CN108977075B - Preparation method of marine organism adhesion resistant cage paint - Google Patents

Preparation method of marine organism adhesion resistant cage paint Download PDF

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CN108977075B
CN108977075B CN201810737168.9A CN201810737168A CN108977075B CN 108977075 B CN108977075 B CN 108977075B CN 201810737168 A CN201810737168 A CN 201810737168A CN 108977075 B CN108977075 B CN 108977075B
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coating
silicon dioxide
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nano silicon
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CN108977075A (en
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张海龙
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Zhejiang Ocean University ZJOU
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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
    • C09D191/00—Coating compositions based on oils, fats or waxes; Coating compositions based on derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
    • C08F283/124—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes on to polysiloxanes having carbon-to-carbon double bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups
    • 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
    • C09D5/1675—Polyorganosiloxane-containing compositions
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter
    • 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
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

Abstract

The invention relates to the field of coatings, in particular to a preparation method of a marine organism adhesion resistant net cage coating. The preparation method comprises the following steps: s.1, preparing modified nano silicon dioxide; s.2, preparing precursor resin; s.3, preparing a coating base material; and S.4, preparing the coating to obtain the marine organism adhesion resistant net cage coating. The invention has the following beneficial effects: (1) the coating obtained in the invention has good marine organism adhesion resistance effect; (2) the coating is nontoxic and harmless, and does not cause harm to the environment; (3) the coating disclosed by the invention has good weather resistance, and the service life of the marine net cage can be effectively prolonged.

Description

Preparation method of marine organism adhesion resistant cage paint
Technical Field
The invention relates to the field of coatings, in particular to a preparation method of a marine organism adhesion resistant net cage coating.
Background
The sea fishery culture can not be opened, and the agricultural department in China currently increases policy inclination and fund supporting strength for the deep sea net cage culture industry, and supports local culture enterprises to do great work. However, the net wires (PE material) of the net cage cannot be attached and propagated by marine organisms mainly including seaweeds, barnacles and other shellfishes, so that extra load of the net cage and blockage and damage of net holes of the net cage are brought, the net cage needs to be cleaned and repaired every year, and economic loss of cultivation all the year is caused! Therefore, how to avoid the attachment of marine organisms to net cages and net wires ensures the net cage aquaculture industry of marine fishes and promotes the continuous increase of the aquaculture scale in China.
For example, a marine culture cage coating for preventing shellfish parasitism disclosed in Chinese patent document with application publication number CN101580674 is prepared by mixing tung oil, asphalt, lithopone and poisoning material which is triphenyl tin chloride or tributyl tin chloride. The invention has simple preparation process, low cost and convenient use, utilizes the organic tin to block and poison the marine shellfish, effectively prevents the marine shellfish from parasitizing the net cage, and has good effect. However, the shellfish cannot be parasitized through the poisoning effect, so that the shellfish has a large influence on the environment, and although the shellfish has no adverse effect on the production and propagation of the fishes in the net cage, toxic components in the shellfish still have accumulated danger, so that the shellfish is finally enriched in the human body, and the health of the human body is seriously threatened.
Disclosure of Invention
The invention provides a preparation method of a marine organism adhesion resistant net cage coating which is nontoxic and harmless to the environment and can effectively prevent marine organisms from adhering, aiming at overcoming the problems that a net cage coating in the prior art is toxic and harmful, causes harm to the environment and causes the toxic and harmful substances to be enriched in the human body.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a net cage coating for resisting marine organism adhesion comprises the following steps:
s.1, preparing modified nano silicon dioxide: condensing the mixed solution of the nano silicon dioxide and the silane coupling agent in the solution to obtain modified nano silicon dioxide;
s.2 preparation of precursor resin: carrying out hydrolytic polycondensation on alkoxy silane containing vinyl and dodecafluoroheptyl propyl trimethoxy silane to obtain precursor resin containing the vinyl and dodecafluoroheptyl propyl;
s.3, preparing a coating base material: carrying out free radical copolymerization on the precursor resin prepared in the step S.2 and methyl methacrylate to obtain a coating base material containing dodecafluoroheptyl propyl;
s.4, preparing the coating: and mixing the coating base material, the modified nano-silica, the auxiliary agent and the solvent oil uniformly to obtain the marine organism adhesion resistant net cage coating.
According to the coating disclosed by the invention, firstly, alkoxysilane containing a vinyl group and dodecafluoroheptyl propyl trimethoxy silane are subjected to hydrolytic polycondensation to obtain matrix resin containing the vinyl group and dodecafluoroheptyl propyl, the vinyl group can be polymerized with double bonds in methyl methacrylate, and the dodecafluoroheptyl propyl has stronger hydrophobicity due to the surface or C-F bonds with lower performance, so that the surface of the mesh wire of the obtained mesh box is not adhered with water, and the bionic micro-nano material covers the surface and can capture air near the surface of the coating to enable the coating to be densified, so that liquid is only contacted with the air and is not contacted with the surface of the mesh wire of the mesh box. The liquid flows only relative to the air, but not relative to the solid surface, thereby reducing the attachment of marine microorganisms. This very smooth surface prevents marine organisms from adhering to the surface of the net wire of the net cage.
According to the invention, a proper process flow is adopted, the silane coupling agent is grafted on the surface of the nano SiO2, and an organic film is formed on the surface of the nano SiO2, so that the surface tension of particles is reduced, the steric hindrance effect is increased, and the particles can be uniformly dispersed in the film. In addition, the modified nano silicon dioxide can also be used as a reinforcing agent, so that the mechanical property of the coating can be effectively improved, the phenomenon that the coating falls off due to daily use is avoided, and the effectiveness of the net cage is ensured.
In addition, the invention only prevents marine organisms from attaching to the net cage by a physical method, and does not have adverse effect on marine environment and marine organisms, thereby laterally ensuring the food safety of people.
Preferably, the preparation process of the modified nano-silica in the step s.1 is as follows:
(a1) surface activation: putting 100 parts of gas phase method nano silicon dioxide and 2-5 parts of glacial acetic acid in a reaction kettle according to parts by weight, introducing steam into the reaction kettle, raising the temperature to 110-115 ℃, keeping the air pressure in the reaction kettle at 8.0-10.5MPa, activating for 30-120 minutes, cooling to room temperature, and carrying out vacuum drying and grinding to obtain surface activated nano silicon dioxide;
(a2) modification: according to the weight portion, 20-35 portions of nano silicon dioxide after surface activation are dispersed into 100 portions of ethanol, 30-45 portions of silane coupling agent mixed solution, 10-15 portions of water and 0.5-3 portions of glacial acetic acid are added into the nano silicon dioxide while stirring, reflux reaction is carried out for 0.5-5 hours, the solvent is evaporated under reduced pressure after the reaction is finished, and bulk modified silicon dioxide is obtained after vacuum drying;
(a3) and (3) post-treatment: and (b) performing ball milling on the blocky modified nano silicon dioxide obtained in the step (a2) until the particle size reaches 500-3000nm to obtain the modified nano silicon dioxide.
The surface of the nano silicon dioxide is activated before the silane coupling agent is grafted, so that the surface of the nano silicon dioxide is provided with a large number of silicon hydroxyl groups, and the silicon hydroxyl groups can react with alkoxy groups in the silane coupling agent, so that the whole grafting reaction is carried out more effectively.
Preferably, in step S.1, the silane coupling agent mixture is a mixture of gamma-methacryloxypropyltrimethoxysilane, gamma-methacryloxypropylmethyldiethoxysilane and phenyltrimethoxysilane in a ratio of 1:1: 1.
The silane coupling agent in the invention is a mixed solution of different silane coupling agents in 3. due to different respective reaction activities, grafting can be carried out on the surface of the nano silicon dioxide in sequence, and finally the nano silicon dioxide is wrapped to form a spherical structure, the interior of the spherical structure is nano silicon dioxide particles, and the exterior of the spherical structure is wrapped by organic silicon resin, so that the compatibility between the silicon dioxide particles and other components of the coating can be effectively improved.
Preferably, the vinyl-containing alkoxysilane in step s.2 is one of vinyltrimethoxysilane, vinyltriacetoxysilane, methylvinyldimethoxysilane, or vinyltri-t-butoxysilane, and the mass ratio of the vinyl-containing alkoxysilane to the dodecafluoroheptylpropyltrimethoxysilane is 1.5-3.5: 1.
Preferably, the copolymerization step in step S.3 is as follows:
(b1) pre-polymerization: under the protection of nitrogen, dissolving 30-40 parts by mass of methyl methacrylate in 100 parts of toluene, adding a solution of 0.3 part of azobisisobutyronitrile in 10 parts of toluene, raising the temperature to 70-75 ℃, and stirring for reaction for 0.5-1.5 hours to obtain a methyl methacrylate prepolymer;
(b2) copolymerization: adding 10-20 parts of the precursor resin prepared in the step S.2 into the methyl methacrylate prepolymer obtained in the step (b1), and continuously reacting for 1-3 hours to obtain a coating base material solution;
(b3) and (3) post-treatment: and (b) dropwise adding the coating base material obtained in the step (b2) into 500 parts of methanol solution slowly while stirring, filtering and drying to obtain the coating base material.
The coating base material provided by the invention is prepared by pre-polymerizing methyl methacrylate to ensure that the molecular chain length reaches a certain degree, the mechanical strength and flexibility of the molecular chain are ensured, and then copolymerizing the methyl methacrylate with the precursor resin prepared in the step S.2 to obtain the coating base material with super-hydrophobic property.
Preferably, the auxiliary agents in step s.4 are a drier, a toughening agent and a defoaming agent.
Preferably, the drier in the auxiliary in step s.4 is a complex of several salts, and the formula of the specific components in parts by weight is as follows: 10-15 parts of cobalt isooctanoate, 8-12 parts of dibutyltin dilaurate, 5-8 parts of zinc isooctanoate, 3-6 parts of copper naphthenate and 2-5 parts of calcium isooctanoate.
The drier can accelerate curing by catalyzing self-oxidation reaction when added into the unsaturated coating, and because a certain amount of unreacted double bonds exist in the coating base material, the crosslinking curing is carried out along with the oxidation process of the metal salt drier, so that the curing efficiency is greatly improved. And the dibutyltin dilaurate can carry out crosslinking curing on unreacted alkoxy, and the unreacted alkoxy and the dibutyltin dilaurate are compounded with each other, so that the dryness of the resin can be effectively ensured.
Preferably, the toughening agent in the assistant of step s.4 is one of dimethyl silicone rubber, silicone MQ resin, low molecular weight polyamide or polysulfide rubber.
Preferably, the leveling agent in the auxiliary agent of step s.3 is one of polyether modified silicone oil, polyester modified silicone oil, polydimethylsiloxane or alkyl modified polysiloxane.
Preferably, the formulation of the net cage paint in the step s.4 is as follows according to parts by weight: 60-80 parts of coating base material, 35-45 parts of modified nano silicon dioxide, 2-5 parts of drier, 2-3 parts of toughening agent, 0.5-1.5 parts of flatting agent and 100 parts of solvent oil.
Therefore, the invention has the following beneficial effects:
(1) the coating obtained in the invention has good marine organism adhesion resistance effect;
(2) the coating is nontoxic and harmless, and does not cause harm to the environment;
(3) the coating disclosed by the invention has good weather resistance, and the service life of the marine net cage can be effectively prolonged.
Detailed Description
The technical solution of the present invention is further described below by means of specific examples.
The raw materials used in the examples of the present invention are those commonly used in the art, and the methods used in the examples are those conventional in the art, unless otherwise specified.
The scope of the invention is not intended to be limited to the exemplary embodiments. Alterations and further modifications of the inventive features illustrated herein, and additional applications of the principles of the inventions as illustrated herein, are contemplated as within the scope of the invention.
Example 1
A preparation method of a net cage coating for resisting marine organism adhesion comprises the following steps:
s.1, preparing modified nano silicon dioxide: condensing the mixed solution of the nano-silica and the silane coupling agent in a solution to obtain the modified nano-silica, wherein the preparation process comprises the following steps:
(a1) surface activation: putting 100 parts of fumed nano-silica and 2 parts of glacial acetic acid in parts by weight into a reaction kettle, introducing steam into the reaction kettle, raising the temperature to 115 ℃, keeping the air pressure in the reaction kettle at 8.0MPa, activating for 120 minutes, cooling to room temperature, and carrying out vacuum drying and grinding to obtain surface-activated nano-silica;
(a2) modification: according to the weight portion, 20 portions of nano silicon dioxide after surface activation are dispersed into 100 portions of ethanol, 30 portions of mixed solution of gamma-methacryloxypropyl trimethoxysilane, gamma-methacryloxypropyl methyldiethoxysilane and phenyl trimethoxysilane, 10 portions of water and 0.5 portion of glacial acetic acid are added while stirring, the reflux reaction is carried out for 0.5 hour, the solvent is evaporated under reduced pressure after the reaction is finished, and the bulk modified silicon dioxide is obtained by vacuum drying;
(a3) and (3) post-treatment: and (b) carrying out ball milling on the blocky modified nano silicon dioxide obtained in the step (a2) until the particle size reaches 500nm, so as to obtain the modified nano silicon dioxide.
S.2 preparation of precursor resin: performing hydrolytic polycondensation on vinyl trimethoxy silane and dodecafluoroheptyl propyl trimethoxy silane to obtain a precursor resin containing vinyl and dodecafluoroheptyl propyl, wherein the mass ratio of the alkoxy silane containing the vinyl to the dodecafluoroheptyl propyl trimethoxy silane is 1.5: 1.
S.3, preparing a coating base material: and (3) carrying out free radical copolymerization on the precursor resin prepared in the step (S.2) and methyl methacrylate to obtain the coating base material containing dodecafluoroheptyl propyl, wherein the copolymerization step is as follows:
(b1) pre-polymerization: under the protection of nitrogen, 30 parts by mass of methyl methacrylate is dissolved in 100 parts of toluene, then 0.3 part of azodiisobutyronitrile solution dissolved in 10 parts of toluene is added, the temperature is raised to 70 ℃, and the stirring reaction is carried out for 0.5 hour, so as to obtain a methyl methacrylate prepolymer;
(b2) copolymerization: adding 10 parts of the precursor resin prepared in the step S.2 into the methyl methacrylate prepolymer obtained in the step (b1), and continuing to react for 1 hour to obtain a coating base material solution;
(b3) and (3) post-treatment: and (b) dropwise adding the coating base material obtained in the step (b2) into 500 parts of methanol solution slowly while stirring, filtering and drying to obtain the coating base material.
S.4, preparing the coating: 60 parts of coating base material, 35 parts of modified nano silicon dioxide, 2 parts of drier, 2 parts of toughening agent dimethyl silicone rubber, 0.5 part of flatting agent polyether modified silicone oil and 100 parts of solvent oil are uniformly mixed to obtain the marine organism adhesion resistant net cage coating; the drier is a complex of a plurality of salts, and comprises the following specific components in parts by weight: 10 parts of cobalt iso-octoate, 8 parts of dibutyltin dilaurate, 5 parts of zinc iso-octoate, 3 parts of copper naphthenate and 2 parts of calcium iso-octoate.
Example 2
A preparation method of a net cage coating for resisting marine organism adhesion comprises the following steps:
s.1, preparing modified nano silicon dioxide: condensing the mixed solution of the nano-silica and the silane coupling agent in a solution to obtain the modified nano-silica, wherein the preparation process comprises the following steps:
(a1) surface activation: putting 100 parts of fumed nano-silica and 5 parts of glacial acetic acid in parts by weight into a reaction kettle, introducing steam into the reaction kettle, raising the temperature to 110 ℃, keeping the air pressure in the reaction kettle at 10.5MPa, activating for 120 minutes, cooling to room temperature, and carrying out vacuum drying and grinding to obtain surface-activated nano-silica;
(a2) modification: according to the weight portion, 35 portions of nano silicon dioxide after surface activation are dispersed into 100 portions of ethanol, 45 portions of mixed solution of gamma-methacryloxypropyl trimethoxysilane, gamma-methacryloxypropyl methyldiethoxysilane and phenyl trimethoxysilane, 15 portions of water and 3 portions of glacial acetic acid are added while stirring, the mixture is refluxed for 5 hours, the solvent is evaporated under reduced pressure after the reaction is finished, and bulk modified silicon dioxide is obtained after vacuum drying;
(a3) and (3) post-treatment: and (b) carrying out ball milling on the blocky modified nano silicon dioxide obtained in the step (a2) until the particle size reaches 500nm, so as to obtain the modified nano silicon dioxide.
S.2 preparation of precursor resin: performing hydrolytic polycondensation on vinyl triacetoxysilane and dodecafluoroheptyl propyl trimethoxy silane to obtain a precursor resin containing vinyl and dodecafluoroheptyl propyl, wherein the mass ratio of the alkoxysilane containing the vinyl to the dodecafluoroheptyl propyl trimethoxy silane is 3.5: 1.
S.3, preparing a coating base material: and (3) carrying out free radical copolymerization on the precursor resin prepared in the step (S.2) and methyl methacrylate to obtain the coating base material containing dodecafluoroheptyl propyl, wherein the copolymerization step is as follows:
(b1) pre-polymerization: under the protection of nitrogen, 40 parts by mass of methyl methacrylate is dissolved in 100 parts of toluene, then 0.3 part of azodiisobutyronitrile solution dissolved in 10 parts of toluene is added, the temperature is raised to 75 ℃, and the stirring reaction is carried out for 1.5 hours, so as to obtain a methyl methacrylate prepolymer;
(b2) copolymerization: adding 20 parts of the precursor resin prepared in the step S.2 into the methyl methacrylate prepolymer obtained in the step (b1), and continuing to react for 3 hours to obtain a coating base material solution;
(b3) and (3) post-treatment: and (b) dropwise adding the coating base material obtained in the step (b2) into 500 parts of methanol solution slowly while stirring, filtering and drying to obtain the coating base material.
S.4, preparing the coating: 80 parts of paint base material, 45 parts of modified nano silicon dioxide, 5 parts of drier, 3 parts of flexibilizer organic silicon MQ resin, 1.5 parts of flatting agent polyester modified silicone oil and 100 parts of solvent oil are uniformly mixed to obtain the marine organism adhesion resistant net cage paint; the drier is a complex of a plurality of salts, and comprises the following specific components in parts by weight: 15 parts of cobalt iso-octoate, 12 parts of dibutyltin dilaurate, 8 parts of zinc iso-octoate, 6 parts of copper naphthenate and 5 parts of calcium iso-octoate.
Example 3
A preparation method of a net cage coating for resisting marine organism adhesion comprises the following steps:
s.1, preparing modified nano silicon dioxide: condensing the mixed solution of the nano-silica and the silane coupling agent in a solution to obtain the modified nano-silica, wherein the preparation process comprises the following steps:
(a1) surface activation: putting 100 parts of fumed nano-silica and 3 parts of glacial acetic acid in parts by weight into a reaction kettle, introducing water vapor into the reaction kettle, raising the temperature to 115 ℃, keeping the air pressure in the reaction kettle at 9MPa, activating for 60 minutes, cooling to room temperature, and carrying out vacuum drying and grinding to obtain surface-activated nano-silica;
(a2) modification: according to the weight portion, dispersing 30 portions of nano silicon dioxide after surface activation into 100 portions of ethanol, adding 35 portions of mixed solution of gamma-methacryloxypropyltrimethoxysilane, gamma-methacryloxypropylmethyldiethoxysilane and phenyltrimethoxysilane, 12 portions of water and 2 portions of glacial acetic acid according to the mass ratio of 1:1:1 while stirring, carrying out reflux reaction for 2 hours, decompressing and steaming out the solvent after the reaction is finished, and carrying out vacuum drying to obtain blocky modified silicon dioxide;
(a3) and (3) post-treatment: and (a) ball-milling the blocky modified nano silicon dioxide obtained in the step (a2) until the particle size reaches 1000nm to obtain the modified nano silicon dioxide.
S.2 preparation of precursor resin: carrying out hydrolytic polycondensation on methylvinyldimethoxysilane and dodecafluoroheptylpropyltrimethoxysilane to obtain a precursor resin containing vinyl and dodecafluoroheptylpropyltrimethoxysilane, wherein the mass ratio of the alkoxysilane containing vinyl to the dodecafluoroheptylpropyltrimethoxysilane is 2: 1.
S.3, preparing a coating base material: and (3) carrying out free radical copolymerization on the precursor resin prepared in the step (S.2) and methyl methacrylate to obtain the coating base material containing dodecafluoroheptyl propyl, wherein the copolymerization step is as follows:
(b1) pre-polymerization: under the protection of nitrogen, 35 parts by mass of methyl methacrylate is dissolved in 100 parts of toluene, then 0.3 part of azodiisobutyronitrile solution dissolved in 10 parts of toluene is added, the temperature is raised to 72 ℃, and the mixture is stirred and reacted for 1 hour to obtain a methyl methacrylate prepolymer;
(b2) copolymerization: adding 15 parts of the precursor resin prepared in the step S.2 into the methyl methacrylate prepolymer obtained in the step (b1), and continuing to react for 2 hours to obtain a coating base material solution;
(b3) and (3) post-treatment: and (b) dropwise adding the coating base material obtained in the step (b2) into 500 parts of methanol solution slowly while stirring, filtering and drying to obtain the coating base material.
S.4, preparing the coating: 75 parts of coating base material, 40 parts of modified nano silicon dioxide, 3 parts of drier, 2.5 parts of toughening agent low molecular weight polyamide, 1 part of flatting agent polydimethylsiloxane and 100 parts of solvent oil are uniformly mixed to obtain the marine organism adhesion resistant net cage coating; the drier is a complex of a plurality of salts, and comprises the following specific components in parts by weight: 12 parts of cobalt iso-octoate, 10 parts of dibutyltin dilaurate, 7 parts of zinc iso-octoate, 4 parts of copper naphthenate and 4 parts of calcium iso-octoate.
Example 4
A preparation method of a net cage coating for resisting marine organism adhesion comprises the following steps:
s.1, preparing modified nano silicon dioxide: condensing the mixed solution of the nano-silica and the silane coupling agent in a solution to obtain the modified nano-silica, wherein the preparation process comprises the following steps:
(a1) surface activation: putting 100 parts of fumed nano-silica and 3.5 parts of glacial acetic acid in parts by weight into a reaction kettle, introducing steam into the reaction kettle, raising the temperature to 112 ℃, keeping the air pressure in the reaction kettle at 8.5MPa, activating for 100 minutes, cooling to room temperature, and carrying out vacuum drying and grinding to obtain surface-activated nano-silica;
(a2) modification: according to the weight portion, 25 portions of nano silicon dioxide after surface activation are dispersed into 100 portions of ethanol, 40 portions of mixed solution of gamma-methacryloxypropyl trimethoxysilane, gamma-methacryloxypropyl methyldiethoxysilane and phenyl trimethoxysilane, the mass ratio of water to phenyl trimethoxysilane is 1:1:1, 40 portions of mixed solution, 12 portions of water and 2.5 portions of glacial acetic acid are added into the ethanol while stirring, the reflux reaction is carried out for 1.5 hours, the solvent is evaporated under reduced pressure after the reaction is finished, and the bulk modified silicon dioxide is obtained by vacuum drying;
(a3) and (3) post-treatment: and (b) carrying out ball milling on the blocky modified nano silicon dioxide obtained in the step (a2) until the particle size reaches 1500nm, thus obtaining the modified nano silicon dioxide.
S.2 preparation of precursor resin: performing hydrolytic polycondensation on vinyl tri-tert-butoxysilane and dodecafluoroheptyl propyl trimethoxy silane to obtain a precursor resin containing vinyl and dodecafluoroheptyl propyl, wherein the mass ratio of the alkoxy silane containing the vinyl to the dodecafluoroheptyl propyl trimethoxy silane is 3: 1.
S.3, preparing a coating base material: and (3) carrying out free radical copolymerization on the precursor resin prepared in the step (S.2) and methyl methacrylate to obtain the coating base material containing dodecafluoroheptyl propyl, wherein the copolymerization step is as follows:
(b1) pre-polymerization: under the protection of nitrogen, 40 parts by mass of methyl methacrylate is dissolved in 100 parts of toluene, then 0.3 part of azodiisobutyronitrile solution dissolved in 10 parts of toluene is added, the temperature is raised to 70 ℃, and the mixture is stirred and reacted for 1 hour to obtain a methyl methacrylate prepolymer;
(b2) copolymerization: adding 18 parts of the precursor resin prepared in the step S.2 into the methyl methacrylate prepolymer obtained in the step (b1), and continuing to react for 2.5 hours to obtain a coating base material solution;
(b3) and (3) post-treatment: and (b) dropwise adding the coating base material obtained in the step (b2) into 500 parts of methanol solution slowly while stirring, filtering and drying to obtain the coating base material.
S.4, preparing the coating: 65 parts of coating base material, 40 parts of modified nano silicon dioxide, 3 parts of drier, 2 parts of toughening agent polysulfide rubber, 1.5 parts of flatting agent alkyl modified polysiloxane and 100 parts of solvent oil are uniformly mixed to obtain the marine organism adhesion resistant net cage coating; the drier is a complex of a plurality of salts, and comprises the following specific components in parts by weight: 13 parts of cobalt iso-octoate, 8 parts of dibutyltin dilaurate, 6 parts of zinc iso-octoate, 6 parts of copper naphthenate and 4 parts of calcium iso-octoate.
Example 5
A preparation method of a net cage coating for resisting marine organism adhesion comprises the following steps:
s.1, preparing modified nano silicon dioxide: condensing the mixed solution of the nano-silica and the silane coupling agent in a solution to obtain the modified nano-silica, wherein the preparation process comprises the following steps:
(a1) surface activation: putting 100 parts of fumed nano-silica and 4.5 parts of glacial acetic acid in parts by weight into a reaction kettle, introducing steam into the reaction kettle, raising the temperature to 110 ℃, keeping the air pressure in the reaction kettle at 10.5MPa, activating for 45 minutes, cooling to room temperature, and carrying out vacuum drying and grinding to obtain surface-activated nano-silica;
(a2) modification: according to the weight portion, 35 portions of nano silicon dioxide after surface activation are dispersed into 100 portions of ethanol, 40 portions of mixed solution of gamma-methacryloxypropyl trimethoxy silane, gamma-methacryloxypropyl methyldiethoxy silane and phenyl trimethoxy silane 1:1:1, 12 portions of water and 2.5 portions of glacial acetic acid are added into the ethanol while stirring, reflux reaction is carried out for 4.5 hours, the solvent is evaporated under reduced pressure after the reaction is finished, and the bulk modified silicon dioxide is obtained by vacuum drying;
(a3) and (3) post-treatment: and (b) carrying out ball milling on the blocky modified nano silicon dioxide obtained in the step (a2) until the particle size reaches 2000nm to obtain the modified nano silicon dioxide.
S.2 preparation of precursor resin: performing hydrolytic polycondensation on vinyl trimethoxy silane and dodecafluoroheptyl propyl trimethoxy silane to obtain a precursor resin containing vinyl and dodecafluoroheptyl propyl, wherein the mass ratio of the alkoxy silane containing the vinyl to the dodecafluoroheptyl propyl trimethoxy silane is 2.5: 1.
S.3, preparing a coating base material: and (3) carrying out free radical copolymerization on the precursor resin prepared in the step (S.2) and methyl methacrylate to obtain the coating base material containing dodecafluoroheptyl propyl, wherein the copolymerization step is as follows:
(b1) pre-polymerization: under the protection of nitrogen, 36 parts by mass of methyl methacrylate is dissolved in 100 parts of toluene, then 0.3 part of azodiisobutyronitrile solution dissolved in 10 parts of toluene is added, the temperature is raised to 70 ℃, and the mixture is stirred and reacted for 1 hour to obtain a methyl methacrylate prepolymer;
(b2) copolymerization: adding 15 parts of the precursor resin prepared in the step S.2 into the methyl methacrylate prepolymer obtained in the step (b1), and continuing to react for 2.5 hours to obtain a coating base material solution;
(b3) and (3) post-treatment: and (b) dropwise adding the coating base material obtained in the step (b2) into 500 parts of methanol solution slowly while stirring, filtering and drying to obtain the coating base material.
S.4, preparing the coating: 66 parts of paint base material, 44 parts of modified nano silicon dioxide, 3 parts of drier, 3 parts of flexibilizer organic silicon MQ resin, 1 part of flatting agent polyether modified silicone oil and 100 parts of solvent oil are mixed uniformly to obtain the marine organism adhesion resistant net cage paint; the drier is a complex of a plurality of salts, and comprises the following specific components in parts by weight: 11 parts of cobalt iso-octoate, 9 parts of dibutyltin dilaurate, 6 parts of zinc iso-octoate, 4 parts of copper naphthenate and 5 parts of calcium iso-octoate.
The coatings prepared in examples 1 to 5 were tested, and the test results are shown in table 1 below.
TABLE 1
Figure GDA0001779644030000091
The data in the table show that the coating has good performance, and the biological coverage area of the net cage is very small, so that the coating has good marine organism attachment capacity and can effectively prevent barnacles, mussels, algae, bacteria or fungal mucus from attaching.

Claims (9)

1. A preparation method of a net cage coating for resisting marine organism adhesion is characterized by comprising the following steps:
s.1, preparing modified nano silicon dioxide: condensing the mixed solution of the nano silicon dioxide and the silane coupling agent in the solution to obtain modified nano silicon dioxide;
s.2 preparation of precursor resin: carrying out hydrolytic polycondensation on alkoxy silane containing vinyl and dodecafluoroheptyl propyl trimethoxy silane to obtain precursor resin containing the vinyl and dodecafluoroheptyl propyl;
s.3, preparing a coating base material: carrying out free radical copolymerization on the precursor resin prepared in the step S.2 and methyl methacrylate to obtain the coating base material containing dodecafluoroheptyl propyl
The method comprises the following specific steps:
(b1) pre-polymerization: under the protection of nitrogen, dissolving 30-40 parts by mass of methyl methacrylate in 100 parts of toluene, adding a solution of 0.3 part of azobisisobutyronitrile in 10 parts of toluene, raising the temperature to 70-75 ℃, and stirring for reaction for 0.5-1.5 hours to obtain a methyl methacrylate prepolymer;
(b2) copolymerization: adding 10-20 parts of the precursor resin prepared in the step S.2 into the methyl methacrylate prepolymer obtained in the step (b1), and continuously reacting for 1-3 hours to obtain a coating base material solution;
(b3) and (3) post-treatment: slowly stirring and dropwise adding the coating base material obtained in the step (b2) into 500 parts of methanol solution, filtering and drying to obtain the coating base material;
s.4, preparing the coating: and mixing the coating base material, the modified nano-silica, the auxiliary agent and the solvent oil uniformly to obtain the marine organism adhesion resistant net cage coating.
2. The method for preparing the marine organism adhesion resistant cage paint according to claim 1, wherein the modified nano silica in the step S.1 is prepared by the following steps:
(a1) surface activation: putting 100 parts of gas phase method nano silicon dioxide and 2-5 parts of glacial acetic acid in a reaction kettle according to parts by weight, introducing steam into the reaction kettle, raising the temperature to 110-115 ℃, keeping the air pressure in the reaction kettle at 8.0-10.5MPa, activating for 30-120 minutes, cooling to room temperature, and carrying out vacuum drying and grinding to obtain surface activated nano silicon dioxide;
(a2) modification: according to the weight portion, 20-35 portions of nano silicon dioxide after surface activation are dispersed into 100 portions of ethanol, 30-45 portions of silane coupling agent mixed solution, 10-15 portions of water and 0.5-3 portions of glacial acetic acid are added into the nano silicon dioxide while stirring, reflux reaction is carried out for 0.5-5 hours, the solvent is evaporated under reduced pressure after the reaction is finished, and bulk modified silicon dioxide is obtained after vacuum drying;
(a3) and (3) post-treatment: and (b) performing ball milling on the blocky modified nano silicon dioxide obtained in the step (a2) until the particle size reaches 500-3000nm to obtain the modified nano silicon dioxide.
3. The method for preparing the marine organism adhesion-resistant net cage coating according to claim 1 or 2, wherein the silane coupling agent mixed solution in the step S.1 is a mixed solution of gamma-methacryloxypropyltrimethoxysilane, gamma-methacryloxypropylmethyldiethoxysilane and phenyltrimethoxysilane in a mass ratio of 1:1: 1.
4. The method for preparing a marine organism adhesion-resistant net cage coating according to claim 1, wherein the vinyl-containing alkoxysilane in the step S.2 is one of vinyltrimethoxysilane, vinyltriacetoxysilane, methylvinyldimethoxysilane or vinyltri-tert-butoxysilane, and the mass ratio of the vinyl-containing alkoxysilane to the dodecafluoroheptylpropyltrimethoxysilane is 1.5-3.5: 1.
5. The method for preparing the marine organism adhesion resistant cage paint according to claim 1, wherein the auxiliary agents in the step S.4 are a drier, a toughening agent and a defoaming agent.
6. The preparation method of the marine organism adhesion-resistant net cage coating as claimed in claim 1, wherein the drier in the auxiliary agent in the step S.4 is a complex of a plurality of salts, and the specific component formula is as follows in parts by weight: 10-15 parts of cobalt isooctanoate, 8-12 parts of dibutyltin dilaurate, 5-8 parts of zinc isooctanoate, 3-6 parts of copper naphthenate and 2-5 parts of calcium isooctanoate.
7. The method for preparing a marine organism adhesion resistant cage paint as claimed in claim 1, wherein the toughening agent in the assistant of step s.4 is one of dimethyl silicone rubber, silicone MQ resin, low molecular weight polyamide or polysulfide rubber.
8. The method for preparing the marine organism adhesion resistant cage paint according to claim 1, wherein the leveling agent in the auxiliary agent of the step S.3 is one of polyether modified silicone oil, polyester modified silicone oil, polydimethylsiloxane or alkyl modified polysiloxane.
9. The method for preparing a marine organism adhesion resistant cage paint according to claim 1, 5, 6, 7 or 8, wherein the formulation of the cage paint in the step S.4 comprises the following components in parts by weight: 60-80 parts of coating base material, 35-45 parts of modified nano silicon dioxide, 2-5 parts of drier, 2-3 parts of toughening agent, 0.5-1.5 parts of flatting agent and 100 parts of solvent oil.
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