CN115029028A - Application of novel photocatalytic antifouling agent - Google Patents
Application of novel photocatalytic antifouling agent Download PDFInfo
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- CN115029028A CN115029028A CN202210679259.8A CN202210679259A CN115029028A CN 115029028 A CN115029028 A CN 115029028A CN 202210679259 A CN202210679259 A CN 202210679259A CN 115029028 A CN115029028 A CN 115029028A
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- antifouling
- photocatalyst
- coating
- photocatalytic
- antifouling agent
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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
- 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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
Abstract
The invention belongs to the technical field of development and development of marine antifouling coatings, and provides application of a novel photocatalytic antifouling agent. The use of g-C in the invention 3 N 4 The photocatalyst is used as an antifouling agent, is added into the coating in proportion, and is uniformly stirred, so that the antifouling effect of the prepared coating is obviously improved. The raw materials used in the invention are cheap and easily available, the preparation method is simple, the control is easy, and the equipment requirement is low. g-C 3 N 4 The photocatalyst has excellent antifouling effect in the antifouling process, and can not release heavy metal, and the photocatalyst accords with the green environmental protection concept and is environment-friendly.
Description
Technical Field
The invention belongs to the technical field of development and development of marine antifouling coatings, relates to application of a novel photocatalytic antifouling agent, and particularly relates to application of modified carbon nitride with photocatalytic activity as an antifouling additive, which can be expanded to other nano photocatalysts with visible light photocatalytic performance.
Background
Blue oceans have abundant resources, and the "marching oceans" have become the future development strategy in China. At present, marine transportation has made an important contribution to the development of human socioeconomic development, but the adverse effects of marine biofouling on ships and other marine engineering are becoming increasingly apparent. Fouling of the hull surface during marine transport increases frictional resistance, resulting in low fuel efficiency. There is evidence that fouling increases fuel costs by 30-40% with a global economic loss of about $ 100 million per year. In order to reduce the damage of marine biofouling, the antifouling paint coated on the surface of the ship body can effectively prevent the growth of marine biofouling organisms.
Early in the development of antifouling coatings, tributyltin (TBT) was used as an antifouling additive, but was banned because of its strong biotoxicity. Currently, most of the commercially used antifouling coatings use cuprous oxide as an antifouling agent, and although the antifouling coating has low ecological toxicity, copper as a heavy metal can still be enriched in organisms, so that the hazards of cell distortion and the like are caused. The research on the copper-free and tin-free eco-friendly antifouling paint conforms to the concept of ecological China and has important significance for protecting the ecological diversity of oceans.
The modified carbon nitride photocatalyst is used as a semiconductor material with strong oxidizing property and no pollution, and shows excellent sterilization performance. Li et al (Li Y, Zhang C, ShuaiD, et al. Water Research,2016,106,249-258) studied polymeric graphite carbon nitride (g-C) using MS2 phage as the subject 3 N 4 ) The experiment shows that the fire extinguishing capability to the virus under the condition of visible light illumination is in g-C 3 N 4 Has a concentration of 150mgL -1 When the initial concentration is 1X 10 after 6h irradiation with visible light 8 PFUmL -1 The MS2 of (a) was completely inactivated and had good stability. Wang et al (Teng Z, Yang N, Lv H, et al chem,2019,5,664- 3 N 4 After modification, the sterilization effect of the modified Escherichia coli can even reach 99.9999% after irradiation for 0.5h under visible light. To sum up, g-C 3 N 4 The photocatalyst exhibits excellent bactericidal effect. At present, there is no g-C 3 N 4 As an antifouling additive in antifouling paints.
In conclusion, the invention is achieved by adding g-C to a laboratory formulated waterborne epoxy resin or a commercial antifouling paint 3 N 4 The photocatalyst and the coating show enhanced antifouling performance, have better application prospect in the antifouling effect of ship bodies and other marine equipment, and have great significance for meeting the requirements of high antifouling effect and high reliability of ships in marine environmentThe economic value and the strategic significance of the design.
Disclosure of Invention
The technical problem to be solved by the invention is to add g-C into the coating 3 N 4 The photocatalyst can achieve the enhanced antifouling effect, the used raw materials are cheap and easy to obtain, the preparation method is simple and easy to control, the equipment requirement is low, and the prepared antifouling paint is environment-friendly.
The technical scheme of the invention is as follows:
modified carbon nitride is used as the novel photocatalytic antifouling agent, and the modified carbon nitride is used for generating active oxygen species such as hydroxyl radicals under illumination, so that the modified carbon nitride has a strong oxidation or inactivation effect on various microorganisms, and the antifouling performance of the coating is enhanced.
The preparation method of the coating added with the photocatalytic antifouling agent comprises the following steps:
1)g-C 3 N 4 preparation of the photocatalyst: calcining urea or melamine as precursor at 550 deg.C for 4h at a heating rate of 2 deg.C/min, grinding into powder with mortar, and calcining at 500 deg.C for 2h at a heating rate of 2 deg.C/min to obtain powder product g-C 3 N 4 A photocatalyst.
2) Preparation of the antifouling paint: g-C obtained in step 1) 3 N 4 The powder is added into the water-based epoxy resin or the commercial antifouling paint in proportion and stirred uniformly, wherein the formula of the water-based epoxy resin is as follows: the mass ratio of the water to the waterborne epoxy resin to the defoaming agent to the dispersing agent is 34: 18: 0.1: 0.1.
furthermore, the addition amount of the novel photocatalytic antifouling agent accounts for 0.2-3% of the mass fraction of the coating.
The modified carbon nitride is replaced by carbon-doped titanium oxide or nitrogen-doped titanium oxide.
The invention has the beneficial effects that: the invention provides g-C 3 N 4 Use of a photocatalyst as a novel antifouling additive, g-C 3 N 4 The photocatalyst is used as an antifouling additive, and compared with the traditional antifouling additive, the photocatalyst does not contain heavy metal elements such as copper, tin and the like, and is more environment-friendly。
Drawings
FIG. 1 is g-C 3 N 4 The abscissa is twice the diffraction angle (2 θ) and the ordinate is the diffraction peak intensity (a.u.).
FIG. 2a is g-C prepared by calcining melamine 3 N 4 Scanning electron micrographs of the photocatalyst; FIG. 2b is g-C prepared by calcining urea 3 N 4 Scanning electron micrograph (c).
FIG. 3 shows g-C for the synthesis of melamine and urea 3 N 4 The photocatalytic antifouling paint prepared by mixing the water-based epoxy resin and other additives as an antifouling additive (the addition amount is 0.6%) can inactivate escherichia coli under simulated sunlight irradiation.
FIG. 4 shows g-C for the synthesis of melamine and urea 3 N 4 The photocatalytic antifouling paint prepared by mixing the antifouling paint as an antifouling additive (with the addition of 0.6%) has the capability of inactivating escherichia coli under the irradiation of simulated sunlight.
FIG. 5 shows g-C for the synthesis of melamine and urea 3 N 4 The photocatalytic antifouling paint prepared by mixing the water-based epoxy resin and other additives as an antifouling additive (the addition amount is 3%) can inactivate escherichia coli under simulated sunlight irradiation.
FIG. 6 shows g-C for the synthesis of melamine and urea 3 N 4 The photocatalytic antifouling paint prepared by mixing the water-based epoxy resin and other additives as an antifouling additive (the addition amount is 0.2%) can inactivate escherichia coli under simulated sunlight irradiation.
Detailed description of the invention
The following describes the specific implementation method of the present invention in detail with reference to the technical scheme and the attached drawings.
Example 1
First of all, g-C 3 N 4 Weighing 25g of precursor by taking urea or melamine as the precursor, placing the precursor into a crucible, sealing the crucible by using tinfoil, placing the crucible into a muffle furnace, calcining the crucible for 4 hours at 550 ℃ at the heating rate of 2 ℃/min, grinding the crucible into powder by using a mortar, calcining the powder for 2 hours at 500 ℃ at the heating rate of 2 ℃/min, and pulverizing the powderThe end product is g-C 3 N 4 A photocatalyst.
Weighing of g-C 3 N 4 0.3g of powder, 34mL of pure water, and mixing to obtain dispersed g-C 3 N 4 An aqueous solution of (a).
Weighing 18g of waterborne epoxy resin, 0.1g of dispersant, 0.1g of defoamer and dispersion g-C 3 N 4 The aqueous solution is mixed evenly to form the photocatalytic antifouling paint.
g-C prepared by using urea or melamine as precursor in antifouling performance simulation test 3 N 4 The inactivation effect of the photocatalytic antifouling paint prepared from the antifouling additive (the addition amount is 0.6%) on escherichia coli in 4 hours under the irradiation of simulated sunlight exceeds 99.9%.
Example 2
Weighing of g-C 3 N 4 0.3g of powder, 50g of the antifouling paint is weighed and uniformly mixed to form the photocatalytic antifouling paint.
g-C prepared by using urea or melamine as precursor in antifouling performance simulation test 3 N 4 The inactivation effect of the photocatalytic antifouling paint prepared from the antifouling additive (the addition amount is 0.6%) on escherichia coli in 4 hours under the irradiation of simulated sunlight is over 99%.
Example 3
In the preparation of the antifouling paint according to example 1, g-C 3 N 4 The mass of the powder was increased to 1.5g, the raw material usage and other experimental procedures were kept constant, and g-C was produced 3 N 4 Photocatalyst antifouling paint.
g-C prepared by using urea or melamine as precursor in antifouling performance simulation test 3 N 4 The inactivation effect of the photocatalytic antifouling paint prepared from the antifouling additive (the addition amount is 3%) on escherichia coli in 4 hours under simulated sunlight irradiation exceeds 99%.
Example 4
In the preparation of the antifouling paint according to example 1, g-C 3 N 4 The mass of the powder is reduced to 0.1g, the raw material dosage and other experimental steps are kept unchanged, and g-C is prepared 3 N 4 Photocatalyst antifouling paint.
g-C prepared by using urea or melamine as precursor in antifouling performance simulation test 3 N 4 The inactivation effect of the photocatalytic antifouling paint prepared from the antifouling additive (the addition amount is 3%) on escherichia coli in 4 hours under simulated sunlight irradiation exceeds 99%.
Example 5
In the preparation of the antifouling paint according to example 2, g-C 3 N 4 The mass of the powder was increased to 1.5g, and the amount of raw materials and other experimental steps were kept constant to obtain g-C 3 N 4 Photocatalyst antifouling paint.
Example 6
In the preparation of the antifouling paint according to example 2, g-C 3 N 4 The mass of the powder is reduced to 0.1g, the raw material dosage and other experimental steps are kept unchanged, and g-C is prepared 3 N 4 Photocatalyst antifouling paint.
Example 7
According to examples 1 to 6, g to C 3 N 4 Photocatalyst is replaced by nitrogen-doped TiO 2 The raw material dosage and other experimental steps are kept unchanged to prepare the nitrogen-doped TiO 2 Photocatalyst antifouling paint.
Nitrogen doped TiO in antifouling performance simulation test 2 The inactivation effect of the photocatalytic antifouling paint prepared from the antifouling additive (the addition amount is 0.6%) on escherichia coli in 4 hours under the irradiation of simulated sunlight is over 99%.
Example 8
According to examples 1 to 6, g to C 3 N 4 Photocatalyst is changed into carbon-doped TiO 2 The raw material consumption and other experimental steps are kept unchanged to prepare the carbon-doped TiO 2 Photocatalyst antifouling paint.
Carbon doped TiO in antifouling performance simulation test 2 The inactivation effect of the photocatalytic antifouling paint prepared from the antifouling additive (the addition amount is 0.6%) on escherichia coli in 4 hours under the irradiation of simulated sunlight exceeds 95%.
Claims (4)
1. The application of the novel photocatalytic antifouling agent is to use modified carbon nitride as the novel photocatalytic antifouling agent and utilize the bactericidal performance of the modified carbon nitride under illumination to enhance the antifouling effect of the coating.
2. Use according to claim 1, wherein the modified carbon nitride is replaced by carbon-doped titanium oxide or nitrogen-doped titanium oxide.
3. The use according to claim 2, wherein the novel photocatalytic antifoulant is added in an amount of 0.2 to 3% by mass based on the coating.
4. Use according to any one of claims 1 to 3, wherein the coating is a waterborne epoxy resin or a commercial antifouling coating.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210679259.8A CN115029028A (en) | 2022-06-16 | 2022-06-16 | Application of novel photocatalytic antifouling agent |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202210679259.8A CN115029028A (en) | 2022-06-16 | 2022-06-16 | Application of novel photocatalytic antifouling agent |
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| CN115029028A true CN115029028A (en) | 2022-09-09 |
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| CN202210679259.8A Withdrawn CN115029028A (en) | 2022-06-16 | 2022-06-16 | Application of novel photocatalytic antifouling agent |
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Citations (10)
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|---|---|---|---|---|
| CN1696228A (en) * | 2005-05-26 | 2005-11-16 | 北京科技大学 | Light catalyzed coating modified by nitrogen dopen Nano titanium dioxide and preparation method |
| US20080187457A1 (en) * | 2007-02-05 | 2008-08-07 | Mangiardi John R | Antibacterial Titanium Dioxide Compositions |
| CN102277051A (en) * | 2010-06-09 | 2011-12-14 | 上海申得欧有限公司 | TiO2 visible light internal wall emulsion paint without volatile organic compounds (VOC) and preparation method thereof |
| EP2407236A1 (en) * | 2010-07-13 | 2012-01-18 | Theta Chemicals Limited | Photocatalyst comprising a doped material |
| CN107541117A (en) * | 2017-08-30 | 2018-01-05 | 深圳先进技术研究院 | Nanometer fishing net waterborne anti-fouling coatings and its preparation method and application |
| CN108997876A (en) * | 2018-09-10 | 2018-12-14 | 成都职业技术学院 | A kind of antibacterial is antifouling, repelling mosquitoes and preventing insects water-borne wood coatings and preparation method thereof |
| CN109942204A (en) * | 2019-04-26 | 2019-06-28 | 湖南飞博环保科技有限公司 | A kind of dirt-resistant self-cleaning material and the preparation method and application thereof |
| CN110655843A (en) * | 2019-09-05 | 2020-01-07 | 哈尔滨工程大学 | C3N4Preparation method of photocatalytic self-polishing resin-based composite coating material |
| CN111138950A (en) * | 2020-01-16 | 2020-05-12 | 沈阳顺风新材料有限公司 | Photoresponse self-cleaning coating and preparation method thereof |
| CN113652166A (en) * | 2021-09-01 | 2021-11-16 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of antibacterial and antiviral environment-friendly interior wall finishing coating and product thereof |
-
2022
- 2022-06-16 CN CN202210679259.8A patent/CN115029028A/en not_active Withdrawn
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1696228A (en) * | 2005-05-26 | 2005-11-16 | 北京科技大学 | Light catalyzed coating modified by nitrogen dopen Nano titanium dioxide and preparation method |
| US20080187457A1 (en) * | 2007-02-05 | 2008-08-07 | Mangiardi John R | Antibacterial Titanium Dioxide Compositions |
| CN102277051A (en) * | 2010-06-09 | 2011-12-14 | 上海申得欧有限公司 | TiO2 visible light internal wall emulsion paint without volatile organic compounds (VOC) and preparation method thereof |
| EP2407236A1 (en) * | 2010-07-13 | 2012-01-18 | Theta Chemicals Limited | Photocatalyst comprising a doped material |
| CN107541117A (en) * | 2017-08-30 | 2018-01-05 | 深圳先进技术研究院 | Nanometer fishing net waterborne anti-fouling coatings and its preparation method and application |
| CN108997876A (en) * | 2018-09-10 | 2018-12-14 | 成都职业技术学院 | A kind of antibacterial is antifouling, repelling mosquitoes and preventing insects water-borne wood coatings and preparation method thereof |
| CN109942204A (en) * | 2019-04-26 | 2019-06-28 | 湖南飞博环保科技有限公司 | A kind of dirt-resistant self-cleaning material and the preparation method and application thereof |
| CN110655843A (en) * | 2019-09-05 | 2020-01-07 | 哈尔滨工程大学 | C3N4Preparation method of photocatalytic self-polishing resin-based composite coating material |
| CN111138950A (en) * | 2020-01-16 | 2020-05-12 | 沈阳顺风新材料有限公司 | Photoresponse self-cleaning coating and preparation method thereof |
| CN113652166A (en) * | 2021-09-01 | 2021-11-16 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of antibacterial and antiviral environment-friendly interior wall finishing coating and product thereof |
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Application publication date: 20220909 |
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