CN113563784A - Graphite copper powder-based contact type antifouling paint and preparation method thereof - Google Patents
Graphite copper powder-based contact type antifouling paint and preparation method thereof Download PDFInfo
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- CN113563784A CN113563784A CN202010359422.3A CN202010359422A CN113563784A CN 113563784 A CN113563784 A CN 113563784A CN 202010359422 A CN202010359422 A CN 202010359422A CN 113563784 A CN113563784 A CN 113563784A
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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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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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
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
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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
- C09D201/00—Coating compositions based on unspecified macromolecular compounds
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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
- C09D5/1687—Use of special additives
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- 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
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Abstract
The graphite copper powder-based contact type antifouling paint is prepared by adopting insoluble resin as a main film forming material, adding graphite, 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. After the coating is completely cured, the coating is polished by abrasive paper to expose the metal color on the surface of the coating, and the copper powder, the copper alloy powder and the graphite slowly release Cu through the electrochemical action in seawater+And Cu2+And the antifouling effect is achieved. The graphite copper powder-based contact antifouling paint is mainly applied to ships,The parts below the waterline, such as wharfs, piers, offshore platforms and the like, have the antifouling effect of more than 5 years.
Description
Technical Field
The invention belongs to the technical field of chemical materials, and particularly relates to a graphite copper powder-based contact type antifouling paint and a preparation method thereof.
Background
Boats and ships are at the navigation in-process, and marine organisms such as barnacle, oyster, diatom can adhere to the growth at the hull bottom, can increase hull bottom surface roughness when growing to a certain extent by a wide margin, improves boats and ships navigation resistance, and then reduces the ship speed, increases fuel consumption. The application of antifouling paint is the most common, effective and economical method for inhibiting the adhesion and growth of fouling organisms.
Currently, many researches and applications are made on abrasion type antifouling paints, tin-free self-polishing antifouling paints, fouling release type antifouling paints, bionic antifouling paints, and the like. The abrasion type antifouling paint and the tin-free self-polishing antifouling paint are prepared by respectively taking brittle insoluble resin or hydrolyzed acrylate resin as a base material, cuprous oxide as a main antifouling agent, copper pyrithione, zinc oxide and other auxiliary antifouling agents, and then adding pigments, fillers and related auxiliary agents, and generally have the antifouling period effect of 2-5 years. The fouling release type antifouling paint and the bionic antifouling paint do not contain antifouling agents, fouling organisms are difficult to attach mainly by means of the characteristic action of the surface of the coating, or the fouling organisms are easy to detach after attachment, but the fouling release type antifouling paint and the bionic antifouling paint are mainly applied to ships with high navigation stop ratio and high navigation speed, most of the fouling release type antifouling paint and the bionic antifouling paint are still in the research stage, products applied to actual ships are few, and the antifouling period effect is generally 1-2 years.
The contact type antifouling paint is the first antifouling paint and is prepared by using insoluble resin as base material and adding antifouling agent and other assistants. After the antifouling agent on the surface of the coating is released, the antifouling agent in the coating cannot smoothly and effectively seep out to meet the requirement of the minimum effective concentration, fouling organisms are easily attached, the antifouling effect is only about 1 year, and the antifouling agent is basically eliminated at present.
In order to overcome the disadvantages of the conventional contact type antifouling paint, patent 202010114017.5 proposes a novel contact type antifouling paint, namely a copper powder-based contact type antifouling paint containing copper and copper alloy powder. The patent slowly releases Cu through the electrochemical action of copper powder and copper alloy powder on the surface of the coating in seawater+And Cu2+The antifouling paint has an antifouling effect for 3-5 years, and provides a new idea for the development of a novel long-acting contact type antifouling paint.
The patent further improves the technical scheme of patent 202010114017.5, provides a graphite copper powder-based contact type antifouling paint and a preparation method thereof, further improves the electrolysis rate of copper powder and copper alloy powder by utilizing the conductivity of graphite, and improves the Cu on the surface of a coating+And Cu2+The antifouling ability is enhanced. The preparation method of the graphite copper powder-based contact type antifouling paint comprises the steps of firstly preparing graphite, copper powder and copperThe alloy powder is fully and uniformly mixed, then added into the insoluble resin base material in batches, and then added with the pigment, the filler, the auxiliary agent and the like to prepare the alloy powder. The graphite copper powder-based contact type antifouling coating is coated on the surface of an anticorrosive coating, and is polished by abrasive paper after being completely cured, so that the metal color of the coating is exposed, and the copper powder, the copper alloy powder and the graphite slowly release Cu under the electrochemical action in seawater+And Cu2+Has antifouling effect of more than 5 years.
Disclosure of Invention
The invention is realized by the following technical scheme.
Specifically, the invention provides a graphite copper powder-based contact type antifouling paint.
The copper powder-based contact antifouling paint provided by the invention mainly comprises insoluble resin, graphite, copper powder, copper alloy powder, pigment, filler, auxiliary agent and the like, and the main components are shown in table 1.
The insoluble resin is one or a mixture of two or three of epoxy resin, organic silicon resin and adhesive, and can be solvent resin or water-based resin.
The graphite is ultrafine graphite with the particle size of 6 mu m-1 mm.
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 particle size distribution range 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 insoluble resin is solvent type resin, the diluent comprises dimethylbenzene, n-butyl alcohol, butyl acetate and the like; when the insoluble 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 of the invention comprises the following steps.
Adding graphite, copper powder and copper alloy powder into a ball mill in proportion, fully mixing for 12 hours, and taking out for later use.
Placing 2-5 parts by weight of diluent into a dispersion tank, and sequentially adding 20-50 parts by weight of insoluble resin and 26-80 parts by weight of graphite-copper mixed powder under the condition of low-speed stirring for 30-180 minutes; then, 0-20 parts by weight of pigment and filler are sequentially added.
After the materials are uniformly mixed, a dispersing agent is added, the stirring speed is controlled to be 800rpm, and the stirring time is controlled to be 30 minutes.
Finally adding other assistants such as anti-settling agent, thixotropic agent and the like, 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.
The graphite copper powder-based contact type antifouling paint is mainly applied to parts below waterlines of ships, wharfs, piers, offshore platforms and the like, and can continuously and stably release Cu in seawater+And Cu2+Has antifouling effect of more than 5 years.
The composition of the copper powder-based contact antifouling paint of the present invention is shown in table 2.
The preparation process of the coating comprises the following steps: adding graphite, copper powder and copper alloy powder into a ball mill in proportion, fully mixing for 12 hours, and taking out for later use. Placing the diluent into a dispersion tank, sequentially adding the insoluble resin and the graphite copper mixed 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 an anti-settling agent and a thixotropic agent, and dispersing at a high speed for 30 minutes at the rotating speed of 800 rpm; returning to room temperature, standing for 30 minutes, filtering and packaging.
Figures and description: FIG. 1 shows the test results of the graphite copper powder-based contact antifouling paint on the hanging plate of the shallow sea in the sea area of Xiamen (3 years, 6 marine life peak seasons). From the test results of the shallow sea hanging plate, the copper powder-based contact type antifouling paint disclosed by the invention has the advantages that the coating surface is complete, no fouling organisms exist, and the antifouling score is 100 points through the test of the real sea hanging plate of 6 marine organisms in 3 years in the sea area of Xiamen.
Claims (9)
1. The graphite copper powder-based contact type antifouling paint provided by the invention adopts insoluble resin as a main film forming material, copper powder and copper alloy powder are added as main antifouling active substance release sources, the electrolysis rate of the copper powder and the copper alloy powder is further improved by utilizing the conductivity of graphite, and the Cu on the surface of a coating is improved+And Cu2+The paint is prepared by adding iron oxide red, titanium dioxide, talcum powder, film-forming auxiliary agent and related auxiliary agent in an auxiliary way, and mainly comprises the following components:
20-50 parts of insoluble resin;
1-10 parts of graphite;
20-40 parts of copper powder;
5-30 parts of copper alloy powder;
0-20 parts of pigment and filler;
2-5 parts of a diluent;
and 1-2 parts of an auxiliary agent.
2. The contact antifouling paint based on graphite copper powder as claimed in claim 1, wherein: the best configuration method comprises the steps of adding graphite, copper powder and copper alloy powder into a ball mill in proportion, fully mixing for 12 hours, and taking out for later use; placing 2-5 parts by weight of diluent into a dispersion tank, and sequentially adding 20-50 parts by weight of insoluble resin and 26-80 parts by weight of graphite-copper mixed powder under the condition of low-speed stirring for 30-180 minutes; then sequentially adding 0-20 parts by weight of pigment and filler; after the materials are uniformly mixed, adding a dispersing agent, and controlling the stirring speed to be 800rpm for 30 minutes; finally adding other additives such as an anti-settling agent, a thixotropic agent and the like, 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.
3. The copper powder-based contact antifouling paint according to claim 1, wherein the graphite has a particle size of 6 μm to 1 mm.
4. The copper powder-based contact antifouling paint according to claim 1, wherein the insoluble resin is one or a mixture of two or three of epoxy resin, silicone resin and adhesive, and can be solvent resin or water-based resin.
5. The copper powder-based contact antifouling paint of claim 1, wherein the particle size of the copper powder is 50 to 500 μm, and the particle size distribution range is 100 μm.
6. The copper powder-based contact antifouling paint as claimed in claim 1, wherein the particle size of the copper alloy powder is 50 to 500 μm, and the particle size distribution range is 100 μm.
7. The copper powder-based contact antifouling paint as claimed in claim 1, wherein the pigment and filler is one or more of iron oxide red, iron oxide black, talcum powder, calcium carbonate powder and titanium dioxide.
8. The copper powder-based contact antifouling paint of claim 1, wherein the diluent, when the insoluble resin is a solvent type resin, comprises xylene, n-butanol, butyl acetate, etc.; when the insoluble resin is an aqueous resin, the diluent is water.
9. The copper powder-based contact antifouling paint of claim 1, wherein the auxiliary agent comprises a thixotropic agent, a dispersing agent, an antifoaming agent, an anti-settling agent, and the like.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010359422.3A CN113563784A (en) | 2020-04-29 | 2020-04-29 | Graphite copper powder-based contact type antifouling paint and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010359422.3A CN113563784A (en) | 2020-04-29 | 2020-04-29 | Graphite copper powder-based contact type antifouling paint and preparation method thereof |
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| Publication Number | Publication Date |
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| CN113563784A true CN113563784A (en) | 2021-10-29 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN202010359422.3A Pending CN113563784A (en) | 2020-04-29 | 2020-04-29 | Graphite copper powder-based contact type antifouling paint and preparation method thereof |
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB715535A (en) * | 1951-04-14 | 1954-09-15 | Mini Of Nat Defence Of Canada | Pigment for anti-fouling paint |
| JPS62142105A (en) * | 1985-12-14 | 1987-06-25 | Akio Sawashita | Antifouling material |
| EP0465172A1 (en) * | 1990-06-29 | 1992-01-08 | Metallisation Service Limited | Anti-biofouling composition, and method of reducing biofouling |
| RU2057203C1 (en) * | 1993-02-01 | 1996-03-27 | Центральный научно-исследовательский институт конструкционных материалов "Прометей" | Corrosion-resistant antifouling material manufacture method |
| US20040197322A1 (en) * | 2003-04-04 | 2004-10-07 | Camp Douglas R. | Anti-fouling coating containing copper and graphite |
| WO2006083155A1 (en) * | 2005-02-03 | 2006-08-10 | Theodorus Wilhelmus Streng | Epoxy-based antifouling |
| WO2016038363A1 (en) * | 2014-09-12 | 2016-03-17 | Richard Foster | Antifouling composition |
| CN110922828A (en) * | 2019-11-26 | 2020-03-27 | 杭州烯创科技有限公司 | Graphene marine antifouling paint and preparation method thereof |
-
2020
- 2020-04-29 CN CN202010359422.3A patent/CN113563784A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB715535A (en) * | 1951-04-14 | 1954-09-15 | Mini Of Nat Defence Of Canada | Pigment for anti-fouling paint |
| JPS62142105A (en) * | 1985-12-14 | 1987-06-25 | Akio Sawashita | Antifouling material |
| EP0465172A1 (en) * | 1990-06-29 | 1992-01-08 | Metallisation Service Limited | Anti-biofouling composition, and method of reducing biofouling |
| RU2057203C1 (en) * | 1993-02-01 | 1996-03-27 | Центральный научно-исследовательский институт конструкционных материалов "Прометей" | Corrosion-resistant antifouling material manufacture method |
| US20040197322A1 (en) * | 2003-04-04 | 2004-10-07 | Camp Douglas R. | Anti-fouling coating containing copper and graphite |
| WO2006083155A1 (en) * | 2005-02-03 | 2006-08-10 | Theodorus Wilhelmus Streng | Epoxy-based antifouling |
| WO2016038363A1 (en) * | 2014-09-12 | 2016-03-17 | Richard Foster | Antifouling composition |
| CN110922828A (en) * | 2019-11-26 | 2020-03-27 | 杭州烯创科技有限公司 | Graphene marine antifouling paint and preparation method thereof |
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Application publication date: 20211029 |
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