CN114231114B - Preparation method of allicin grafted amphiphilic photocatalytic antifouling paint special for aquaculture net cage - Google Patents
Preparation method of allicin grafted amphiphilic photocatalytic antifouling paint special for aquaculture net cage Download PDFInfo
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- CN114231114B CN114231114B CN202111411338.2A CN202111411338A CN114231114B CN 114231114 B CN114231114 B CN 114231114B CN 202111411338 A CN202111411338 A CN 202111411338A CN 114231114 B CN114231114 B CN 114231114B
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- allicin
- carbon nitride
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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
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- 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
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
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- 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
- C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
- Y02A40/80—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in fisheries management
- Y02A40/81—Aquaculture, e.g. of fish
Abstract
The invention discloses a preparation method of allicin grafted amphiphilic photocatalytic antifouling paint special for a culture net cage, which is characterized in that a silane coupling agent KH-570 is used for modifying multidimensional carbon nitride, and the modified multidimensional carbon nitride is used as an antifouling agent; and (3) carrying out free radical polymerization reaction on a mixed monomer formed by mixing a fluorine-containing acrylic ester monomer, functionalized polyethylene glycol, allicin and an acrylic ester monomer and modified multidimensional carbon nitride under the action of a transition metal catalyst to obtain the allicin grafted amphiphilic photocatalytic antifouling paint special for the culture net cage. The coating formed by the antifouling paint has good antifouling and antibacterial effects and strong adhesive force.
Description
Technical Field
The invention relates to a preparation method of allicin grafted amphiphilic photocatalytic antifouling paint special for a culture net cage.
Background
As fishery resources decay, a great shift from fishing to farming has occurred. The fishing production focus is changed from the traditional fishing industry to the marine development cage culture industry, and the change is already the consensus of the mariculture country. Due to poor water exchange of the common net cages, the substrate and water quality of the sea area are deteriorated after long-term high-density cultivation, so that the fishes grow slowly and are epidemic, the common net cage cultivation is difficult to continuously develop, the human activities are adversely affected, and negative economic benefits are brought to investors. The most economical and effective means for solving the marine fouling problem of the aquaculture industry is to brush marine antifouling paint.
Ma Xing of the national academy of sciences of China provides a series of polyethylene fishing net antifouling paint prepared through the steps of matrix resin screening, paint formula design and the like in the paper of preparation and safety evaluation of polyethylene fishing net antifouling paint. The prepared fishing net antifouling paint has good flexibility and can be used in the following fieldsThe fishing net is well attached, and after 5 months of real sea hanging net, the surface of the fishing net has no obvious fouling organism attached. However, the anti-fouling paint formula system screened by the method contains Cu 2 The copper-containing anti-fouling agents such as O, cuSCN and the like, and the release of copper ions not only can accumulate in aquatic products to influence the quality of the aquatic products, but also can further influence the health of human bodies at the top end of a food chain; the polyurethane for history of the major open laboratory of the fishery of the ocean and estuary of the department of agriculture is used as a base material, and polytetrafluoroethylene and capsaicin are added to prepare the novel low-surface-energy net cage anti-fouling paint. Compared with a blank nylon fishing net, through a real sea experiment for 210 days, the novel low-surface-energy net cage anti-fouling coating has fewer attached fouling organisms on the fishing net, and a better anti-fouling effect is obtained. However, the special soft material and smooth surface of the fishing net cause poor adhesion of the low surface energy coating to the fishing net, and the coating is easy to fall off, so that the protection effect is lost; in the method, epoxy resin is used as a resin matrix to solve the problem of poor coating adhesion, and nano particles such as titanium dioxide, zinc oxide and the like are used as an antifouling agent to solve the problem of serious pollution of traditional heavy metal antifouling agents such as cuprous oxide and the like. However, the nanoparticle anti-fouling agents such as titanium dioxide, zinc oxide and the like are mainly used for sterilizing and anti-fouling by Reactive Oxygen Species (ROS) generated by illumination, do not generate ROS basically when illumination conditions are poor, and have poor anti-fouling effect.
Disclosure of Invention
Aiming at the defects, the invention provides a preparation method of an allicin grafted amphiphilic photocatalytic antifouling paint special for a culture net cage.
The technical scheme adopted by the invention comprises the following steps:
(1) Adding multidimensional carbon nitride and silane coupling agent KH-570 into absolute ethyl alcohol, carrying out surface treatment on the multidimensional carbon nitride for 3-6 hours at the temperature of 40-55 ℃, carrying out solid-liquid separation after the surface treatment is finished, washing separated solid particles with a detergent, and then carrying out vacuum drying on the solid particles at the temperature of 60-70 ℃ to obtain modified multidimensional carbon nitride; toluene is selected as the detergent;
(2) And (3) carrying out free radical solution polymerization reaction on a mixed monomer formed by mixing a fluorine-containing acrylic ester monomer, functionalized polyethylene glycol, allicin and an acrylic ester monomer and modified multidimensional carbon nitride under the action of a transition metal catalyst to obtain the allicin grafted amphiphilic photocatalytic antifouling paint special for the culture net cage.
The specific operation of the step (2) is as follows: adding the modified multidimensional carbon nitride and the transition metal catalyst into dimethylbenzene, dropwise adding the mixed monomer at the temperature of 55-70 ℃ under the protection of nitrogen and stirring, finishing dropwise adding within 3-8 hours, and continuously reacting the added dimethylbenzene solution of benzoyl peroxide for 4-12 hours after finishing dropwise adding, thereby obtaining the allicin grafted amphipathic photocatalytic antifouling paint special for the aquaculture net cage after finishing the reaction.
The dosage of the modified multidimensional carbon nitride is 0.1-12% of the mass of the mixed monomer, and the dosage of the transition metal catalyst is 0.1-0.2% of the mass of the mixed monomer; the dosage of the dimethylbenzene is 2-5%; the dosage of the dimethylbenzene solution of the benzoyl peroxide is 3-5% of the mass of the mixed monomer, and the mass ratio of the benzoyl peroxide to the dimethylbenzene in the dimethylbenzene solution of the benzoyl peroxide is 1:12-25; the weight ratio of the fluorine-containing acrylic ester monomer to the functional polyethylene glycol to the allicin to the acrylic ester monomer is 1-11:1-12:1-5:6-12.
The dosage of the modified multidimensional carbon nitride is 0.5-5% of the mass of the mixed monomer.
The mass volume ratio of the multidimensional carbon nitride to the silane coupling agent KH-570 is 1-5 g:0.5-6.5 mL; preferably, the mass-volume ratio of the multidimensional carbon nitride to the silane coupling agent KH-570 is 1-5 g:2.5-5 mL.
The fluorine-containing acrylate monomer is hexafluorobutyl methacrylate.
The functionalized polyethylene glycol is polyethylene glycol diallyl ether (cas: 59788-01-1); for example, shanghai Michael chemical technology Co., ltd.
The acrylic monomer is any one of butyl acrylate and ethyl acrylate or a mixture of the butyl acrylate and the ethyl acrylate in any proportion.
The transition metal catalyst is cuprous bromide.
Carrying out ultrasonic dispersion treatment on the antifouling paint for 120s; the anti-fouling paint is coated on a net cage and a net cover, and is placed in a shade place for hanging and airing, so that the allicin grafted amphiphilic photocatalytic anti-fouling coating can be formed on the net cage and the net cover.
The invention uses silane coupling agent KH-570 to carry out surface treatment on the multidimensional carbon nitride, and the silane coupling agent KH-570 combines with the multidimensional carbon nitride by molecular force to obtain the modified multidimensional carbon nitride. The modified multidimensional carbon nitride is used as an antifouling agent, and the antifouling agent is prepared into the allicin grafted amphiphilic antifouling paint through free radical polymerization reaction with allicin, fluorine-containing acrylate monomer, functionalized polyethylene glycol and acrylate monomer in a chemical bond mode. The functionalized polyethylene glycol (PEG), fluorine-containing acrylic acid monomer, allicin and acrylic ester monomer are synthesized into the amphiphilic allicin crosslinked network polymer, the formed coating has a crosslinked network structure, and the multidimensional carbon nitride is distributed on the surface of the polymer coating, so that a multifunctional synergistic antifouling composite coating can be constructed. The garlicin structure in the coating not only can play a role in sterilizing, but also can prevent the formation of a fouling biological film on the culture net cage and reduce the death rate of aquatic products, and can play a role in food calling, shorten the culture period and improve the meat quality of the aquatic products. The amphiphilic coating surface formed by the fluorine-containing side chains of the polyethylene glycol and the fluorine-containing acrylic acid ester monomer not only can provide a carrier for porous carbon nitride and overcome the defect that a photocatalyst cannot resist fouling directionally, but also can enhance the adhesive force of the coating by adjusting the proportion of the polyethylene glycol and the fluorine-containing acrylic acid monomer and overcome the defect of poor general adhesive force of cage coating.
Compared with the prior art, the invention has the following advantages:
1. due to the allicin structure, the allicin grafted amphiphilic photocatalytic antifouling coating special for the culture net cage not only can play a role in antifouling and antibacterial of the traditional antifouling coating, but also can reduce the morbidity of aquatic products, plays a role in food calling, shortens the culture period and meets the requirements of a multifunctional integrated coating;
2. the coating with different adhesive force and surface energy is obtained by adjusting the monomer proportion of the fluorine-containing acrylic ester monomer and the functionalized polyethylene glycol, so that the controllable adjustment of the adhesive force of the net cage is realized, and the problem of poor adhesive force of the traditional net cage coating is solved;
3. the multidimensional carbon nitride photocatalysis antifouling is combined with the intrinsic antifouling of the allicin resin matrix, so that the antifouling effect is enhanced, meanwhile, heavy metal ions are not generated, and the influence on aquatic products is further reduced.
Detailed Description
The following examples illustrate the feasibility of the technical solution of the invention without limiting the scope of protection of the invention to the following specific examples.
Example 1
The preparation method of the allicin grafted amphiphilic photocatalytic antifouling paint special for the culture net cage comprises the following steps:
(1) Putting the multi-dimensional carbon nitride prepared by a template method into 100 mL absolute ethyl alcohol, adding 4.5 mL silane coupling agent KH-570 into the alcohol, heating to 45 ℃ in a water bath, carrying out surface treatment on the multi-dimensional carbon nitride under stirring for 5.5 h, carrying out solid-liquid separation after the surface treatment is finished, washing the separated solid particles with toluene, and then carrying out vacuum drying on the solid particles at the temperature of 60 ℃ to obtain the modified multi-dimensional carbon nitride;
(2) 1.5g of modified multidimensional carbon nitride and 0.24g of cuprous bromide are added into 120mL of dimethylbenzene, under the conditions of temperature 65 ℃ and nitrogen protection and magnetic stirring at the speed of 500 rpm, mixed monomers formed by mixing 25g of hexafluorobutyl methacrylate, 50g of polyethylene glycol diallyl ether, 5g of allicin and 35g of ethyl acrylate are dropwise added, 21g of dimethylbenzene solution of benzoyl peroxide is added after the dropwise addition, the reaction is continued for 8 hours under the conditions of temperature 65 ℃ and nitrogen protection and magnetic stirring at the speed of 500 rpm, and the allicin grafted amphipathic photocatalytic antifouling paint special for the culture net cage is obtained after the reaction is completed. The mass ratio of benzoyl peroxide to xylene in the xylene solution of benzoyl peroxide was 1:20.
Example 2 of the embodiment
Substantially the same as in example 1, except that: the amount of allicin added in example 1 was 5g, and the amount of allicin added in this example was 10g.
Example 3
Substantially the same as in example 1, except that: the amount of allicin added in example 1 was 5g, and the amount of allicin added in this example was 15g.
Example 4
Substantially the same as in example 1, except that: the amount of allicin added in example 1 was 5g, and the amount of allicin added in this example was 20g.
Example 5
Substantially the same as in example 1, except that: the amount of allicin added in example 1 was 5g, and the amount of allicin added in this example was 25g.
Taking the allicin grafted amphipathic photocatalytic antifouling paint special for the culture net cage prepared by the method described in the embodiment 1-5, and respectively carrying out ultrasonic dispersion treatment for 120s to obtain five allicin grafted amphipathic photocatalytic antifouling paint special for the culture net cage; and then respectively immersing the five pieces of netting into five parts of allicin grafted amphiphilic photocatalytic antifouling paint special for the culture net cage, taking out after 5min, and hanging and airing in a shade place to obtain the netting with the anti-corrosion coating. Shellfish culture experiments were performed with a netting with an anti-corrosive coating. The results of testing the relevant properties and traits after the test are shown in Table 1.
TABLE 1
| Numbering device | Allicin addition amount/g | Wet mass adhesion (kg) of 90 days old fouling organisms | Growth rate/%of shellfish cultivated in 90 days | Coating flexibility/mm | Adhesion of coating |
| Example 1 | 5 | 1.18 | 121 | 0.5 | 0 |
| Example 2 | 10 | 0.99 | 141 | 0.5 | 0 |
| Example 3 | 15 | 0.85 | 179 | 0.5 | 0 |
| Example 4 | 20 | 0.74 | 211 | 0.5 | 0 |
| Example 5 | 25 | 0.56 | 227 | 0.5 | 0 |
The attachment rate of the wet mass of the fouling organisms is calculated according to the following formula:
fouling organism wet mass adhesion = ("a m 1 -m 2 )/S；
Wherein:m 1 the weight (kg) of the net sheet after being hung on the sea,m 2 the net piece is dip-coated and dried to obtain the mass (kg),Sfor the surface area of the mesh (m 2 ）。
The growth rate of the cultured shellfish is calculated according to the following formula:
shellfish growth rate = (in the course of cultivation)W 1 -W 2 )/W 1 ×100%；
Wherein:W 1 the quality (g) of the young shellfish,W 2 the parent shellfish quality (g).
Coating flexibility was tested according to national standard coating flexibility determination method GB/T1731-1993; the adhesion of the coating was tested according to national standard GB/T9286-1998.
The practical applicability of the present invention is illustrated by using ethyl acrylate as the acrylic monomer in the above examples 1-5, and the present invention can be achieved and expected effect can be achieved if butyl acrylate is used instead of ethyl acrylate in the above examples 1-5. In the same way, in the above embodiments 1 to 5, the use amount of each material, the reaction temperature, the reaction time, and the like are all selected to describe the feasibility of the present invention, but not only the specific value selected in the embodiment can achieve the purpose of the present invention, but also any specific value of the use amount range of the material, the numerical range of the reaction temperature, and the numerical range of the reaction time in the claims can achieve the purpose of the present invention and achieve the expected effect, only for brevity and redundancy of the description, and no further description is given.
Claims (5)
1. The preparation method of the allicin grafted amphiphilic photocatalytic antifouling paint special for the culture net cage is characterized by comprising the following steps of:
(1) Adding multidimensional carbon nitride and silane coupling agent KH-570 into absolute ethyl alcohol, carrying out surface treatment on the multidimensional carbon nitride for 3-6 hours at the temperature of 40-55 ℃, carrying out solid-liquid separation after the surface treatment is finished, washing separated solid particles with a detergent, and then carrying out vacuum drying on the solid particles at the temperature of 60-70 ℃ to obtain modified multidimensional carbon nitride; the mass volume ratio of the multidimensional carbon nitride to the silane coupling agent KH-570 is 1-5 g:0.5-6.5 mL;
(2) Carrying out free radical solution polymerization reaction on a mixed monomer formed by mixing a fluorine-containing acrylic ester monomer, functionalized polyethylene glycol, allicin and an acrylic ester monomer and modified multidimensional carbon nitride under the action of a transition metal catalyst to obtain the allicin grafted amphiphilic photocatalytic antifouling paint special for the culture net cage;
the specific operation of the step (2) is as follows: adding modified multidimensional carbon nitride and a transition metal catalyst into dimethylbenzene, dropwise adding a mixed monomer at the temperature of 55-70 ℃ under the protection of nitrogen and stirring, and after the dropwise adding is finished, continuously reacting the added dimethylbenzene solution of benzoyl peroxide for 4-12 hours, thereby obtaining the allicin grafted amphipathic photocatalytic antifouling paint special for the culture net cage;
the fluorine-containing acrylate monomer is hexafluorobutyl methacrylate, the functionalized polyethylene glycol is polyethylene glycol diallyl ether, and the transition metal catalyst is cuprous bromide.
2. The preparation method of the allicin grafted amphiphilic photocatalytic antifouling paint special for the culture net cage, which is disclosed in claim 1, is characterized by comprising the following steps: the dosage of the modified multidimensional carbon nitride is 0.1-12% of the mass of the mixed monomer, and the dosage of the transition metal catalyst is 0.1-0.2% of the mass of the mixed monomer; the dosage of the dimethylbenzene is 2-5% of the mass of the mixed monomer; the dosage of the dimethylbenzene solution of the benzoyl peroxide is 3-5% of the mass of the mixed monomer, and the mass ratio of the benzoyl peroxide to the dimethylbenzene in the dimethylbenzene solution of the benzoyl peroxide is 1:12-25; the weight ratio of the fluorine-containing acrylic ester monomer to the functional polyethylene glycol to the allicin to the acrylic ester monomer is 1-11:1-12:1-5:6-12.
3. The preparation method of the allicin grafted amphiphilic photocatalytic antifouling paint special for the culture net cage, which is disclosed in claim 2, is characterized by comprising the following steps: the dosage of the modified multidimensional carbon nitride is 0.5-5% of the mass of the mixed monomer.
4. The preparation method of the allicin grafted amphiphilic photocatalytic antifouling paint special for the culture net cage, which is disclosed in claim 1, is characterized by comprising the following steps: the mass volume ratio of the multidimensional carbon nitride to the silane coupling agent KH-570 is 1-5 g:2.5-5 mL.
5. The preparation method of the allicin grafted amphiphilic photocatalytic antifouling paint special for the culture net cage, which is disclosed in claim 1, is characterized by comprising the following steps: the acrylic monomer is any one of butyl acrylate and ethyl acrylate or a mixture of the butyl acrylate and the ethyl acrylate in any proportion.
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