CN113956763B - Marine organism adhesion preventing paint and preparation method thereof - Google Patents
Marine organism adhesion preventing paint and preparation method thereof Download PDFInfo
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- CN113956763B CN113956763B CN202111355282.3A CN202111355282A CN113956763B CN 113956763 B CN113956763 B CN 113956763B CN 202111355282 A CN202111355282 A CN 202111355282A CN 113956763 B CN113956763 B CN 113956763B
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- 230000010071 organism adhesion Effects 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000003973 paint Substances 0.000 title claims description 25
- 230000003405 preventing effect Effects 0.000 title claims description 23
- 238000000576 coating method Methods 0.000 claims abstract description 35
- 239000011248 coating agent Substances 0.000 claims abstract description 32
- 239000011347 resin Substances 0.000 claims abstract description 22
- 229920005989 resin Polymers 0.000 claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 claims abstract description 21
- 239000002184 metal Substances 0.000 claims abstract description 21
- 239000003242 anti bacterial agent Substances 0.000 claims abstract description 17
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 16
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 13
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 17
- 239000004626 polylactic acid Substances 0.000 claims description 17
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 15
- 239000008187 granular material Substances 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 12
- 238000005507 spraying Methods 0.000 claims description 9
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 8
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 8
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 8
- BKHMEJJDSMFDFK-UHFFFAOYSA-L copper;pyridine;sulfate Chemical compound [Cu+2].[O-]S([O-])(=O)=O.C1=CC=NC=C1 BKHMEJJDSMFDFK-UHFFFAOYSA-L 0.000 claims description 8
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 8
- 229940112669 cuprous oxide Drugs 0.000 claims description 8
- 239000012188 paraffin wax Substances 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 229920001169 thermoplastic Polymers 0.000 claims description 8
- 239000004416 thermosoftening plastic Substances 0.000 claims description 8
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 8
- 239000011787 zinc oxide Substances 0.000 claims description 8
- 230000008014 freezing Effects 0.000 claims description 7
- 238000007710 freezing Methods 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 7
- 238000005303 weighing Methods 0.000 claims description 7
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052919 magnesium silicate Inorganic materials 0.000 claims description 6
- 235000019792 magnesium silicate Nutrition 0.000 claims description 6
- 239000000391 magnesium silicate Substances 0.000 claims description 6
- 239000006229 carbon black Substances 0.000 claims description 5
- 238000007590 electrostatic spraying Methods 0.000 claims description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 abstract description 8
- 230000006750 UV protection Effects 0.000 abstract description 4
- 230000007227 biological adhesion Effects 0.000 abstract description 4
- 238000013329 compounding Methods 0.000 abstract description 4
- 238000003912 environmental pollution Methods 0.000 abstract description 4
- 239000004310 lactic acid Substances 0.000 abstract description 4
- 235000014655 lactic acid Nutrition 0.000 abstract description 4
- 239000002904 solvent Substances 0.000 abstract description 4
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 230000007062 hydrolysis Effects 0.000 abstract description 3
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 101000572976 Homo sapiens POU domain, class 2, transcription factor 3 Proteins 0.000 description 20
- 102100026466 POU domain, class 2, transcription factor 3 Human genes 0.000 description 20
- 101000986981 Tropidechis carinatus Acidic phospholipase A2 1 Proteins 0.000 description 20
- 101000585299 Tropidechis carinatus Acidic phospholipase A2 2 Proteins 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000002981 blocking agent Substances 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 239000013535 sea water Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
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- 244000005700 microbiome Species 0.000 description 2
- 230000004224 protection Effects 0.000 description 2
- 238000004876 x-ray fluorescence Methods 0.000 description 2
- 229910000619 316 stainless steel Inorganic materials 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
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- 231100000252 nontoxic Toxicity 0.000 description 1
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- 238000011002 quantification Methods 0.000 description 1
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- 229910052725 zinc Inorganic materials 0.000 description 1
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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
-
- 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
-
- 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
-
- 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
-
- 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
- C08K2003/2248—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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- Chemical & Material Sciences (AREA)
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Plant Pathology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Paints Or Removers (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention relates to the technical field of coatings, in particular to a marine organism adhesion-preventing coating, which comprises degradable resin, auxiliary agent, metal antibacterial agent, antioxidant and ultraviolet resistance agent, wherein the components have good marine organism adhesion resistance through reasonable compounding of the components, the auxiliary agent and the metal antibacterial agent provide good biological adhesion resistance, meanwhile, 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-preventing effect of the application can be further improved, meanwhile, no solvent is added in the application, the use process can not cause environmental pollution, the environment is green, the coating is powdery, and the coating can be sprayed on site and can be used for rapidly repairing a coating damage part, so that the application convenience of the coating is improved; the preparation method has the advantages of simple process and easy preparation, and can meet the requirements of industrial production and manufacture.
Description
Technical Field
The invention relates to the technical field of coatings, in particular to a marine organism adhesion preventing coating and a preparation method thereof.
Background
More than 18000 organisms in each sea area of the world are attached animals and more than 600 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 attachment of marine organisms also damages a paint film, accelerates corrosion of a ship steel plate, increases maintenance times and time of the ship, reduces the on-board navigation rate of the ship, and simultaneously easily spreads marine microorganisms across a water area to damage ecological environment.
In order to better lift the ship, the outer wall of the ship is required to be uniformly coated with the coating for protection treatment, but the existing coating has an unsatisfactory effect of preventing marine organisms from adhering to, and is not beneficial to long-term use of the ship.
Therefore, there is a need for a marine coating that prevents marine organisms from adhering to it and a method for preparing it, 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 adhering to the coating and a preparation method thereof, so as to solve the problems in the prior art.
The technical scheme adopted by the invention is as follows:
a paint for preventing marine organism from adhering comprises the following components in percentage by mass:
further, the weight average molecular weight of the degradable resin is 5000 to 300000g/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 pyridine copper sulfate.
Further, the antioxidant is any one of AO-1010, AO-168 and AO-68.
Further, the ultraviolet resistance agent is carbon black or HALS.
The preparation method of the marine organism adhesion preventing paint comprises the following steps:
s1: weighing the components according to mass for standby;
s2: the components are melted, blended, extruded and granulated through a double screw;
s3: and (3) freezing the blending granules in the step S2, and grinding the blending granules into powder to obtain the coating.
Further, in S3, it is necessary to grind the powder into a particle size of not more than 200 μm.
Further, in S3, the powder is coated on the metal surface by adopting a thermoplastic spraying or electrostatic spraying mode, so that the marine organism adhesion resistant coating is obtained.
The beneficial effects of the invention are as follows:
1. the marine organism adhesion preventing paint provided by the invention comprises the components of degradable resin, auxiliary agent, metal antibacterial agent, antioxidant and ultraviolet resistant agent, and has good marine organism adhesion resistance through reasonable compounding of the components, the auxiliary agent and the metal antibacterial agent provide good biological adhesion resistance, meanwhile, the degradable resin has good adhesion with metal due to containing polar groups, and lactic acid generated after hydrolysis also has a certain antibacterial effect, so that the marine organism adhesion preventing effect of the paint can be further improved, meanwhile, no solvent is added in the paint, the use process does not cause environmental pollution, the paint is environment-friendly, is powdery, can be used for rapidly repairing a coating damage part, and further increases the application convenience of the paint, and the paint provided by the invention has the advantages of simple components, good marine organism adhesion resistance, and good application prospect;
2. the preparation method has the advantages of simple process, easy preparation, simple and convenient operation, no special equipment in the preparation process, no solvent addition, little environmental pollution and convenient preparation, and can meet the requirements of industrial production and manufacture.
Drawings
FIG. 1 is a preparation flow chart in examples 1 to 5 of the present invention.
Detailed Description
In order that the invention may be understood more fully, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended claims. 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 materials used in the examples, unless otherwise indicated, are commonly commercially available 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. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
The values disclosed in the embodiments of the present invention are approximate values, and are not determined values. Where the error or experimental conditions allow, all values within the error range may be included without limiting the specific values disclosed in the embodiments of the present invention.
The numerical ranges disclosed in the examples of the present invention are intended to represent relative amounts of the components in the mixture, as well as ranges of temperatures or other parameters recited in the examples of other methods.
The marine organism adhesion preventing coating comprises the following components in percentage by mass:
further, the weight average molecular weight of the degradable resin is 5000 to 300000g/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 pyridine copper sulfate.
Further, the antioxidant is any one of AO-1010, AO-168 and AO-68.
Further, the ultraviolet resistance agent is carbon black or HALS.
The marine organism adhesion preventing paint provided by the invention comprises the components of degradable resin, auxiliary agent, metal antibacterial agent, antioxidant and ultraviolet resistant agent, and has good marine organism adhesion resistance through reasonable compounding of the components, the auxiliary agent and the metal antibacterial agent provide good biological adhesion resistance, meanwhile, the degradable resin has good adhesion with metal due to the fact that the degradable resin contains polar groups, lactic acid generated after hydrolysis also has a certain antibacterial effect, the marine organism adhesion preventing effect of the paint can be further improved, meanwhile, no solvent is added in the paint, the use process does not cause environmental pollution, the paint is environment-friendly, is powdery, can be used for rapidly repairing a coating damage part, and further increases the application convenience of the paint.
The following are specific examples of the present application:
example 1
A paint for preventing marine organism adhesion comprises the following raw materials in parts by weight:
degradable resin: PLA-1 and PLA-2.30%, wherein PLA-1 Mw=10000 g/mol, PLA-2 Mw=200000 g/mol, and the ratio of PLA-1 to PLA-1 is 1:5;
metal antibacterial agent: 42% of cuprous oxide, 4% of zinc oxide and 5% of copper pyridine sulfate;
auxiliary agent: 12% of rosin and 4% of chlorinated paraffin;
antioxidant: 0.25% of AO-1010 and 0.25% of AO-68;
uv-blocking agent: carbon black 2.5%.
The preparation method comprises the following steps:
s1: weighing the components according to mass for standby;
s2: the components are melted, blended, extruded and granulated through a double screw;
s3: and (3) freezing the blending granules in the step S2, and grinding the blending granules into powder with the particle size of 120 microns to obtain the coating.
Example 2
A paint for preventing marine organism adhesion comprises the following raw materials in parts by weight:
degradable resin: PLA-1 and PLA-2 50%, wherein PLA-1 Mw=50000 g/mol, PLA-2 Mw=150000 g/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 pyridine sulfate;
auxiliary agent: 13% of rosin, 6% of chlorinated paraffin and 0.5% of magnesium silicate;
antioxidant: 0.125% of AO-1010 and 0.125% of AO-68;
uv-blocking agent: HALS 0.25%.
The preparation method comprises the following steps:
s1: weighing the components according to mass for standby;
s2: the components are melted, blended, extruded and granulated through a double screw;
s3: and (3) freezing the blending granules in the step S2, and grinding the blending granules into powder with the particle size of 120 microns to obtain the coating.
Example 3
A paint for preventing marine organism adhesion comprises the following raw materials in parts by weight:
degradable resin: PLA-1 and PLA-2.50%, wherein PLA-1 Mw=10000 g/mol, PLA-2 Mw=150000 g/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 pyridine sulfate;
auxiliary agent: 13% of rosin, 6% of chlorinated paraffin and 0.5% of magnesium silicate;
antioxidant: 0.125% of AO-1010 and 0.125% of AO-68;
uv-blocking agent: HALS 0.25%.
The preparation method comprises the following steps:
s1: weighing the components according to mass for standby;
s2: the components are melted, blended, extruded and granulated through a double screw;
s3: and (3) freezing the blending granules in the step S2, and grinding the blending granules into powder with the particle size of 120 microns to obtain the coating.
Example 4
A paint for preventing marine organism adhesion comprises the following raw materials in parts by weight:
degradable resin: PLA-1 and PLA-2.30%, wherein PLA-1 Mw=10000 g/mol, PLA-2 Mw=200000 g/mol, and the ratio of PLA-1 to PLA-1 is 1:3;
metal antibacterial agent: 42% of cuprous oxide, 4% of zinc oxide and 5% of copper pyridine sulfate;
auxiliary agent: 12% of rosin and 4% of chlorinated paraffin;
antioxidant: 0.25% of AO-1010 and 0.25% of AO-68;
uv-blocking agent: carbon black 0.25%.
The preparation method comprises the following steps:
s1: weighing the components according to mass for standby;
s2: the components are melted, blended, extruded and granulated through a double screw;
s3: and (3) freezing the blending granules in the step S2, and grinding the blending granules into powder with the particle size of 150 microns to obtain the coating.
Example 5
A paint for preventing marine organism adhesion comprises the following raw materials in parts by weight:
degradable resin: PLA-1 and PLA-2 50%, wherein PLA-1 Mw=50000 g/mol, PLA-2 Mw=150000 g/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 pyridine sulfate;
auxiliary agent: 13% of rosin, 6% of chlorinated paraffin and 0.5% of magnesium silicate;
antioxidant: 0.125% of AO-1010 and 0.125% of AO-68;
uv-blocking agent: HALS 0.25%.
The preparation method comprises the following steps:
s1: weighing the components according to mass for standby;
s2: the components are melted, blended, extruded and granulated through a double screw;
s3: and (3) freezing the blending granules in the step S2, and grinding the blending granules into powder with the particle size of 100 microns to obtain the coating.
The coatings prepared in examples 1 to 5 above were appliedRespectively forming coating samples of 0.2mm, 0.3mm, 0.4mm, 0.5mm and 0.6mm on the surface of the 316 stainless steel sheet by adopting a thermoplastic powder spraying mode for testing; 200X200X2, placing the sheet after the coating treatment on a rotating water wheel, placing the water wheel in sea water of Shenzhen bay for 1 year, continuously rotating for 12hr for a stop period, taking out the sample every 3 months at a linear speed of 10km/hr during rotation, observing the surface to evaluate the biological adhesion effect, measuring the copper element content of the residual coating on the 20X20mm surface of the central area of the sample, calculating the consumption speed, using the original coating copper element content as a reference, and testing the copper content by using an X-ray fluorescence (XRF), wherein the test method is as described in reference: maria (Maria)
Erik Ytreberg, "Quantification of Cu and Zn in antifoulingpaint films by XRF", talanta, volume 223,Part 2,1February 2021, copper element content consumption rate speculated effective time against marine organism attachment, test structure is shown in the following table:
| examples/items | Particle size (micron) | Spray coating mode | Coating thickness (mm) | Anti-adhesion expiration date |
| Example 1 | 120 | Thermoplastic spraying | 0.2 | For 6 years |
| Example 2 | 120 | Thermoplastic spraying | 0.3 | For 3 years |
| Example 3 | 120 | Thermoplastic spraying | 0.4 | For 3 years |
| Example 4 | 150 | Thermoplastic spraying | 0.5 | 3.5 years |
| Example 5 | 100 | Thermoplastic spraying | 0.6 | 4.5 years |
As can be seen from the table, the coating has good marine organism adhesion resistance through reasonable compounding of degradable resin, auxiliary agent, metal antibacterial agent, antioxidant and ultraviolet resistance agent, and is obviously superior to the marine organism adhesion resistance of commercial products for 1-2 years, in particular, in the application, the degradation speed is controlled by blending polylactic acid with different molecular weights, the polylactic acid is hydrolyzed and degraded into nontoxic pollution-free lactic acid monomers, the environment is friendly, meanwhile, the growth of bacteria or microorganisms can be inhibited, the polylactic acid in the application is taken as a base material to be continuously hydrolyzed and dissolved in sea water, the antibacterial agent is released to prevent organism adhesion, the thickness of the coating is thinned along with the use time, the degradation speed of the polylactic acid in the sea water is related to the molecular weight, the low molecular weight is rapidly degraded, the high molecular weight is slowly degraded, therefore, the marine organism adhesion resistance effective time of the coating can reach 2-6 years through adjusting the addition ratio of the high molecular weight polylactic acid, the raw material is simple, the marine organism adhesion resistance is good, and the application prospect is good.
The foregoing examples illustrate only a few embodiments of the invention and are described in detail herein without thereby limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (4)
1. The marine organism adhesion preventing paint is characterized by comprising the following components in percentage by mass:
30-50% of degradable resin;
5-30% of an auxiliary agent;
30-60% of a metal antibacterial agent;
0.01-2% of antioxidant;
0.01-2% of anti-ultraviolet agent;
wherein the degradable resin is mixed resin composed of low molecular weight polylactic acid and high molecular weight polylactic acid, the ratio of the low molecular weight polylactic acid to the high molecular weight polylactic acid is 1:1.5-5, and the weight average molecular weight is 5000-300000 g/mol;
wherein the auxiliary agent is any one of rosin, chlorinated paraffin and magnesium silicate;
wherein the metal antibacterial agent comprises cuprous oxide, zinc oxide and copper pyridine sulfate;
wherein the antioxidant is any one of AO-1010, AO-168 and AO-68;
wherein the anti-ultraviolet agent is carbon black or HALS;
the preparation method of the marine organism adhesion preventing paint comprises the following steps:
s1: weighing the components according to mass for standby;
s2: the components are melted, blended, extruded and granulated through a double screw;
s3: and (3) freezing the blending granules in the step S2, and grinding the blending granules into powder to obtain the marine organism adhesion preventing coating.
2. A process for the preparation of a marine organism adhesion-preventing coating, characterized in that it is prepared by the steps as described in claim 1.
3. The process for producing marine organism adhesion preventing paint as claimed in claim 2, wherein in S3, powder having a particle size of not more than 200 μm is ground.
4. The method for preparing marine organism adhesion preventing paint as claimed in claim 2, wherein in S3, powder is coated on the metal surface by adopting a thermoplastic spraying or electrostatic spraying mode, so as to obtain the marine organism adhesion preventing coating.
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