CN109957307B - Quaternary ammonium salt modified epoxy coating with algae inhibiting effect and preparation method thereof - Google Patents

Quaternary ammonium salt modified epoxy coating with algae inhibiting effect and preparation method thereof Download PDF

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CN109957307B
CN109957307B CN201910219932.8A CN201910219932A CN109957307B CN 109957307 B CN109957307 B CN 109957307B CN 201910219932 A CN201910219932 A CN 201910219932A CN 109957307 B CN109957307 B CN 109957307B
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quaternary ammonium
ammonium salt
epoxy coating
coating
stirring
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CN109957307A (en
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王志伟
陈颖青
李震
陈广
汪喜生
张厚强
王雪野
王天霖
吴志超
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Tongji University
Shanghai Chengtou Waste Water Treatment Co Ltd
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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
    • 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
    • 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
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    • C09D5/1625—Non-macromolecular compounds organic
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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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
    • 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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Abstract

The invention discloses a preparation method of a quaternary ammonium salt modified epoxy coating with an algae inhibiting effect, and belongs to the technical field of coating processing. Firstly, adding quaternary ammonium salt solid powder into glycidyl ether epoxy paint, and obtaining uniform quaternary ammonium salt/epoxy paint mixed solution after ultrasonic treatment and stirring; then adding a curing agent into the obtained mixed solution, uniformly stirring, and standing for reaction to obtain a quaternary ammonium salt/epoxy coating composite emulsion; and (3) finally, brushing the quaternary ammonium salt/epoxy coating composite emulsion obtained in the step (2) on a substrate material by using a brushing method, and drying to obtain the quaternary ammonium salt modified epoxy coating. The preparation method is simple to operate, low in cost and beneficial to realizing industrial production, and the quaternary ammonium salt modified epoxy coating prepared by the method has no obvious influence on the basic performance of the coating while combining the algae inhibiting effect of the quaternary ammonium salt, and has a good and lasting algae inhibiting effect.

Description

Quaternary ammonium salt modified epoxy coating with algae inhibiting effect and preparation method thereof
Technical Field
The invention relates to a quaternary ammonium salt modified epoxy coating with an algae inhibiting effect and a preparation method thereof, belonging to the technical field of coating processing.
Background
Biofouling refers to the phenomenon of organic matter and microorganisms, especially algae, adhering to and damaging the surfaces of underwater equipment, structures. Hitherto, coating antifouling paint on the surface of underwater equipment and structures to inhibit the adhesion and growth of organisms is one of the most economic and effective strategies for solving the problem of biological pollution, and the development of novel broad-spectrum, efficient, low-toxicity and environment-friendly antifouling paint has become a hot research field.
The quaternary ammonium salt compound is the most important one of the cationic surfactants, has the advantages of broad spectrum, low toxicity, environmental protection and the like, and is widely applied to the fields of bactericides, disinfectants and the like. In addition to bacteriostatic effects, quaternary ammonium salts also have inhibitory effects on the growth and reproduction of algae. The inhibition of algae growth by quaternary ammonium salts mainly goes through the following processes: after the alkyl long chain of the quaternary ammonium salt breaks the cell membrane/wall structure, the quaternary ammonium salt can react with the leaf alcohol group of chlorophyll to break the function that the chlorophyll, protein and phospholipid are combined into a stable complex to carry out photosynthesis; meanwhile, the long alkyl chain can also react with protein and enzyme in algae cells, so that the metabolism of the algae cells is abnormal. Therefore, the quaternary ammonium salt has the characteristics of high efficiency, low toxicity, difficult influence of pH value change, convenient use, stable chemical performance and the like, and is suitable for resisting the adhesion of microorganisms, particularly bacteria and algae on the surface of the coating, thereby achieving the purpose of preventing the surface of the coating from being polluted by the microorganisms, the algae and secretions thereof.
Although the quaternary ammonium salt is added into the coating, the obtained coating material has an algae inhibiting function, the algae inhibiting effect of the coating material is influenced by factors such as the binding force between the quaternary ammonium salt and the coating, if the binding force between the quaternary ammonium salt and the coating is low, the quaternary ammonium salt in the coating material cannot exert a good algae inhibiting effect, and in addition, the quaternary ammonium salt possibly influences the performances of the coating material, such as hydrophily and hydrophobicity and stability, so that the adhesion effect of the coating on the surface of the base material is influenced, and therefore, the problem that how to exert the algae inhibiting effect of the quaternary ammonium salt as far as possible on the basis of not changing the basic performance of the coating material is a great need to be solved.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides the quaternary ammonium salt modified epoxy coating with the algae inhibiting effect and the preparation method thereof, the preparation method is simple to operate and low in cost, and is beneficial to realizing industrial production, the quaternary ammonium salt modified epoxy coating prepared by the method has no obvious influence on the basic performance of the coating while combining the algae inhibiting effect of the quaternary ammonium salt, and has good and lasting algae inhibiting effect.
In order to achieve the technical purpose, the technical scheme of the invention is as follows:
a preparation method of a quaternary ammonium salt modified epoxy coating with an algae inhibiting effect comprises the following steps:
(1) adding the quaternary ammonium salt solid powder into the glycidyl ether epoxy coating, and obtaining uniform quaternary ammonium salt/epoxy coating mixed solution after ultrasonic treatment and stirring;
(2) adding a curing agent into the mixed solution obtained in the step (1), uniformly stirring, and standing for reaction to obtain a quaternary ammonium salt/epoxy coating composite emulsion;
(3) coating the quaternary ammonium salt/epoxy coating composite emulsion obtained in the step (2) on a substrate material by a coating method, and drying to obtain a quaternary ammonium salt modified epoxy coating;
the quaternary ammonium salt is dodecyl dimethyl benzyl ammonium chloride or dodecyl dimethyl benzyl ammonium bromide, and the curing agent is a phenolic aldehyde amine curing agent; based on the parts by weight of the quaternary ammonium salt/epoxy coating composite emulsion, every 100 parts of the quaternary ammonium salt/epoxy coating composite emulsion contains 5-15 parts of a curing agent, 0.1-2 parts of quaternary ammonium salt and the balance of epoxy coating; the ultrasonic time in the step (1) is 10-30 min, and the stirring is performed by using a magnetic stirrer with the rotating speed of 500-1500 rpm for 60-180 min; the stirring in the step (2) is performed for 1-10 min by using a magnetic stirrer with the rotating speed of 100-1000 rpm; the standing time in the step (2) is 30-150 s; the drying time in the step (3) is 8-24 hours; the substrate material is non-woven fabric.
The quaternary ammonium salt modified epoxy coating prepared by the method.
Compared with the prior art, the invention innovatively adopts the broad-spectrum bactericide quaternary ammonium salt to modify the epoxy coating by a mechanical stirring and mixing method, successfully introduces the algae inhibiting function of the quaternary ammonium salt into the quaternary ammonium salt modified epoxy coating, and develops the quaternary ammonium salt modified epoxy coating with obvious algae adhesion inhibiting effect. The method of the invention has the following beneficial effects:
(1) according to the invention, by selecting the glycidyl ether epoxy coating with high adhesion to the quaternary ammonium salt and the quaternary ammonium salt with the hydrophobic long carbon chain, and utilizing the inherent polar hydroxyl and ether bond in the molecular chain of the glycidyl ether epoxy resin and the amphiphilic property of the quaternary ammonium salt, the quaternary ammonium salt and the epoxy resin have stronger binding force and fusion degree, the quaternary ammonium salt is fully adsorbed to the molecular chain of the epoxy resin, and when the quaternary ammonium salt is dried and formed in the air, the hydrophobic long carbon chain of the quaternary ammonium salt can segregate to the surface of the epoxy coating, so that the algae inhibiting behavior of the quaternary ammonium salt can be well exerted, and the basic performance of the quaternary ammonium salt modified epoxy coating cannot be influenced.
(2) According to the invention, by optimizing the preparation conditions of the quaternary ammonium salt/epoxy coating composite emulsion and the using amount of each substance in the composite emulsion, the binding force between the epoxy resin and the quaternary ammonium salt can be improved, on one hand, more quaternary ammonium salt can be adsorbed onto the epoxy resin molecular chain, the algae inhibition effect of the quaternary ammonium salt modified epoxy coating is improved, and on the other hand, the existence time of the quaternary ammonium salt in the quaternary ammonium salt modified epoxy coating can be prolonged, so that the quaternary ammonium salt modified epoxy coating has a long algae inhibition effect and a long service life.
(3) The method has the advantages of simple operation, low requirement on equipment, low cost and contribution to realizing industrial production.
Drawings
FIG. 1 is a C L SM picture of the surface of epoxy coating F0 after 5 days of contact culture with Chlorella vulgaris;
FIG. 2 is a C L SM picture of the coated surface of an epoxy coating F1 after 5 days of contact culture with Chlorella vulgaris;
FIG. 3 is a C L SM picture of the coated surface of an epoxy coating F5 after 5 days of contact culture with Chlorella vulgaris;
FIG. 4 is a C L SM picture of the surface of epoxy coating F6 after 5 days of contact culture with Chlorella
FIG. 5 is a C L SM picture of the surface of epoxy coating F7 after 5 days of contact culture with Chlorella
Detailed Description
The features of the invention will be further elucidated by the following examples, without limiting the claims of the invention in any way.
Example 1
(1) Adding 1.0g of dodecyl dimethyl benzyl ammonium chloride into 89g of glycidyl ether epoxy coating (epoxy anticorrosion primer, Anhui Linghu paint, Inc.), ultrasonically dispersing for 30min, and stirring in a magnetic stirrer with the rotation speed of 1200rpm for 150min to obtain a uniform quaternary ammonium salt/epoxy coating mixed solution;
(2) adding 10g of phenolic aldehyde amine curing agent (NX-5444, Kadelia) into the mixed solution obtained in the step (1), stirring for 5min in a magnetic stirrer with the rotation speed of 500rpm, standing for 60s, and enabling the quaternary ammonium salt/epoxy coating mixed solution and the curing agent to fully react to obtain 100g of quaternary ammonium salt/epoxy coating composite emulsion;
(3) and (3) coating the quaternary ammonium salt/epoxy coating composite emulsion obtained in the step (2) on non-woven fabric by using a coating method, drying at normal temperature for 12 hours, and then drying at 50 ℃ in vacuum for 12 hours to obtain the quaternary ammonium salt modified epoxy coating. (as F1)
Example 2
(1) Adding 0.2g of dodecyl dimethyl benzyl ammonium bromide into 94.8g of glycidyl ether epoxy paint (epoxy anticorrosion primer, Anhui Ling lake paint, Inc.), ultrasonically dispersing for 10min, and stirring in a magnetic stirrer at 1500rpm for 60min to obtain a uniform quaternary ammonium salt/epoxy paint mixed solution;
(2) adding 5g of phenolic aldehyde amine curing agent (NX-5444, Kadelia) into the mixed solution obtained in the step (1), stirring for 10min in a magnetic stirrer with the rotation speed of 100rpm, standing for 30s, and enabling the quaternary ammonium salt/epoxy coating mixed solution and the curing agent to fully react to obtain 100g of quaternary ammonium salt/epoxy coating composite emulsion;
(3) and (3) coating the quaternary ammonium salt/epoxy coating composite emulsion obtained in the step (2) on non-woven fabric by using a coating method, drying at normal temperature for 12 hours, and then drying at 50 ℃ in vacuum for 12 hours to obtain the quaternary ammonium salt modified epoxy coating. (as F2)
Example 3
(1) Adding 1.1g of dodecyl dimethyl benzyl ammonium chloride and 0.9g of dodecyl dimethyl benzyl ammonium bromide into 83g of glycidyl ether epoxy coating (epoxy anticorrosion primer, Anhui Linghu paint Co., Ltd.), ultrasonically dispersing for 20min, and stirring in a magnetic stirrer with the rotation speed of 500rpm for 180min to obtain a uniform quaternary ammonium salt/epoxy coating mixed solution;
(2) adding 15g of phenolic aldehyde amine curing agent (NX-5444, Kadelia) into the mixed solution obtained in the step (1), stirring for 1min in a magnetic stirrer with the rotation speed of 1000rpm, standing for 150s, and enabling the quaternary ammonium salt/epoxy coating mixed solution and the curing agent to fully react to obtain 100g of quaternary ammonium salt/epoxy coating composite emulsion;
(3) and (3) coating the quaternary ammonium salt/epoxy coating composite emulsion obtained in the step (2) on non-woven fabric by using a coating method, drying at normal temperature for 12 hours, and then drying at 50 ℃ in vacuum for 12 hours to obtain the quaternary ammonium salt modified epoxy coating. (as F3)
Comparative example 1
(1) Dispersing 90g of glycidyl ether epoxy paint (epoxy anticorrosion primer, Anhui Ling lake paint, Inc.) by ultrasonic for 30min, and stirring in a magnetic stirrer at 1200rpm for 150min to obtain uniform epoxy paint;
(2) adding 10g of phenolic aldehyde amine curing agent (NX-5444, Kadelia) into the epoxy coating obtained in the step (1), stirring for 5min in a magnetic stirrer with the rotation speed of 500rpm, standing for 60s, and enabling the epoxy coating and the curing agent to fully react to obtain 100g of epoxy coating composite emulsion;
(3) and (3) coating the epoxy coating composite emulsion obtained in the step (2) on non-woven fabric by using a coating method, drying for 12 hours at normal temperature, and then drying for 12 hours in vacuum at 50 ℃ to obtain an epoxy coating. (as F0)
Comparative example 2
(1) Adding 5g of dodecyl dimethyl benzyl ammonium chloride into 85g of epoxy coating (epoxy anticorrosion primer, Anhui Linghu paint, Inc.), ultrasonically dispersing for 30min, and stirring in a magnetic stirrer at 1200rpm for 150min to obtain a uniform quaternary ammonium salt/epoxy coating mixed solution;
(2) adding 10g of phenolic aldehyde amine curing agent (NX-5444, Kadelia) into the mixed solution obtained in the step (1), stirring for 5min in a magnetic stirrer with the rotation speed of 500rpm, standing for 60s, and enabling the quaternary ammonium salt/epoxy coating mixed solution and the curing agent to fully react to obtain 100g of quaternary ammonium salt/epoxy coating composite emulsion;
(3) and (3) coating the quaternary ammonium salt/epoxy coating composite emulsion obtained in the step (2) on non-woven fabric by using a coating method, drying at normal temperature for 12 hours, and then drying at 50 ℃ in vacuum for 12 hours to obtain the quaternary ammonium salt modified epoxy coating. (as F4)
Comparative example 3
The antibacterial coating is prepared by adopting the method disclosed in the Chinese invention patent with the publication number of CN108753104A, the antibacterial coating is coated on non-woven fabric by a coating method, and after drying for 12 hours at normal temperature, the coating is dried for 12 hours under vacuum at 50 ℃ to obtain the antibacterial coating. (as F5)
Comparative example 4
(1) Adding 1.0g of dodecyl dimethyl benzyl ammonium chloride into 89g of glycidyl ester epoxy paint (ED1000 epoxy primer, Shinji paint Co., Ltd., Tianjin), performing ultrasonic dispersion for 30min, and stirring in a magnetic stirrer with the rotation speed of 1200rpm for 150min to obtain a uniform quaternary ammonium salt/epoxy paint mixed solution;
(2) adding 10g of phenolic aldehyde amine curing agent (NX-5444, Kadelia) into the mixed solution obtained in the step (1), stirring for 5min in a magnetic stirrer with the rotation speed of 500rpm, standing for 60s, and enabling the quaternary ammonium salt/epoxy coating mixed solution and the curing agent to fully react to obtain 100g of quaternary ammonium salt/epoxy coating composite emulsion;
(3) and (3) coating the quaternary ammonium salt/epoxy coating composite emulsion obtained in the step (2) on non-woven fabric by using a coating method, drying at normal temperature for 12 hours, and then drying at 50 ℃ in vacuum for 12 hours to obtain the quaternary ammonium salt modified epoxy coating. (as F6)
Comparative example 5
(1) Adding 1.0g of dodecyl dimethyl benzyl ammonium chloride into 89g of glycidyl ether epoxy coating (epoxy anticorrosion primer, Anhui Linghu paint, Inc.), ultrasonically dispersing for 30min, and stirring in a magnetic stirrer with the rotation speed of 1200rpm for 150min to obtain a uniform quaternary ammonium salt/epoxy coating mixed solution;
(2) adding 10g of polyester amine curing agent (D.E.H.140, Dow chemical) into the mixed solution obtained in the step (1), stirring for 5min in a magnetic stirrer with the rotating speed of 500rpm, standing for 60s, and enabling the quaternary ammonium salt/epoxy coating mixed solution and the curing agent to fully react to obtain 100g of quaternary ammonium salt/epoxy coating composite emulsion;
(3) and (3) coating the quaternary ammonium salt/epoxy coating composite emulsion obtained in the step (2) on non-woven fabric by using a coating method, drying at normal temperature for 12 hours, and then drying at 50 ℃ in vacuum for 12 hours to obtain the quaternary ammonium salt modified epoxy coating. (as F7)
And (3) performance testing:
zeta potential test: the surfaces of the epoxy coatings F0, F1, F2 and F3 obtained in comparative example 1 and examples 1 to 3 were tested for the Zeta potential on the solid surface by means of a Zeta potential Analyzer (SurPASS 3). The results are shown in Table 1.
TABLE 1
Epoxy coating F0 F1 F2 F3
Zeta potential (mV) -33.7262 -0.0145 -27.0029 2.0013
As can be seen from table 1, the Zeta potentials of F1, F2 and F3 are all much higher than that of F0, and the surface potentials of the films all tend to be positive as the concentration of the quaternary ammonium salt on the surfaces of the coatings increases, because the surfaces of the coatings of F1, F2 and F3 are all covered with the positively charged quaternary ammonium salt, so that the coatings of F1, F2 and F3 are all successful in introducing the quaternary ammonium salt.
Contact angle test: the contact angle of water on the surfaces of the epoxy coatings F0, F1, F2 and F3 was measured by a contact angle tester (JC 20 CODI). The results are shown in Table 2.
TABLE 2
Epoxy coating F0 F1 F2 F3
Contact angle (°) 113.7 113.2 111.4 114.4
As can be seen from Table 2, there is no significant difference in the contact angle of water on the surfaces of the coatings F0, F1, F2 and F3, which indicates that the addition of the quaternary ammonium salt has no significant influence on the hydrophilicity and hydrophobicity of the coatings under a certain concentration range.
And (3) stability testing: stability tests were performed on the F0, F1, F2, F3, F4 coated samples. The method comprises the following steps: sample weighing (m)0) Then the sample is soaked in water for 4 weeks, then the sample is taken out, the water on the surface of the sample is removed by filter paper, and the sample is weighed to obtain the equilibrium swelling mass m of the samples(ii) a Then dried in vacuum to a constant weight mfPercent swelling Ws (%) and mass loss ratio W1(%) was calculated as follows:
Figure GDA0002465184570000071
Figure GDA0002465184570000072
the results are shown in Table 3.
TABLE 3
Epoxy coating F0 F1 F2 F3 F4
Percent swelling Ws (%) 9.1 10.1 9.4 10.8 14.2
Mass loss ratio W1(％) 1.3 0.5 0.4 0.7 7.3
Compared with F0, the swelling percentages of F1, F2 and F3 are not much different, the swelling of the sample is mainly related to hydrophily and hydrophobicity, the data is consistent with the results of a contact angle test, and in addition, the swelling problem of F4 is obvious, which indicates that the hydrophily and hydrophobicity of the epoxy coating can be influenced by excessive addition of the quaternary ammonium salt. For the mass loss ratio of the sample, compared with F0, after soaking in water for 4 weeks, F1, F2 and F3 have only small mass loss, which indicates that the coating is stable; the mass loss of F4 was high (> 5.0%), indicating that the F4 coating was unstable. This indicates that, within a certain range, the addition of quaternary ammonium salt has no effect on the stability of the coating; if the quaternary ammonium salt is added beyond the range, the structure of the coating is damaged, so that the coating is easy to fall off in water and cannot be used.
Chlorella adhesion experiment comprises placing samples coated with F0, F1, F5, F6, and F7 in 24-well plate, ultraviolet sterilizing for 30min, and adding 2m L Chlorella solution (concentration: 10)7cell/m L), placing the 24-well plate in a light incubator, culturing for 5 days under the conditions of 25 +/-1 ℃, 12h day, 12h night and 4800L UX illumination, taking out the sample to a new 24-well plate, adding 2m L PBS solution, placing the plate in a shaking table, shaking for 10min under the condition of 150rpm, observing the taken-out sample by using a laser confocal scanning microscope (C L SM), and observing the results of C L SM as shown in figures 1 to 3.
C L SM analysis shows that more chlorella adheres to the surface of F0, a small amount of chlorella adheres to the surfaces of F5, F6 and F7, and almost no algae cells exist on the surface of F1, so that compared with F0, F1, F5, F6 and F7 can obviously inhibit the growth and adhesion of the chlorella on the surface of the chlorella, have good anti-pollution performance, and compared with F5, F6 and F7, the F1 has a better algae inhibition effect.
It should be understood that the detailed description of the invention is merely illustrative of the invention and is not intended to limit the invention to the specific embodiments described. It will be appreciated by those skilled in the art that the present invention may be modified or substituted equally as well to achieve the same technical result; as long as the use requirements are met, the method is within the protection scope of the invention.

Claims (2)

1. A preparation method of a quaternary ammonium salt modified epoxy coating with an algae inhibiting effect is characterized by comprising the following steps:
(1) adding the quaternary ammonium salt solid powder into the glycidyl ether epoxy coating, and obtaining uniform quaternary ammonium salt/epoxy coating mixed solution after ultrasonic treatment and stirring;
(2) adding a curing agent into the mixed solution obtained in the step (1), uniformly stirring, and standing for reaction to obtain a quaternary ammonium salt/epoxy coating composite emulsion;
(3) coating the quaternary ammonium salt/epoxy coating composite emulsion obtained in the step (2) on a substrate material by a coating method, and drying to obtain a quaternary ammonium salt modified epoxy coating;
the quaternary ammonium salt is dodecyl dimethyl benzyl ammonium chloride or dodecyl dimethyl benzyl ammonium bromide, and the curing agent is a phenolic aldehyde amine curing agent; based on the parts by weight of the quaternary ammonium salt/epoxy coating composite emulsion, every 100 parts of the quaternary ammonium salt/epoxy coating composite emulsion contains 5-15 parts of a curing agent, 0.1-2 parts of quaternary ammonium salt and the balance of epoxy coating; the ultrasonic time in the step (1) is 10-30 min, and the stirring is performed by using a magnetic stirrer with the rotating speed of 500-1500 rpm for 60-180 min; the stirring in the step (2) is performed for 1-10 min by using a magnetic stirrer with the rotating speed of 100-1000 rpm; the standing time in the step (2) is 30-150 s; the drying time in the step (3) is 8-24 hours; the substrate material is non-woven fabric.
2. The quaternary ammonium salt modified epoxy coating prepared by the preparation method of claim 1.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006238735A (en) * 2005-03-01 2006-09-14 Mitsubishi Gas Chem Co Inc Seaweed resistant, moss resistant hydroculture material
CN102634276A (en) * 2012-04-25 2012-08-15 厦门大学 Heavy-duty anticorrosive polyaniline coating and preparation method thereof

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4866106A (en) * 1988-02-08 1989-09-12 Waitomo Industrial Investments Ltd. Antifouling composition
US7232210B2 (en) * 2003-12-17 2007-06-19 Samsung Electronics Co., Ltd. Foam, method of forming the foam, print cartridge including the foam, and printing apparatus including the print cartridge
CN103232587A (en) * 2013-04-19 2013-08-07 淮海工学院 Antibacterial polyurethane and preparation method thereof
CN103571302A (en) * 2013-09-30 2014-02-12 浙江工业大学 Water-based fluorine-containing epoxy paint
CN105542632B (en) * 2016-02-29 2017-12-01 华南理工大学 A kind of antibiotic fungus-resisting paint of natural environmental-protective and preparation method and application
CN105694053B (en) * 2016-03-16 2018-09-11 泉州亚林新材料科技有限公司 A kind of quaternary ammonium salt-modified chitosan antimicrobial agent and its preparation method and application
CN106752677A (en) * 2016-11-22 2017-05-31 俞潮军 A kind of large surface fungicidal paint for exterior wall

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006238735A (en) * 2005-03-01 2006-09-14 Mitsubishi Gas Chem Co Inc Seaweed resistant, moss resistant hydroculture material
CN102634276A (en) * 2012-04-25 2012-08-15 厦门大学 Heavy-duty anticorrosive polyaniline coating and preparation method thereof

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