance reduction and speed increase. The antifouling paint which takes acrylic resin with a hydrolyzed side chain as a base material and has a polishing phenomenon under the action of seawater scouring is called self-polishing antifouling paint.
The service life of the organic tin self-polishing antifouling paint can reach 5 years, but the organic tin is found to cause serious damage to marine ecological environment at the end of the 70 th 20 th century, and the International Maritime Organization (IMO) forbids the use of tributyltin or other organic tin containing antifouling paint poison from 1/2003 and completely forbids the existence of the product from 1/2008.
In the search for a way of replacing organotin self-polishing antifouling paint, copper acrylate or zinc acrylate resin is mainly used as a base material, cuprous oxide is added as a main antifouling agent, and zinc oxide, copper pyrithione, zinc pyrithione, Irgarol 1051, TCPM and the like are added as auxiliary antifouling agents. The release layer thickness of the tin-free self-polishing antifouling paint is closely related to the resin hydrolysis performance, the release layer of the self-polishing antifouling paint with excellent resin hydrolysis performance is thinner, and the antifouling period effect can reach 3-5 years. If the resin has poor hydrolysis performance, the release layer of the coating layer is thickened, the seepage rate of the internal antifouling agent is greatly reduced, and the antifouling period can only reach 1-2 years.
In order to overcome the adverse factor that the antifouling period of the self-polishing antifouling paint is greatly influenced by the hydrolysis performance of resin, the invention provides a copper powder-based self-polishing antifouling paint containing copper and copper alloy powder. The paint is prepared by using hydrolysis type acrylate resin such as copper acrylate, zinc acrylate, silane acrylate and the like as a base material and adding copper powder, copper alloy powder, pigment and filler and related auxiliary agents. The copper powder-based self-polishing antifouling paint realizes coating self-polishing through the hydrolysis of resin, and the copper powder and the copper alloy powder are not dissolved in seawater and are always on the outermost surface of the coating, so that the antifouling coating does not have a release layer all the time, and the antifouling performance of the antifouling coating is not influenced by the hydrolysis performance of the resin.
Therefore, in the using process of the copper powder-based self-polishing antifouling paint, the surface of the coating always keeps relatively dense copper powder and copper alloy powder, and the copper powder and the copper alloy powder slowly release Cu through electrochemical action in seawater+And Cu2+The anti-fouling effectiveness can be ensured, and the anti-fouling period can reach 3 to 5 years.
The action principle of the copper powder-based self-polishing antifouling paint is shown in figure 1.
Disclosure of Invention
The invention is realized by the following technical scheme.
Specifically, the invention provides a copper powder-based self-polishing antifouling paint containing copper and copper alloy powder.
The copper powder-based self-polishing antifouling paint provided by the invention mainly comprises hydrolysis type acrylate resin, copper powder, copper alloy powder, pigment, filler, auxiliary agent and the like, and the main components are shown in Table 1.
Table 1 copper powder based self-polishing antifouling paint composition.
Figure 795675DEST_PATH_IMAGE001
The hydrolysis type acrylate resin is one or a mixture of more of copper acrylate resin, zinc acrylate resin, silane acrylate resin and the like, and can be solvent resin or water-based resin.
The particle size of the copper powder is 50-500 mu m, and the particle size distribution range is 100 mu m.
The particle size of the copper alloy powder is 50-500 mu m, and the distribution range of the particle size is 100 mu m.
The pigment and filler of the invention is one or a mixture of iron oxide red, iron oxide black, talcum powder, calcium carbonate powder, titanium dioxide and the like.
When the hydrolytic acrylate resin is solvent type resin, the diluent comprises dimethylbenzene, n-butyl alcohol, butyl acetate and the like; when the hydrolysis type acrylate resin is an aqueous resin, the diluent is water.
The auxiliary agent comprises a thixotropic agent, a dispersing agent, a defoaming agent, an anti-settling agent and the like.
The preparation process comprises the following steps: (1) placing 2-5 parts by weight of diluent into a dispersion tank, sequentially adding 0.5 part of defoaming agent and 0.5 part of anti-settling agent under the condition of low-speed stirring, stirring for 10 minutes, and sequentially adding 10-20 parts by weight of pigment and filler, 30-40 parts by weight of hydrolysis type acrylate resin, 20-40 parts by weight of copper powder and 20-40 parts by weight of copper alloy powder, wherein the stirring time is 30-180 minutes; (2) after the materials are uniformly mixed, adding a dispersing agent, and controlling the stirring speed to be 800rpm for 30 minutes; (3) finally, 0.5 part of thixotropic agent is added, and high-speed dispersion is carried out for 30 minutes under the condition of the rotating speed of 800 rpm; (4) returning to room temperature, standing for 30 minutes, filtering, discharging and packaging.
The copper powder-based self-polishing antifouling paint containing copper and copper alloy powder is mainly applied to parts below a waterline of ships, wharfs, piers, offshore platforms and the like, the adhesion force of the coating is about 2MPa, the surface of the coating is continuously updated through the hydrolysis action of resin, the surface of the coating is always full of copper powder and copper alloy powder, no release layer exists, and Cu can be slowly released in seawater+And Cu2+The antifouling efficiency can be ensured, and the antifouling performance of the resin is not influenced by the hydrolysis performance of the resin, and the antifouling period is 3-5.
FIG. 1 is a schematic diagram showing the operation of a copper powder-based self-polishing antifouling paint.
FIG. 2 shows a shallow sea hanging plate test (Xiamen, 3 years), from which it can be seen that the copper powder based self-polishing antifouling paint of the present invention has a perfect coating surface, no fouling organisms and an antifouling rating of 100 points, according to a real sea hanging plate test of Xiamen in 3 years.
The composition of the copper powder-based self-polishing antifouling paint of the present invention is shown in table 2.
Table 2 composition of copper powder based self-polishing antifouling paint.
Figure 250271DEST_PATH_IMAGE002
The preparation process of the coating comprises the following steps: placing the diluent into a dispersion tank, sequentially adding a defoaming agent, an anti-settling agent, a pigment filler, hydrolysis type acrylate resin, copper powder and copper alloy powder under the condition of low-speed stirring, and uniformly mixing for about 30-180 minutes; after uniformly mixing, adding a dispersing agent into the mixture, and controlling the stirring speed to be 800rpm and the stirring time to be 30 minutes; finally, adding a thixotropic agent, and dispersing for 30 minutes at a high speed under the condition of the rotating speed of 800 rpm; returning to room temperature, standing for 30 minutes, filtering and packaging.

Claims (9)

1. The copper powder-based self-polishing antifouling paint containing copper and copper alloy powder realizes coating self-polishing through the hydrolysis of resin, the copper powder and the copper alloy powder cannot be dissolved in seawater and are always on the outermost surface of the coating, and the copper powder and the copper alloy powder slowly release Cu through electrochemical action in seawater+And Cu2+The antifouling efficiency can be ensured, and the antifouling performance is not affected by the hydrolysis performance of the resin.
2. The invention provides a copper powder-based self-polishing antifouling paint containing copper and copper alloy powder, which is prepared by taking hydrolysis type acrylate resin as a base material and adding copper powder, copper alloy powder, pigment and filler and related auxiliary agents, and mainly comprises the following components:
10-30 parts of hydrolysis type acrylate resin;
20-40 parts of copper powder;
20-40 parts of copper alloy powder;
10-20 parts of pigment and filler;
2-5 parts of a diluent;
and 1-2 parts of an auxiliary agent.
3. The copper powder-based self-polishing antifouling paint as claimed in claim 1 and claim 2, wherein: the optimal preparation method comprises the steps of firstly placing the diluent in a dispersion tank, sequentially adding the defoaming agent and the anti-settling agent under the condition of low-speed stirring, stirring for 10 minutes, and then sequentially adding the pigment and filler, the hydrolysis type acrylate resin, the copper powder and the copper alloy powder, wherein the stirring time is 30-180 minutes; after the materials are uniformly mixed, adding a dispersing agent, and controlling the stirring speed to be 800rpm for 30 minutes; finally adding a thixotropic agent, and dispersing for 30 minutes at a high speed under the condition of the rotating speed of 800 rpm; returning to room temperature, standing for 30 minutes, filtering, discharging and packaging.
4. The copper powder-based self-polishing antifouling paint as claimed in claim 1 and claim 2, wherein: the hydrolysis type acrylate resin is one or a mixture of copper acrylate resin, zinc acrylate resin, silane acrylate resin and the like, and can be solvent type resin or water-based resin.
5. The copper powder-based self-polishing antifouling paint as claimed in claim 1 and claim 2, wherein: the particle size of the copper powder is 50-500 mu m, and the particle size distribution range is 100 mu m.
6. The copper powder-based self-polishing antifouling paint as claimed in claim 1 and claim 2, wherein: the particle size of the copper alloy powder is 50-500 mu m, and the particle size distribution range is 100 mu m.
7. The copper powder-based self-polishing antifouling paint as claimed in claim 1 and claim 2, wherein: the pigment and filler is one or a mixture of iron oxide red, iron oxide black, talcum powder, calcium carbonate powder, titanium dioxide and the like.
8. The copper powder-based self-polishing antifouling paint as claimed in claim 1 and claim 2, wherein: when the diluent and the hydrolysis type acrylate resin are solvent type resins, the diluent comprises dimethylbenzene, n-butyl alcohol, butyl acetate and the like; when the hydrolysis type acrylate resin is an aqueous resin, the diluent is water.
9. The copper powder-based self-polishing antifouling paint as claimed in claim 1 and claim 2, wherein: the auxiliary agent comprises a thixotropic agent, a dispersing agent, a defoaming agent, an anti-settling agent and the like.
CN202010239092.4A 2020-03-30 2020-03-30 Copper powder-based self-polishing antifouling paint containing copper and copper alloy powder and preparation method thereof Pending CN113462241A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104974631A (en) * 2015-07-06 2015-10-14 海洋化工研究院有限公司 Matrix resin having self-polishing performance and self-polishing antifouling coating prepared by same
CN110511633A (en) * 2018-05-22 2019-11-29 海洋化工研究院有限公司 A kind of aqueous marine antifouling coating of low VOC content

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104974631A (en) * 2015-07-06 2015-10-14 海洋化工研究院有限公司 Matrix resin having self-polishing performance and self-polishing antifouling coating prepared by same
CN110511633A (en) * 2018-05-22 2019-11-29 海洋化工研究院有限公司 A kind of aqueous marine antifouling coating of low VOC content

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Application publication date: 20211001