CN-121975368-A - Modified shell antifouling material and preparation method and application thereof

Abstract

The invention provides a modified shell anti-fouling material, a preparation method and application thereof, wherein the modified shell anti-fouling material is specifically modified shell powder with an anti-fouling agent loaded on the surface, the porous structure of the shell is an ideal slow-release carrier of the natural anti-fouling agent, the problem that the anti-fouling agent is easy to burst in a coating can be solved through loading of the carrier, the anti-fouling agent is slowly released in the coating, the anti-fouling action time of the anti-fouling agent is prolonged, and in addition, the modified shell powder carrier is the shell powder subjected to activation and hydrophobic treatment and has high affinity with organic resin in the anti-fouling coating. The antifouling paint can be used for the netting of the marine culture net cage, and the modified oyster shell powder is added into the finish paint, so that the modified oyster shell powder is not only dispersed in the paint as rigid particles, reduces the damage of water erosion to the coating, prolongs the service life of the netting, but also plays a main antifouling role, creates a weak alkaline microenvironment which is unfavorable for adhesion of most marine organisms, and has huge application potential in antifouling of the marine culture net cage and the netting.

Inventors

• BI JINYE
• ZHU JIANHUA
• ZHAO CAILING
• CHEN HUIKAI
• LU GUOQIANG
• WANG JIANMING

Assignees

• 南方海洋科学与工程广东省实验室(湛江)

Dates

Publication Date

20260505

Application Date

20260318

Claims (10)

1. 1. The modified shell antifouling material is characterized by comprising a modified shell powder carrier, wherein an antifouling agent is loaded on the surface of the modified shell powder carrier; the modified shell powder carrier is shell powder subjected to activation treatment, and the activating agent adopted in the activation treatment comprises a silane coupling agent, fatty acid and a metal coupling agent.
2. 2. The modified shell stain repellent material of claim 1, wherein the silane coupling agent comprises at least one of gamma-aminopropyl triethoxysilane, gamma-aminopropyl trimethoxysilane, gamma-glycidoxypropyl trimethoxysilane, N-beta- (aminoethyl) -gamma-aminopropyl methyldimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropylmethyldiethoxysilane, 3-chloropropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyl trichlorosilane, 3-bromopropyl trichlorosilane, 3-fluoropropyl trichlorosilane, mercaptopropyl trimethoxysilane, mercaptopropyl triethoxysilane, mercaptopropyl methyldimethoxysilane; and/or the fatty acid is a long chain fatty acid with the carbon number of more than 12; and/or the metal coupling agent comprises at least one of aluminate, titanate and zirconate.
3. 3. The modified shell stain repellent material of claim 1, wherein the stain repellent agent comprises at least one of capsaicin, citronellal, magnolol, gingerol, tannic acid; and/or the kind of shell powder comprises at least one of mussel shell, scallop shell, oyster shell, clam shell, pearl shell and clam shell.
4. 4. The modified shell stain repellent material of claim 1, wherein the method of preparing the modified shell powder carrier comprises the steps of: And adding shell powder into an activator solution to perform an activation reaction to obtain the modified shell powder carrier.
5. 5. The modified shell stain repellent material of claim 4, wherein the solvent of the activator solution comprises an alcohol solvent.
6. 6. The modified shell stain resist material of claim 4, wherein when the activator is a silane coupling agent, the pH of the activator solution is 3 to 5.
7. 7. The method for producing a modified shell stain-proofing material as defined in any one of claims 1 to 6, comprising the steps of: and (3) placing the modified shell powder carrier and the antifouling agent in a solvent, and separating a solid product after a period of time to obtain the modified shell antifouling material.
8. 8. Use of the modified shell stain resist material of any of claims 1-6 in stain resist coatings.
9. 9. An antifouling paint is characterized by comprising a primer and a finish; The topcoat comprises the modified shell stain resist material of any of claims 1-6.
10. 10. An antifouling paint according to claim 9, wherein the topcoat is prepared from a raw material comprising an aqueous aliphatic polyurethane dispersion, a modified shell antifouling material, an additive and water.

Description

Modified shell antifouling material and preparation method and application thereof Technical Field The invention belongs to the technical field of antifouling materials, and particularly relates to a modified shell antifouling material and a preparation method and application thereof. Background The tropical marine climate has the characteristics of high temperature, high humidity and high salt, and various marine organisms such as seaweed, mussels and the like are extremely easy to adhere to the surface of the net cover due to the fact that the marine culture net box is soaked in seawater for a long time. The marine organisms not only can block the netting to prevent the exchange of water bodies inside and outside the net cage, but also can aggravate the weight and the resistance of the netting, quicken the ageing and the damage of the netting and increase the maintenance cost of the net cage. Thus, the antifouling of marine aquaculture net cages is a problem that needs to be solved by those skilled in the marine antifouling art. The common marine antifouling paint has good antifouling effect in steel plate tests, and is suitable for antifouling of marine metal facilities such as ships, wharfs, buoys and the like. However, most marine antifouling paints are not effective for use in cage clothing. The marine aquaculture net cage is made of a high polymer material with extremely low surface energy, unlike the common metal materials of the common ocean platform, so that common paint is difficult to attach, and in addition, due to the fact that the density of fish in the aquaculture net cage is high, metabolites of fish shoals are easier to attract marine organisms such as bacteria, algae and shellfish to attach to the aquaculture net cage, and the antifouling effect of the antifouling paint needs to be enhanced. In view of the above, it is necessary to develop an antifouling paint for marine culture cages. Disclosure of Invention In order to overcome the problems of the prior art, one of the purposes of the present invention is to provide a modified shell antifouling material. The second object of the present invention is to provide a method for producing the modified shell stain-proofing material. The invention also aims to provide application of the modified shell antifouling material. The fourth object of the present invention is to provide an antifouling paint. In order to achieve the above purpose, the technical scheme adopted by the invention is as follows: the invention provides a modified shell antifouling material, which comprises a modified shell powder carrier, wherein an antifouling agent is loaded on the surface of the modified shell powder carrier; the modified shell powder carrier is shell powder subjected to activation treatment, and the activating agent adopted in the activation treatment comprises a silane coupling agent, fatty acid and a metal coupling agent. Preferably, the silane coupling agent comprises at least one of gamma-aminopropyl triethoxysilane, gamma-aminopropyl trimethoxysilane, gamma-glycidol ether oxypropyl trimethoxysilane, N-beta- (aminoethyl) -gamma-aminopropyl methyldimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropylmethyldiethoxysilane, 3-chloropropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltrichlorosilane, 3-bromopropyl trichlorosilane, 3-fluoropropyl trichlorosilane, mercaptopropyl trimethoxysilane, mercaptopropyl triethoxysilane, mercaptopropyl methyldimethoxysilane. Preferably, the fatty acid is a long chain fatty acid having a number of carbon atoms greater than 12. More preferably, the fatty acid comprises at least one of stearic acid and oleic acid. Preferably, the metal-based coupling agent comprises at least one of aluminate, titanate, zirconate. Preferably, the anti-fouling agent comprises at least one of capsaicin, citronellal, magnolol, gingerol, tannic acid; Preferably, the kind of shell powder comprises at least one of mussel shell, scallop shell, oyster shell, clam shell, pearl shell and clam shell. The oyster shell has a layered porous structure, can provide nano-scale roughness, and can construct a micro-scale and nano-scale double coarse structure in the resin if being added into the coating, so that air is wrapped in gaps, and the free energy of the surface of the coating is reduced. Therefore, the existing research is to prepare the oyster shell into the super-hydrophobic material, and the super-hydrophobic material can be used in industries such as plastics, rubber, daily chemicals and the like, and other application values of the oyster shell are yet to be developed. The oyster shell is rich in natural mineral components such as calcium carbonate and the like, so that the calcined oyster shell has strong alkalinity, can destroy the cell structure of microorganisms, denature the protein of bacteria, can be used as a natural environment-friendly bactericide for sterilizing soil and water, and in addition, the por