CN113956763A - Coating for preventing marine organism adhesion and preparation method thereof - Google Patents
Coating for preventing marine organism adhesion and preparation method thereof Download PDFInfo
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- CN113956763A CN113956763A CN202111355282.3A CN202111355282A CN113956763A CN 113956763 A CN113956763 A CN 113956763A CN 202111355282 A CN202111355282 A CN 202111355282A CN 113956763 A CN113956763 A CN 113956763A
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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
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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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
- C09D5/1618—Non-macromolecular compounds inorganic
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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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- 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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- 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
- C08K2003/2248—Oxides; Hydroxides of metals of copper
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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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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Abstract
The invention relates to the technical field of coatings, in particular to a coating for preventing marine organism adhesion, which comprises degradable resin, an auxiliary agent, a metal antibacterial agent, an antioxidant and an ultraviolet resistant agent, wherein the auxiliary agent and the metal antibacterial agent provide good biological adhesion resistance through reasonable compounding of the components, the degradable resin has good adhesion with metal due to polar groups, lactic acid generated after hydrolysis also has a certain antibacterial effect, and the marine organism adhesion resistance effect can be further improved; the preparation method is simple in process and easy to prepare, and can meet the requirements of industrial production and manufacturing.
Description
Technical Field
The invention relates to the technical field of coatings, in particular to a coating for preventing marine organism adhesion and a preparation method thereof.
Background
More than 18000 organisms in various sea areas of the world are attached animals, and more than 600 organisms are attached plants. After marine organisms are attached to the bottom of the ship, the resistance is increased, the navigational speed is reduced, the fuel consumption is increased, and the mechanical abrasion is increased. The adhesion of marine organisms also damages a paint film, the corrosion of a ship steel plate is accelerated, the maintenance times and time of the ship are increased, the sailing rate of the ship is reduced, and the damage to the ecological environment caused by the spread of marine microorganisms across water areas is easy to occur.
In order to better promote the use of the ship, the outer wall of the ship needs to be uniformly coated with the coating for protection treatment, but the effect of preventing the marine organisms from attaching by the existing coating is not ideal, so that the long-term use of the ship is not facilitated.
Therefore, it is necessary to provide a marine coating for preventing marine organisms from attaching and a method for preparing the same to solve the above problems.
Disclosure of Invention
In order to solve the above problems, the present invention provides a coating for preventing marine organisms from attaching and a preparation method thereof, so as to solve the problems in the background art.
The technical scheme adopted by the invention is as follows:
the coating for preventing marine organism adhesion comprises the following components in percentage by mass:
further, the weight average molecular weight of the degradable resin is 5000-300000 g/mol.
Further, the degradable resin is a mixed resin composed of low-molecular-weight polylactic acid and high-molecular-weight polylactic acid, and the ratio of the low-molecular-weight polylactic acid to the high-molecular-weight polylactic acid is 1: 1.5-5.
Further, the auxiliary agent is any one of rosin, chlorinated paraffin and magnesium silicate.
Further, the metal antibacterial agent is any one of copper powder, cuprous oxide, zinc oxide and copper sulfate pyridine.
Further, the antioxidant is any one of AO-1010, AO-168 and AO-68.
Further, the ultraviolet resistant agent is carbon black or HALS.
The preparation method of the coating for preventing marine organism adhesion comprises the following steps:
s1: weighing the components according to the mass for later use;
s2: melting, blending, extruding and granulating all the components by a double screw;
s3: and (5) freezing the blended granules in the S2, and grinding the frozen blended granules into powder to obtain the coating.
Further, in S3, grinding is required to obtain powder with a particle size of not more than 200 μm.
Further, in S3, the powder is coated on the metal surface by thermal plastic spraying or electrostatic spraying, so as to obtain the marine organism adhesion-resistant coating.
The invention has the following beneficial effects:
1. the marine organism adhesion preventing paint provided by the invention comprises degradable resin, an auxiliary agent, a metal antibacterial agent, an antioxidant and an anti-ultraviolet agent, and has good marine organism adhesion resisting performance through reasonable compounding of the components, the auxiliary agent and the metal antibacterial agent provide good biological adhesion resisting performance, the degradable resin has good adhesion with metal due to containing polar groups, lactic acid generated after hydrolysis also has a certain antibacterial effect, the marine organism adhesion resisting effect of the paint can be further improved, meanwhile, no solvent is added in the paint, no environmental pollution is caused in the using process, the paint is environment-friendly, powdery, can be suitable for field spraying in a construction site, and can be used for quickly repairing a damaged part of a coating, so that the convenience in application is improved, and the paint provided by the invention has simple components, the raw materials are available, the marine organism adhesion resistance is good, and the application prospect is good;
2. the preparation method has the advantages of simple process, easiness in preparation, simplicity and convenience in operation, no special equipment in the preparation process, no addition of a solvent, low environmental pollution and convenience in preparation, and can meet the requirements of industrial production and manufacturing.
Drawings
FIG. 1 is a flow chart of the preparation in examples 1 to 5 of the present invention.
Detailed Description
In order that the invention may be more readily understood, reference will now be made to the following more particular description of the invention, examples of which are set forth below. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. These embodiments are provided so that this disclosure will be thorough and complete. The various starting materials used in the examples are, unless otherwise indicated, conventional commercial products.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The numerical values set forth in the examples of the present invention are approximations, not necessarily values. All values within the error range may be included without limiting to the specific values disclosed in the embodiments of the present invention, where the error or experimental conditions allow.
The numerical ranges disclosed in the examples of the present invention are intended to indicate the relative amounts of the components in the mixture and the ranges of temperatures or other parameters recited in the other method examples.
The coating for preventing marine organism adhesion comprises the following components in percentage by mass:
further, the weight average molecular weight of the degradable resin is 5000-300000 g/mol.
Further, the degradable resin is a mixed resin composed of low-molecular-weight polylactic acid and high-molecular-weight polylactic acid, and the ratio of the low-molecular-weight polylactic acid to the high-molecular-weight polylactic acid is 1: 1.5-5.
Further, the auxiliary agent is any one of rosin, chlorinated paraffin and magnesium silicate.
Further, the metal antibacterial agent is any one of copper powder, cuprous oxide, zinc oxide and copper sulfate pyridine.
Further, the antioxidant is any one of AO-1010, AO-168 and AO-68.
Further, the ultraviolet resistant agent is carbon black or HALS.
The marine organism adhesion preventing paint provided by the invention comprises degradable resin, an auxiliary agent, a metal antibacterial agent, an antioxidant and an anti-ultraviolet agent, and has good marine organism adhesion resisting performance through reasonable compounding of the components, the auxiliary agent and the metal antibacterial agent provide good biological adhesion resisting performance, the degradable resin has good adhesion with metal due to containing polar groups, lactic acid generated after hydrolysis also has a certain antibacterial effect, the marine organism adhesion resisting effect of the paint can be further improved, meanwhile, no solvent is added in the paint, no environmental pollution is caused in the using process, the paint is environment-friendly, powdery, can be suitable for field spraying in a construction site, and can be used for quickly repairing a damaged part of a coating, so that the application convenience is improved, the paint provided by the invention has simple components and available raw materials, good marine organism adhesion resistance and good application prospect.
The following are specific examples of the present application:
example 1
The coating for preventing marine organism adhesion comprises the following raw materials in parts by weight:
degradable resin: PLA-1 and PLA-230%, wherein PLA-1Mw is 10000g/mol, PLA-2Mw is 200000g/mol, and the ratio of PLA-1/PLA-1 is 1: 5;
metal antibacterial agent: 42% of cuprous oxide, 4% of zinc oxide and 5% of copper sulfate pyridine;
auxiliary agent: 12% of rosin and 4% of chlorinated paraffin;
antioxidant: AO-10100.25%, AO-680.25%;
anti-ultraviolet agent: carbon black 2.5%.
The preparation method comprises the following steps:
s1: weighing the components according to the mass for later use;
s2: melting, blending, extruding and granulating all the components by a double screw;
s3: and (3) freezing the blended granules in the S2, and grinding the frozen blended granules into powder with the particle size of 120 microns to obtain the coating.
Example 2
The coating for preventing marine organism adhesion comprises the following raw materials in parts by weight:
degradable resin: PLA-1 and PLA-250%, wherein PLA-1Mw is 50000g/mol, PLA-2Mw is 150000g/mol, the ratio of PLA-1/PLA-1 is 1: 1.5;
metal antibacterial agent: 25% of cuprous oxide, 3% of zinc oxide and 2% of copper sulfate pyridine;
auxiliary agent: 13% of rosin, 6% of chlorinated paraffin and 0.5% of magnesium silicate;
antioxidant: AO-10100.125%, AO-680.125%;
anti-ultraviolet agent: HALS 0.25%.
The preparation method comprises the following steps:
s1: weighing the components according to the mass for later use;
s2: melting, blending, extruding and granulating all the components by a double screw;
s3: and (3) freezing the blended granules in the S2, and grinding the frozen blended granules into powder with the particle size of 120 microns to obtain the coating.
Example 3
The coating for preventing marine organism adhesion comprises the following raw materials in parts by weight:
degradable resin: PLA-1 and PLA-250%, wherein PLA-1Mw is 10000g/mol, PLA-2Mw is 150000g/mol, and the ratio of PLA-1/PLA-1 is 1: 1.5;
metal antibacterial agent: 25% of cuprous oxide, 3% of zinc oxide and 2% of copper sulfate pyridine;
auxiliary agent: 13% of rosin, 6% of chlorinated paraffin and 0.5% of magnesium silicate;
antioxidant: AO-10100.125%, AO-680.125%;
anti-ultraviolet agent: HALS 0.25%.
The preparation method comprises the following steps:
s1: weighing the components according to the mass for later use;
s2: melting, blending, extruding and granulating all the components by a double screw;
s3: and (3) freezing the blended granules in the S2, and grinding the frozen blended granules into powder with the particle size of 120 microns to obtain the coating.
Example 4
The coating for preventing marine organism adhesion comprises the following raw materials in parts by weight:
degradable resin: PLA-1 and PLA-230%, wherein PLA-1Mw is 10000g/mol, PLA-2Mw is 200000g/mol, and the ratio of PLA-1/PLA-1 is 1: 3;
metal antibacterial agent: 42% of cuprous oxide, 4% of zinc oxide and 5% of copper sulfate pyridine;
auxiliary agent: 12% of rosin and 4% of chlorinated paraffin;
antioxidant: AO-10100.25%, AO-680.25%;
anti-ultraviolet agent: 0.25 percent of carbon black.
The preparation method comprises the following steps:
s1: weighing the components according to the mass for later use;
s2: melting, blending, extruding and granulating all the components by a double screw;
s3: and (3) freezing the blended granules in the S2, and grinding the frozen blended granules into powder with the particle size of 150 microns to obtain the coating.
Example 5
The coating for preventing marine organism adhesion comprises the following raw materials in parts by weight:
degradable resin: PLA-1 and PLA-250%, wherein PLA-1Mw is 50000g/mol, PLA-2Mw is 150000g/mol, and the ratio of PLA-1/PLA-1 is 1: 4;
metal antibacterial agent: 25% of cuprous oxide, 3% of zinc oxide and 2% of copper sulfate pyridine;
auxiliary agent: 13% of rosin, 6% of chlorinated paraffin and 0.5% of magnesium silicate;
antioxidant: AO-10100.125%, AO-680.125%;
anti-ultraviolet agent: HALS 0.25%.
The preparation method comprises the following steps:
s1: weighing the components according to the mass for later use;
s2: melting, blending, extruding and granulating all the components by a double screw;
s3: and (3) freezing the blended granules in the S2, and grinding the frozen blended granules into powder with the particle size of 100 microns to obtain the coating.
The coatings prepared in the above examples 1 to 5 were sprayed with thermoplastic powder to form 0.2mm, 0.3mm, 0.4mm, 0.5mm and 0.6mm coating samples on the surface of 316 stainless steel sheet for testing; 200X200X2, placing the coated sheet on a rotating water wheel, placing the water wheel in Shenzhen gulf seawater for 1 year, continuously rotating for 12hr for a stop period of 12hr, taking out the sample at a linear speed of 10km/hr during rotation, taking out the sample every 3 months, observing the surface to evaluate the biological adhesion effect, taking out the residual coating on the surface of a sample central area 20X20mm to measure the copper element content to calculate the consumption rate, taking the copper element content of the original coating as a reference, and testing the copper content by using X-ray fluorescence (XRF), wherein the test method is as follows: maria
Erik Ytreberg, "Quantification of Cu and Zn in anti-fouling paint films by XRF", Talanta, Volume 223, Part 2,1February 2021, the consumption rate of copper element content presumes the effective time of anti-marine organism adhesion, the test structure is shown in the following table:
| examples/items | Particle size (micron) | Spraying method | Coating thickness (mm) | Anti-adhesion effective period |
| Example 1 | 120 | Thermoplastic spray coating | 0.2 | 6 years old |
| Example 2 | 120 | Thermoplastic spray coating | 0.3 | For 3 years |
| Example 3 | 120 | Thermoplastic spray coating | 0.4 | For 3 years |
| Example 4 | 150 | Thermoplastic spray coating | 0.5 | 3.5 years old |
| Example 5 | 100 | Thermoplastic spray coating | 0.6 | 4.5 years old |
As seen from the above table, the coating has good marine organism adhesion resistance through reasonable compounding of degradable resin, auxiliary agent, metal antibacterial agent, antioxidant and anti-ultraviolet agent, and is obviously superior to the marine organism adhesion resistance effective period of 1-2 years of the commercial products, specifically, in the application, the degradation speed is controlled by blending different molecular weight polylactic acids, the polylactic acid is hydrolyzed and degraded into nontoxic pollution-free lactic acid monomer, the coating is environment-friendly, and can inhibit the growth of bacteria or microorganisms, the polylactic acid in the application is continuously hydrolyzed and dissolved in seawater as a base material to release the antibacterial agent to prevent the adhesion of organisms, the coating thickness is thinned along with the use time, the degradation speed of the polylactic acid in seawater is related to the molecular weight, the low molecular weight is rapidly degraded, the high molecular weight is slowly degraded, so the addition ratio of the high molecular weight polylactic acid can be adjusted, and the coating thickness, so that the biological adhesion resistant effective time of the coating can reach 2-6 years, the components are simple, the raw materials are available, the marine organism adhesion resistance is good, and the coating has a good application prospect.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The coating for preventing marine organism adhesion is characterized by comprising the following components in percentage by mass:
2. the marine organism adhesion preventing coating as claimed in claim 1, wherein the degradable resin has a weight average molecular weight of 5000 to 300000 g/mol.
3. The coating for preventing marine organism adhesion as claimed in claim 1, wherein the degradable resin is a mixed resin composed of low molecular weight polylactic acid and high molecular weight polylactic acid, and the ratio of the low molecular weight polylactic acid to the high molecular weight polylactic acid is 1: 1.5-5.
4. The marine organism adhesion-preventing paint as claimed in claim 1, wherein the auxiliary agent is any one of rosin, chlorinated paraffin and magnesium silicate.
5. The marine organism adhesion-preventing coating as claimed in claim 1, wherein the metal antibacterial agent is any one of copper powder, cuprous oxide, zinc oxide and copper sulfate.
6. The marine organism adhesion preventing paint as claimed in claim 1, wherein the antioxidant is any one of AO-1010, AO-168 and AO-68.
7. The marine organism adhesion-preventing coating as claimed in claim 1, wherein the anti-ultraviolet agent is carbon black or HALS.
8. The method for preparing marine organism adhesion preventing paint according to any one of claims 1 to 7, characterized by comprising the following steps:
s1: weighing the components according to the mass for later use;
s2: melting, blending, extruding and granulating all the components by a double screw;
s3: and (5) freezing the blended granules in the S2, and grinding the frozen blended granules into powder to obtain the coating.
9. The method of claim 8, wherein the step of grinding the mixture of S3 to powder with a particle size of not more than 200 μm.
10. The method of claim 8, wherein the coating for preventing marine organism adhesion is prepared by applying the powder to the metal surface by thermal spraying or electrostatic spraying, thereby obtaining the marine organism adhesion-resistant coating in S3.
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