CN112852246A - Preparation method of organic-inorganic three-phase composite antifouling paint with spirulina biochar as carrier - Google Patents
Preparation method of organic-inorganic three-phase composite antifouling paint with spirulina biochar as carrier Download PDFInfo
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- CN112852246A CN112852246A CN202110243409.6A CN202110243409A CN112852246A CN 112852246 A CN112852246 A CN 112852246A CN 202110243409 A CN202110243409 A CN 202110243409A CN 112852246 A CN112852246 A CN 112852246A
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- biochar
- cuprous oxide
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/10—Homopolymers or copolymers of methacrylic acid esters
- C09D133/12—Homopolymers or copolymers of methyl methacrylate
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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
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
A preparation method of an organic-inorganic three-phase composite antifouling paint taking spirulina biochar as a carrier. The invention relates to a preparation method of an organic-inorganic three-phase composite antifouling paint, which takes acrylic resin as a base film and spirulina biochar loaded with cuprous oxide nanoparticles as a filler. Firstly, preparing spirulina biochar through high-temperature thermal decomposition; then, cuprous oxide nano particles prepared by using ascorbic acid as a reducing agent are compounded on the biochar by adopting a chemical liquid phase precipitation method to prepare cuprous oxide/biochar composite filler; then, preparing acrylic resin emulsion according to the monomer ratio; and finally, adding the cuprous oxide/biochar composite filler into the resin emulsion, uniformly dispersing, coating the cuprous oxide/biochar composite filler on the surface of the 304 stainless steel sheet, and curing to obtain the composite coating. The cuprous oxide/biochar composite filler is used, so that a micro-nano rough structure is formed on the surface of the resin film, the mechanical property of the film structure is improved, the agglomeration of the antifouling agent is reduced, the release of the antifouling agent is facilitated, and the attachment of fouling organisms can be effectively inhibited.
Description
Technical Field
The invention relates to an organic-inorganic three-phase composite antifouling paint taking acrylic resin as a basal membrane and cuprous oxide nanoparticles as an antifouling agent by using spirulina biochar as a carrier, in particular to a preparation method of the composite material, and the composite material has good antifouling performance.
Background
Today, the development and utilization of marine resources occupying about seven elements of the earth become strategic targets of human social sustainable development, but the complex marine environment poses serious threats to the service of marine equipment, wherein the damage caused by fouling damage every year is huge, so the research of antifouling coating materials at present becomes a research hotspot in the antifouling field.
The prior art, such as the patent granted by the Chinese invention with the publication number of CN107022043B, discloses a preparation method of a cuprous oxide composite material. The template compound, the soluble copper salt, the acrylamide monomer, the composite emulsifier and the deionized water are mixed, and the cuprous oxide composite acrylamide polymer material existing on the template compound is prepared through a one-pot redox reaction and a polymerization reaction. The method is simple to operate, and has good marine antifouling property and antibacterial property.
Cuprous oxide plays an important role as the most commonly used antifouling and bactericidal agent in antifouling coating materials. Compared with micron-scale cuprous oxide and nano-scale cuprous oxide, the micron-scale cuprous oxide has stable chemical properties, but cannot exert the small-size effect of the nano-scale cuprous oxide, and has poor dispersibility when used as a filler, so that the use efficiency is greatly reduced; the nano cuprous oxide is easy to agglomerate, is easy to be coated in the coating, is not easy to release, and cannot exert corresponding effect. Therefore, the design and development of a composite coating capable of avoiding the problems have important research and application values.
Biochar is generally prepared by biomass pyrolysis, and due to the production form of changing waste into valuable, the biochar draws wide attention today with attention paid to environmental and ecological protection, and has wide application in the fields of agriculture, environment, energy and the like. Microalgae is a kind of aquatic organism, and has a wide variety of species, and the advantages of short culture period, large yield, wide application and the like attract attention of related researchers. Wherein the spirulina is an ancient low-grade aquatic plant, has the body length of 200-500 mu m and the width of 5-10 mu m, is in spiral blue-green color, and is one of the cyanobacteria phyla. Due to the special biological structure, the biological activated carbon is prepared by pyrolysis, a micron-sized layered structure with a high specific surface area can be easily obtained, cuprous oxide nano particles are compounded with the micron-sized layered structure to obtain a cuprous oxide/biological carbon composite structure, and the organic-inorganic composite coating can be obtained by compounding the cuprous oxide/biological carbon composite structure with an organic film, so that the antifouling effect of nano cuprous oxide can be effectively exerted, the agglomeration is reduced, and the effect of reinforcing the mechanical property of the coating by using a carbon material as a filler can be exerted.
Disclosure of Invention
The invention provides a preparation method and application of an organic-inorganic three-phase composite antifouling paint taking spirulina biochar as a carrier, aiming at the technical problems. The prepared composite coating can be used for preventing fouling of fresh water or seawater, and has the advantages of good antifouling performance, strong application performance, no harm and pollution to the environment and the like, and the preparation process has stronger operability.
The invention aims at the preparation method of the organic-inorganic three-phase composite antifouling paint with spirulina biochar as a carrier, which adopts the following preparation steps.
(1) Preparing biochar: the biochar is made from spirulina powder, and the preprocessed spirulina biomass is made into biochar through a 600-800 ℃ high-temperature pyrolysis reaction after being preprocessed by dilute hydrochloric acid.
(2) Preparing cuprous oxide/biochar composite filler: adding the obtained biochar into a liquid phase system containing soluble copper salt, and under the conditions that an alkaline environment is provided by sodium hydroxide, polyvinylpyrrolidone is used as a surfactant and ascorbic acid is used as a reducing agent, providing active sites for cuprous oxide nanoparticles to be loaded by the biochar to generate a micro/nano-scale composite structure. The load capacity of the cuprous oxide on the biochar is 10-30 wt%.
(3) Preparation of acrylic resin emulsion: the monomer ratio is that the mass fraction ratio of methyl methacrylate to ethyl acrylate to styrene is 4.0-5.0: 2.5-3.0: 1.5-2.0, the dosage of the initiator azodiisobutyronitrile is 0.8-1.0 wt%, the polymerization reaction is carried out in a system using 8-12 mL of toluene as a solvent, and 10 wt% of silane coupling agent (KH-570) is added to enhance the overall combination degree. The acrylic resin emulsion prepared according to the proportion has moderate viscosity, not only has better film forming performance, but also is convenient for the uniform dispersion of the filler in the acrylic resin emulsion, so that the obtained composite coating has stable physical and chemical properties, simultaneously, the combination of all phases is beautiful and firm, and the integral practicability is improved.
(4) The prepared filler is added into the emulsion according to 0.5 weight percent of the emulsion, and the film can be coated after uniform oscillation.
The organic-inorganic three-phase composite antifouling paint prepared by taking the spirulina biochar as the cuprous oxide nanoparticle carrier can be directly applied to the metal surface of fresh water or seawater equipment or the inner surface of facilities needing antifouling and antibiosis, such as pipelines, cavities and the like.
Compared with the prior art, the invention has the beneficial effects that: the spirulina biological carbon is introduced as an antifouling agent carrier, is derived from biomass of lower organisms, can be prepared by recycling waste, has lower cost and is non-toxic and harmless to the environment. The carrier plays an intermediate role in starting and stopping, is compounded with the nano cuprous oxide into a micro-nano structure, is beneficial to the dispersion and play of the nano antifouling agent, is used as a filler to be combined with the acrylic resin, not only keeps the protective effect of the acrylic resin on a bottom layer metal material, but also enhances the mechanical durability of a coating, and enables the coating to have higher antifouling performance. The invention has good stability and antifouling performance when used for antifouling paint, and the adopted technology has low requirement on equipment, simple operation and low cost.
Drawings
FIG. 1 is a schematic structural diagram of the composite coating prepared by the present invention. When the paint is coated on a metal substrate, the cuprous oxide/biochar composite filler is embedded in the coating, and part of cuprous oxide nano particles are exposed, so that the antifouling performance of the paint is facilitated, and the filler blocks the formation of a dirt film on the surface of the coating, so that the integral antifouling performance and mechanical performance are improved.
FIG. 2 is an X-ray diffraction (XRD) pattern of the organic-inorganic three-phase composite antifouling paint obtained in example 1 of the present invention.
FIG. 3 is a Scanning Electron Microscope (SEM) image of the organic-inorganic three-phase composite antifouling paint obtained in example 1 of the present invention.
Fig. 4 is an XRD pattern of the cuprous oxide/biochar composite filler obtained in example 2 of the present invention.
FIG. 5 is an SEM image of a cuprous oxide/biochar composite filler obtained in example 2 of the present invention. Cuprous oxide particles are loaded on the surface of the biochar, and the particle size of the cuprous oxide particles is 50-200 nm.
FIG. 6 is a graph showing the change with time of the amount of chlorella adhered to the surface of a film obtained in example 1 of the present invention.
FIG. 7 is a graph showing the change with time of the amount of chlorella adhered to the surface of a film obtained in example 2 of the present invention.
Detailed Description
A preparation method of an organic-inorganic three-phase composite antifouling paint with spirulina biochar as a carrier comprises the following steps.
(1) Soaking spirulina powder in water at a concentration of 0.4-0.6 mol.L-1Stirring at 500-800 rpm for 20-24 h in the dilute hydrochloric acid, washing with deionized water for 3-5 times, washing with absolute ethyl alcohol for 1-2 times, and drying. Fully grinding the dried solid into powder, and heating at the temperature rising rate of 5-8 ℃ per minute in an argon atmosphere-1Heating to 600-800 ℃, pyrolyzing for 2.0-2.5 h, cooling, taking out, and fully grinding to obtain the spirulina charcoal powder.
(2) Adding part of charcoal powder into a beaker containing 40 mL of deionized water, stirring at 500 rpm for 30 min, sequentially adding copper sulfate pentahydrate and polyvinylpyrrolidone powder at a mass ratio of 2:1, stirring for 30 min, and finally adding 10 mL of 0.5 mol.L-1The mass ratio of copper salt to a reducing agent is controlled to be 4:5, the mixture is stirred and reacted for 1.0-1.2 h, the particles after the reaction are washed for 3-5 times by deionized water and washed for 1-2 times by absolute ethyl alcohol, and the cuprous oxide/biochar composite filler is obtained.
(3) Weighing methyl methacrylate, ethyl acrylate and styrene according to the mass ratio of 4.0-5.0: 2.5-3.0: 1.5-2.0, putting the materials into a beaker, uniformly stirring, putting the beaker into a separating funnel, and preparing for titration; adding 8-12 mL of toluene, 10 wt% of KH-570 and 0.8-1.0 wt% of initiator azobisisobutyronitrile into a three-neck flask, continuously stirring at 500 rpm, heating to 80-85 ℃, uniformly and continuously dropping the prepared dropping monomer into the flask within 1.0 h, condensing and refluxing, continuously reacting for 1.5-2.0 h, supplementing 0.0-0.2 wt% of initiator, keeping the total amount of initiator at 1.0 wt%, and reacting for 1.0 h under heat preservation to obtain the acrylic resin emulsion.
(4) Adding the particles prepared in the step (2) into the emulsion prepared in the step (3) according to the mass fraction of 0.5%, uniformly oscillating, uniformly coating the particles on a 304 stainless steel sheet by using a dropper, and curing at 60 ℃ to obtain the inorganic-organic three-phase composite antifouling coating film taking the spirulina biochar as a carrier.
Example 1 (1) Spirulina powder was soaked in 0.4 mol. L-1Stirring at 500 rpm for 20 hr, washing with deionized water for 3 times, washing with anhydrous ethanol for 1 time, and oven drying. Fully grinding the dried solid into powder, and heating at the temperature rising rate of 5 ℃ for min in an argon atmosphere-1Heating to 600 deg.C, pyrolyzing for 2.5 hr, cooling, and grinding to obtain Spirulina charcoal powder.
(2) Adding part of charcoal powder into a beaker containing 40 mL of deionized water, stirring at 500 rpm for 30 min, sequentially adding copper sulfate pentahydrate and polyvinylpyrrolidone powder at a mass ratio of 2:1, stirring for 30 min, and finally adding 10 mL of 0.5 mol.L-1The weight ratio of copper salt to a reducing agent is 4:5, stirring and reacting for 1.2 h, washing the reacted particles for 3 times with water, and washing for 1 time with absolute ethyl alcohol to obtain the cuprous oxide/biochar composite filler with the load of 10%.
(3) Putting methyl methacrylate, ethyl acrylate and styrene into a beaker according to the mass ratio of 5.0:2.5:1.5, uniformly stirring, putting into a separating funnel, and preparing for titration; adding 10 mL of toluene, 10 wt% of KH-570 and 0.8 wt% of initiator azobisisobutyronitrile into a three-neck flask, continuously stirring at 500 rpm, heating to 80 ℃, uniformly and continuously dripping the prepared dripping monomer into the flask within 1.0 h, condensing and refluxing, continuously reacting for 2.0 h, supplementing 0.2 wt% of initiator, and reacting for 1.0 h under heat preservation to obtain the acrylic resin emulsion.
(4) Adding the particles prepared in the step (2) into the emulsion prepared in the step (3) according to the mass fraction of 0.5%, uniformly oscillating, uniformly coating the emulsion on a 304 stainless steel sheet by using a dropper, and curing at 60 ℃ to obtain the organic-inorganic composite antifouling coating taking the spirulina biochar as a carrier.
The particle prepared in step (2) of this example was subjected to X-ray diffraction, and the XRD spectrum obtained is shown in fig. 2, since biochar is amorphous carbon, no diffraction peak is present, and the diffraction peak of cuprous oxide is not obvious.
When the particles prepared in step (2) of this example were observed by a scanning electron microscope, the SEM image obtained is shown in fig. 3, and it is known that the nano cuprous oxide was uniformly distributed on the surface of the biochar.
Hanging the stainless steel sheet coated with the paint in an algae pond (inoculation concentration of 0.37 g.L) in which chlorella is cultured-1) And testing the antifouling performance, wherein the culture medium is BG-11, a proper amount of air and carbon dioxide are introduced to ensure sufficient illumination, and the adhesion amount of the chlorella per unit area is shown in figure 6. As can be seen from the figure, after the cuprous oxide/biochar composite filler is added, the biomass of the adhered chlorella is obviously reduced and slowly rises in the whole experimental period, which indicates that the prepared composite coating has better antifouling property.
Example 2 (1) Spirulina powder was soaked in 0.6 mol. L-1Stirring at 800 rpm for 24 hr, washing with deionized water for 5 times, washing with anhydrous ethanol for 2 times, and oven drying. Fully grinding the dried solid into powder, and heating at the temperature rising rate of 8 ℃ for min in an argon atmosphere-1Heating to 800 deg.C, pyrolyzing for 2.0 hr, cooling, and grinding to obtain Spirulina charcoal powder.
(2) Adding part of charcoal powder into a beaker containing 40 mL of deionized water, stirring at 500 rpm for 30 min, sequentially adding copper sulfate pentahydrate and polyvinylpyrrolidone powder at a mass ratio of 2:1, stirring for 30 min, and finally adding 10 mL of 0.5 mol.L-1Aqueous sodium hydroxide solution and 10 mL aqueous ascorbic acid solutionAnd the mass ratio of the copper salt to the reducing agent is 4:5, stirring and reacting for 1.0 h, washing the reacted particles for 5 times with water and washing the particles for 2 times with absolute ethyl alcohol to obtain the cuprous oxide/spirulina biochar composite filler with the load of 30%.
(3) Putting methyl methacrylate, ethyl acrylate and styrene into a beaker according to the mass ratio of 4.0:3.0:2.0, uniformly stirring, putting into a separating funnel, and preparing for titration; adding 12 mL of toluene, 10 wt% of KH-570 and 0.9 wt% of initiator azobisisobutyronitrile into a three-neck flask, continuously stirring at 800 rpm, heating to 85 ℃, uniformly and continuously dripping the prepared dripping monomer into the flask within 1.0 h, condensing and refluxing, continuously reacting for 1.5 h, supplementing 0.1 wt% of initiator, and reacting for 1.0 h under heat preservation to obtain the acrylic resin emulsion.
(4) Adding the particles prepared in the step (2) into the emulsion prepared in the step (3) according to the mass fraction of 0.5%, uniformly oscillating, uniformly coating the particles on a 304 stainless steel sheet by using a dropper, and curing at 60 ℃ to obtain the organic-inorganic composite antifouling coating taking the spirulina biochar as a carrier.
The particle prepared in step (2) of this example was subjected to X-ray diffraction, and the XRD spectrogram obtained is shown in fig. 4, the diffraction peak of the image matches the position and intensity of the diffraction peak of cuprous oxide in standard PDF card 78-2076, and the obtained cuprous oxide/biochar composite filler contains almost no impurities.
Scanning electron microscope observation is performed on the particles prepared in step (2) of this example, and an obtained SEM image is shown in fig. 5, which shows that the nano cuprous oxide particles are compounded on the surface of the biochar, and the loading amount is significantly improved compared with fig. 3.
The stainless steel sheet coated with the paint was hung in a chlorella culture pond and tested for antifouling performance under the same conditions as in example 1, and the amount of adhesion of chlorella per unit area is shown in fig. 7. As can be seen from the figure, compared with a pure coating, the composite coating prepared by the invention has good antifouling performance, the antifouling efficiency can reach 93% through calculation, and the effect is achieved when the load of cuprous oxide is 10%, so that the preparation cost is saved.
Claims (4)
1. The construction idea and preparation method of an organic-inorganic three-phase composite antifouling paint take acrylic resin as a basal membrane, spirulina biochar as a carrier and cuprous oxide nanoparticles as an antifouling agent.
2. The preparation method is characterized in that the spirulina biochar with high specific surface area provides load active sites for cuprous oxide nanoparticles to form a micro-nano composite structure, and then the composite material is added into acrylic resin emulsion in the form of filler, coated and cured to form a film.
3. The method for preparing the organic-inorganic three-phase composite antifouling paint according to claim 1, wherein the cuprous oxide/charcoal composite filler is added to control the appearance, structure and antifouling property of the acrylic resin film and enhance the mechanical property of the system.
4. The preparation method of the organic-inorganic three-phase composite antifouling paint as claimed in claim 1, wherein after the spirulina biological carbon is introduced as a carrier, the agglomeration of cuprous oxide nanoparticles can be effectively reduced, the bonding state of the antifouling agent and the organic film is changed, and the release of the antifouling agent is facilitated, so that the service performance of the antifouling coating is improved.
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| CN113583533A (en) * | 2021-08-25 | 2021-11-02 | 中国海洋大学 | Preparation method of sodium chloride modified double-layer composite coating with dual effects of antifouling and protection |
| CN113943054A (en) * | 2021-10-25 | 2022-01-18 | 常熟理工学院 | Method for efficiently cleaning fluorine-containing micro-plastic in water body by using spirulina |
| CN114907766A (en) * | 2022-03-14 | 2022-08-16 | 中海石油(中国)有限公司 | Novel marine antifouling material based on biochar micro-nano structure and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113583533A (en) * | 2021-08-25 | 2021-11-02 | 中国海洋大学 | Preparation method of sodium chloride modified double-layer composite coating with dual effects of antifouling and protection |
| CN113943054A (en) * | 2021-10-25 | 2022-01-18 | 常熟理工学院 | Method for efficiently cleaning fluorine-containing micro-plastic in water body by using spirulina |
| CN113943054B (en) * | 2021-10-25 | 2023-09-15 | 常熟理工学院 | Method for efficiently cleaning fluorine-containing microplastic in water body by using spirulina |
| CN114907766A (en) * | 2022-03-14 | 2022-08-16 | 中海石油(中国)有限公司 | Novel marine antifouling material based on biochar micro-nano structure and preparation method and application thereof |
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| CN112852246B (en) | 2022-01-07 |
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