CN115368794B - Method for removing biological pollution of marine ship - Google Patents
Method for removing biological pollution of marine ship Download PDFInfo
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- 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
- C09D133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B63—SHIPS OR OTHER WATERBORNE VESSELS; RELATED EQUIPMENT
- B63B—SHIPS OR OTHER WATERBORNE VESSELS; EQUIPMENT FOR SHIPPING
- B63B59/00—Hull protection specially adapted for vessels; Cleaning devices specially adapted for vessels
- B63B59/04—Preventing hull fouling
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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- C09D5/1687—Use of special additives
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Abstract
The invention discloses a method for removing biological pollution of a marine ship, and belongs to the technical field of biological pollutant removal. The self-repairing hydrogel is prepared from polyvinyl alcohol and modified chitosan, then the water-based polyacrylic acid and the self-repairing hydrogel are mixed, and the mixture is uniformly stirred and coated on the surface of a ship body to form a self-repairing hydrogel coating; the modified chitosan is obtained by modifying chitosan with soyasaponin. The hydrogel coating prepared by the invention has good self-repairing performance, excellent antibacterial, anti-swelling and anti-diatom adhesion performances, and wide application prospect in the field of marine decontamination.
Description
Technical Field
The invention belongs to the technical field of biological pollutant removal, and particularly relates to a method for removing biological pollution of a marine ship.
Background
The ocean is a natural complex equilibrium system and has the characteristics of high salt content, strong conductivity, high biological activity and the like. Marine fouling organisms, also known as marine fouling organisms, are animals, plants and microorganisms that grow on the surface of all facilities at the bottom of ships and in the sea. The marine periphyton is a great variety of organisms, among which barnacles, oysters, ascidians, diatoms, etc. are more harmful and common, and most of them live on the coast and in estuaries. The harm of marine biofouling is mainly manifested in three aspects: 1. after the organisms are attached, the navigation resistance of the ship is increased, the navigation speed is reduced, the power consumption is increased, and the warship fighting capacity is influenced. It is statistical that hull fouling increases energy consumption by 40% and capital costs by 77%. 2. Ships need to frequently enter a dock for overhaul, which wastes a great deal of time and resources. During the refurbishment process, a large amount of toxic waste is also generated. 3. The attachment of microorganisms can also exacerbate the corrosive destruction of marine engineering materials. 4. Bringing new species to allopatrics threatens local ecosystem. Marine biofouling is one of the important problems to be solved urgently in ferry and offshore operation, has an important effect on reducing surface corrosion of marine facilities or ship equipment, reducing oil consumption and the like except marine biofouling, and has great significance in the fields of military affairs, economy, environment and the like. With the progress of science and technology, toxic antifouling materials no longer meet the requirements of the times and are gradually replaced by non-toxic antifouling materials; research and preparation of environment-friendly and efficient antifouling materials are one of the current hot topics.
The hydrogel is a hydrophilic high polymer with a three-dimensional network system and a large number of hydrophilic groups on a molecular chain, is insoluble in water, can absorb a large amount of water in the water to swell, and can continuously keep a semisolid state while absorbing water. In recent years, hydrogel application and research are greatly developed and widely applied to various fields, and the development and development of hydrogel decontamination materials are based on organisms in the nature, are environment-friendly and pollution-free, and show excellent application prospects. The self-repairing hydrogel is prepared from polyvinyl alcohol, modified chitosan and sodium tetraborate, the problems of decontamination and practical application of the self-repairing hydrogel are researched, and a thought is provided for the preparation and application of a marine decontamination material.
Disclosure of Invention
The invention aims to provide a method for removing biological pollution of a marine ship, which adopts self-repairing hydrogel to show good antibacterial, anti-swelling, anti-diatom attachment and self-repairing performances and has wide application prospect in the field of marine pollution removal.
The technical scheme adopted by the invention for realizing the purpose is as follows:
a method of removing biological fouling of a marine vessel, comprising: preparing self-repairing hydrogel from polyvinyl alcohol and modified chitosan, blending the water-based polyacrylic acid and the self-repairing hydrogel, uniformly stirring, and coating the mixture on the surface of a ship body to form a self-repairing hydrogel coating; the modified chitosan is obtained by modifying chitosan with soyasaponin.
The invention provides a method for removing biological pollution of a marine ship, which selects a natural environment-friendly material, is pollution-free and easy to degrade, and has an antibacterial effect, soyasaponin is adopted to modify the chitosan, then the modified chitosan is added into polyvinyl alcohol to prepare hydrogel, and a sodium tetraborate solution is added in the preparation process, so that the modified chitosan and the polyvinyl alcohol form a hydrogel self-repairing system to prepare the self-repairing hydrogel; in addition, the self-repairing hydrogel also shows good performances in the aspects of swelling resistance, diatom attachment resistance and self-repairing; and the self-repairing hydrogel can be recycled, so that the waste of resources is avoided.
The invention also provides a method for removing biological pollution of the marine vessel, which comprises the following steps: adding polyvinyl alcohol and modified chitosan into hot water at 98-100 ℃ for dissolving for 1-1.5h, adding sodium tetraborate solution with the concentration of 0.035-0.04mol/L, stirring and mixing at constant temperature for 1-1.5h, pouring the solution into a mould, standing and defoaming to prepare self-repairing hydrogel, then blending the water-based polyacrylic acid and the self-repairing hydrogel, stirring uniformly, and coating on the surface of a ship body to form a self-repairing hydrogel coating.
Preferably, the mass ratio of the polyvinyl alcohol to the hot water is 1; the mass ratio of the polyvinyl alcohol to the modified chitosan is 1; the mass ratio of the polyvinyl alcohol to the sodium tetraborate is 1.
Preferably, the mass ratio of the water-based polyacrylic acid to the self-repairing hydrogel is 5-8.
Preferably, the thickness of the self-repairing hydrogel coating is 100-120 μm.
The invention also provides a preparation method of the modified chitosan, which comprises the following steps: the chitosan and the soyasaponin are subjected to chemical grafting reaction to prepare the modified chitosan.
Specifically, the preparation method of the modified chitosan specifically comprises the following steps: dissolving chitosan in deionized water, stirring at room temperature for 6-8 hr, standing, adding hydrogen peroxide and ascorbic acid, stirring for 0.5-1 hr, adding soybean saponin, and reacting at constant temperature for 8-10 hr; the whole reaction system is always carried out under the protection of nitrogen; and after the reaction is finished, dialyzing the reaction solution by using a dialysis bag, dialyzing for 65-72h, and freeze-drying to obtain the modified chitosan.
Preferably, the mass volume ratio of the chitosan to the deionized water is 1g; the mass ratio of the chitosan to the soybean saponin is 1.7-1; the mass ratio of the chitosan to the hydrogen peroxide is 1.03-0.05; the mass ratio of the chitosan to the ascorbic acid is 1.003-0.005.
Preferably, the self-healing hydrogel component further comprises dihydroquercetin.
In the process of preparing the self-repairing hydrogel, the dihydroquercetin is added, so that the bacteriostatic performance of the self-repairing hydrogel is further improved, the self-repairing hydrogel has more excellent self-repairing performance, and the attaching capability of marine fouling organisms is inhibited; provides a new theoretical basis for the preparation of the antifouling material; in addition, due to the hydrophobic property of the dihydroquercetin, the swelling resistance of the self-repairing hydrogel is further improved.
Preferably, the mass ratio of the polyvinyl alcohol to the dihydroquercetin is 1.03-0.04.
The invention also discloses application of the self-repairing hydrogel prepared by the preparation method in removing biological pollution of marine ships.
The beneficial effects of the invention include:
the invention provides a method for removing biological pollution of a marine ship, which is characterized in that soyasaponin is adopted to modify chitosan, the prepared modified chitosan is added into polyvinyl alcohol, and after the modified chitosan is uniformly mixed, sodium tetraborate is added, so that the prepared self-repairing hydrogel has good antibacterial, anti-swelling, anti-diatom attachment and self-repairing performances; in addition, the dihydroquercetin is added in the process of preparing the self-repairing hydrogel, so that the antibacterial, anti-swelling, anti-diatom attachment and self-repairing performances of the self-repairing hydrogel are further improved.
The invention provides a method for removing biological pollution of a marine ship, which adopts self-repairing hydrogel to show good antibacterial, anti-swelling, anti-diatom attachment and self-repairing performances, and has wide application prospect in the field of marine pollution removal.
Drawings
FIG. 1 shows the results of IR spectroscopy on modified chitosan prepared in example 1 and chitosan;
FIG. 2 is a diatom attachment resistance test result of the self-healing hydrogels prepared in examples 1-5;
FIG. 3 is a result of a swelling resistance test on the self-healing hydrogels prepared in examples 1 to 5;
FIG. 4 shows the self-repairing performance test results of the self-repairing hydrogels prepared in examples 1 to 5;
FIG. 5 shows the results of the bacteriostatic performance tests of the self-repairing hydrogels prepared in examples 1 to 5.
Detailed Description
The technical solution of the present invention is further described in detail below with reference to the following detailed description and the accompanying drawings:
the chitosan used in the embodiment of the invention is purchased from Shanghai Aladdin Biotechnology Co., ltd, the molecular weight is 179.17KDa, and the deacetylation degree is more than or equal to 95%.
Example 1:
a method for removing biological pollution of a marine vessel specifically comprises the following steps: adding polyvinyl alcohol and modified chitosan into hot water at 98 ℃ for dissolving for 1 hour, adding a sodium tetraborate solution with the concentration of 0.035mol/L, stirring and mixing for 1 hour at constant temperature, pouring the solution into a mould, standing and defoaming to prepare self-repairing hydrogel, then blending water-based polyacrylic acid and the self-repairing hydrogel, stirring uniformly, and coating on the surface of a ship body to form a self-repairing hydrogel coating with the thickness of about 100 mu m; wherein the mass ratio of the polyvinyl alcohol to the hot water is 1; the mass ratio of the polyvinyl alcohol to the modified chitosan is 1; the mass ratio of the polyvinyl alcohol to the sodium tetraborate is 1; the mass ratio of the water-based polyacrylic acid to the self-repairing hydrogel is 5.
The preparation method of the modified chitosan comprises the following steps: dissolving chitosan in deionized water (the mass volume ratio of the chitosan to the deionized water is 1g, 100mL), stirring at room temperature for 6h, standing for later use, adding hydrogen peroxide and ascorbic acid, continuously stirring for 0.5h, adding soybean saponin, and reacting at constant temperature for 8h; the whole reaction system is always carried out under the protection of nitrogen; after the reaction is finished, dialyzing the reaction solution by using a dialysis bag, dialyzing for 65 hours (changing dialysis water every 12 hours), and freeze-drying to obtain a sample; wherein the mass ratio of the chitosan to the soybean saponin is 1; the mass ratio of chitosan to hydrogen peroxide is 1; the mass ratio of chitosan to ascorbic acid is 1.
Example 2:
a method for removing biological pollution of a marine vessel is different from the method in the embodiment 1:
the mass ratio of the polyvinyl alcohol to the hot water is 1; the mass ratio of the polyvinyl alcohol to the modified chitosan is 1; the mass ratio of polyvinyl alcohol to sodium tetraborate is 1; the mass ratio of the water-based polyacrylic acid to the self-repairing hydrogel is 8.
The difference between the preparation method of the modified chitosan and the example 1 is that: the mass ratio of the chitosan to the soybean saponin is 1; the mass ratio of the chitosan to the hydrogen peroxide is 1; the mass ratio of chitosan to ascorbic acid is 1.
Example 3:
a method for removing biological pollution of a marine vessel is different from the method in the embodiment 1: the chitosan is adopted to replace the modified chitosan.
Example 4:
a method for removing biological pollution of a marine vessel is different from the method in the embodiment 1: adding dihydroquercetin;
the method comprises the following specific steps: adding polyvinyl alcohol and modified chitosan into hot water at 98 ℃ for dissolving for 1h, then adding sodium tetraborate solution with the concentration of 0.035mol/L and dihydroquercetin, stirring and mixing for 1h at constant temperature, pouring the solution into a mould, standing and defoaming to prepare self-repairing hydrogel; then blending the water-based polyacrylic acid and the self-repairing hydrogel, uniformly stirring, and coating the mixture on the surface of a ship body to form a self-repairing hydrogel coating;
wherein the mass ratio of the polyvinyl alcohol to the hot water is 1; the mass ratio of the polyvinyl alcohol to the modified chitosan is 1; the mass ratio of the polyvinyl alcohol to the sodium tetraborate is 1; the mass ratio of the water-based polyacrylic acid to the self-repairing hydrogel is 5; the mass ratio of the polyvinyl alcohol to the dihydroquercetin is 1.
The modified chitosan was prepared in the same manner as in example 1.
Example 5:
a difference between the method for removing biological pollution of a marine vessel and the embodiment 3 is that: adding dihydroquercetin; the mass ratio of the polyvinyl alcohol to the dihydroquercetin is 1.
Test example 1:
1.1 Infrared Spectroscopy
Analyzing by Fourier infrared spectrometer and KBr tabletting method, and scanning wavelength is 4000-500cm -1 。
The modified chitosan prepared in example 1 and chitosan were subjected to the above-described test, and the results are shown in fig. 1. As can be seen from FIG. 1, 1692cm -1 The characteristic absorption peak of C = C bond exists, which indicates that the soyasaponin participates in the generation reaction of the modified chitosan.
1.2 anti-Diatom attachment test
The experimental groups are: the self-healing hydrogel prepared in example 1 is designated as N1; the self-healing hydrogel prepared in example 2 was designated as N2; the self-healing hydrogel prepared in example 3 is designated as N3; the self-healing hydrogel prepared in example 4 was designated as N4; the self-healing hydrogel prepared in example 5 was designated as N5; respectively take 10 6 10mL of small Nitzschia closterium per mL are added into a six-well plate, then a gel sample with the width of 1cm is added, and the gel sample is cultured in a light incubator with the illumination intensity of 3 levels and the light dark period (12 h/12 h), the temperature is 23 ℃, and the gel sample is cultured for 24h. And taking out the gel sample, washing for 5 times by using sterile seawater, removing the non-adhered small crescent rhombohedral algae, observing by using a polarizing microscope, taking 5 visual fields for each sample, counting the area of the small crescent rhombohedral algae adhered to the surface of the sample by using Image J, and calculating an average value.
The self-healing hydrogels prepared in examples 1-5 were tested as described above, and the results are shown in fig. 2. As can be seen from fig. 2, in example 1, compared with example 3, the density of diatoms is reduced, which indicates that modification effect of soyasaponin on chitosan enhances anti-diatom attachment performance of the self-repairing hydrogel; compared with the embodiment 1, in the embodiment 4, compared with the embodiment 3, the density of the diatom is obviously reduced in the embodiment 5, which shows that the diatom attachment resistance of the self-repairing hydrogel can be effectively improved by adding the dihydroquercetin in the preparation process of the self-repairing hydrogel; wherein, dihydroquercetin is added while the soyasaponin acts on the chitosan, so as to further enhance the diatom attachment resistance of the self-repairing hydrogel.
1.3 swelling resistance test
The experimental groups are the same as those in test example 1.2; taking a gel sample, removing water in a vacuum oven at 40 ℃, weighing the sample and recording the mass as m 1 Soaking in deionized water to reach saturation state, i.e. swelling equilibrium state, removing excess water on the surface of hydrogel, and weighing mass as m 2 And calculating the gel equilibrium swelling degree SR, wherein the formula is as follows:
SR=[(m 2 -m 1 )/m 1 ]×100%。
the self-healing hydrogels prepared in examples 1 to 5 were tested as described above, and the results are shown in fig. 3. As can be seen from fig. 3, in example 1, compared with example 3, the difference in the equilibrium swelling degree is small, which indicates that the modification effect of soyasaponin on chitosan has no negative influence on the swelling resistance of the self-repairing hydrogel; compared with the examples 1 and 5 and 3, the equilibrium swelling degree of the self-repairing hydrogel in the example 4 is obviously reduced, which shows that the anti-swelling performance of the self-repairing hydrogel is improved when the dihydroquercetin is added.
1.4 self-repair Performance test
The experimental groups are the same as those in test example 1.2; the hydrogel sample was cut in half and the two sections of hydrogel were then contacted under water. There is no other stress or external stimulus during the self-healing process. And after self-repairing, a universal testing machine is adopted to carry out tensile test, and the self-repairing efficiency M is calculated.
M/%=(T1/T0)×100%
Wherein T1 is the tensile strength after self-repairing, KPa; t0 is the tensile strength, KPa, of the original hydrogel sample.
The self-healing hydrogels prepared in examples 1 to 5 were tested as described above, and the results are shown in fig. 4. As can be seen from fig. 4, in example 1, compared with example 3, the self-repairing efficiency is improved, which indicates that the modification effect of soyasaponin on chitosan enhances the self-repairing performance of the self-repairing hydrogel; compared with the embodiment 1, the self-repairing efficiency of the embodiment 5 is obviously improved compared with that of the embodiment 3, which shows that the self-repairing performance of the self-repairing hydrogel can be effectively improved by adding the dihydroquercetin in the preparation process of the self-repairing hydrogel; the dihydroquercetin is added while the soyasaponin acts on the chitosan, so that the self-repairing performance of the self-repairing hydrogel can be further enhanced.
1.5 bacteriostatic Property test
The experimental groups are the same as those in test example 1.2; taking staphylococcus aureus as a test strain, placing the test strain into 10mL of liquid bacterial nutrient solution, culturing for 12h in a constant temperature oscillator at 37 ℃, taking out the test strain, testing the concentration of the staphylococcus aureus, and then diluting the test strain to a target concentration by using PBS buffer solution. Taking 0.75g of sample gel to be tested, cutting into small pieces, adding the small pieces into 75mL of staphylococcus aureus solution, oscillating and contacting for 24 hours in a constant-temperature oscillator, then taking out a proper amount of bacterial liquid for plate-coating culture, calculating the concentration of the bacterial liquid according to the number of growing colonies and calculating the bacteriostatic rate, wherein the R formula of the bacteriostatic rate is as follows:
R/%=[(Q0-Q1)/Q0]×100%
wherein Q0 is the concentration of the blank control group bacterial liquid; q1 is the concentration of the bacterial liquid after the sample contacts the bacterial liquid.
The self-healing hydrogels prepared in examples 1 to 5 were tested as described above, and the results are shown in fig. 5. As can be seen from fig. 5, in example 1, compared with example 3, the bacteriostatic rate is improved, which indicates that the modification effect of soyasaponin on chitosan enhances the bacteriostatic performance of the self-repairing hydrogel; compared with the embodiment 1, the embodiment 5 has obviously improved bacteriostatic rate compared with the embodiment 3, which shows that the bacteriostatic performance of the self-repairing hydrogel can be effectively improved by adding dihydroquercetin in the preparation process of the self-repairing hydrogel; when the dihydroquercetin is added while the soyasaponin acts on the chitosan, the bacteriostatic performance of the self-repairing hydrogel is further improved.
Conventional techniques in the above embodiments are known to those skilled in the art, and therefore, will not be described in detail herein.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (8)
1. The application of the self-repairing hydrogel in biological pollution removal of marine ships is characterized in that the self-repairing hydrogel is prepared from polyvinyl alcohol and modified chitosan, wherein the modified chitosan is obtained by modifying chitosan with soyasaponin; the application specifically comprises the following steps: and blending the water-based polyacrylic acid and the self-repairing hydrogel, uniformly stirring, and coating the mixture on the surface of a ship body to form the self-repairing hydrogel coating.
2. Use according to claim 1, characterized in that: the mass ratio of the polyvinyl alcohol to the modified chitosan is 1.5-0.8.
3. Use according to claim 1, characterized in that: the mass ratio of the water-based polyacrylic acid to the self-repairing hydrogel is 5-8.
4. Use according to claim 1, characterized in that: the thickness of the self-repairing hydrogel coating is 100-120 mu m.
5. Use according to claim 1, characterized in that: the preparation method of the modified chitosan comprises the following steps: the chitosan and the soyasaponin are subjected to chemical grafting reaction to prepare the modified chitosan.
6. Use according to claim 1, characterized in that: the mass ratio of the chitosan to the soybean saponin is 1.7-1.
7. Use according to claim 1, characterized in that: the self-healing hydrogel component further comprises dihydroquercetin.
8. Use according to claim 7, characterized in that: the mass ratio of the polyvinyl alcohol to the dihydroquercetin is 1.03-0.04.
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Denomination of invention: Methods for removing biological pollution from marine vessels Granted publication date: 20230321 Pledgee: Zhejiang Zhoushan Putuo Rural Commercial Bank Co.,Ltd. Zhujiajian sub branch Pledgor: ZHEJIANG HANGHAI ENVIRONMENTAL PROTECTION TECHNOLOGY Co.,Ltd. Registration number: Y2024330001517 |
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