CN118165594A - Ship antifouling paint containing biological repellent and preparation method thereof - Google Patents

Abstract

The invention prepares the anti-fouling paint which is coated by beta-cyclodextrin and dihydrocapsaicin to form an inclusion compound, and uses the inclusion compound as a biological anti-fouling repellent for ships, and the prepared paint can slowly release the anti-fouling agent for a long time and has good repellent and inhibition effects on algae, barnacles, bacteria and other fouling organisms in the sea, thereby reducing the attachment of the marine organisms, having broad-spectrum and efficient anti-fouling effects and effectively solving the problems of anti-fouling and marine environment pollution of the marine ships.

Description

Ship antifouling paint containing biological repellent and preparation method thereof

Technical Field

The invention belongs to the technical field of anti-fouling paint, in particular to the technical field of anti-fouling paint for marine vessels, and particularly provides an anti-fouling paint for vessels, which takes dihydro capsaicin-beta-cyclodextrin inclusion compound as a biological repellent and a preparation method thereof.

Background

Along with the development and utilization of ocean resources and development requirements in the national defense field in China in recent years, the development of industries such as ships, aircraft carriers and ships is promoted, but the surfaces of the vehicles, such as ship bottoms, submarine shells and the like, which are contacted with the ocean in the ocean navigation process can gradually grow with marine organisms, such as barnacles, seaweeds and the like, to cause fouling and corrosion of the ship bodies, on the one hand, the self weight of the ships, the aircraft carriers, the ships and the ships is increased due to marine organism fouling, the navigation friction resistance is increased, the navigation speed is slowed down, and the energy fuel consumption is increased; on the other hand, the corrosion of the ship body is aggravated, and the service life of the ship body and the naval vessel is shortened. In the case of vessels, more than 80% of the frictional resistance during sailing comes from the hull surface, and when the fouling rate of the hull by marine organisms is 5%, the sailing resistance of the vessel increases by 3 to 5 times that of the net surface of the vessel, and the fuel consumption increases by about 30% (Min Shaosong, peng Fei, wang Zhanzhi, etc.. The prediction method of the influence of marine fouling on the frictional resistance of the hull [ J ]. Vessel mechanics, 2017, 21 (12): 1460-1467). Therefore, how to prevent marine biofouling is one of the important issues that is urgent.

The conventional chemical biocidal marine antifouling paint used at present achieves the aim of antifouling by releasing toxic agents in the paint to the sea and killing marine organisms attached to ships; the antifouling agent usually comprises heavy metal compounds with high toxicity and various organic matters such as tributyltin (TBT), drop-in-water (DDT) and the like, and the coating has a good antifouling effect, but researches show that the organic tin can cause biological distortion and cause serious damage to marine organism diversity and marine ecology; the dripping nasal discharge can threaten the health and ecological environment of human bodies through a food chain, and the use of the antifouling agent can cause serious and irreversible harm to the environment, thereby causing the pollution of marine environment. With the international awareness of marine environmental protection, international convention for disabling harmful organotin in ship bottom hull antifouling paint, international convention for controlling harmful ship bottom antifouling system, will take effect on 9 months and 17 days of 2008, and use of such antifouling agent in production of antifouling paint will be prohibited. Therefore, the development and research of novel environment-friendly antifouling agents are key to preparing marine antifouling paints.

The dihydro capsaicin is a vanilla amide alkaloid extracted from capsicum with extremely pungency (the pungency degree is 1610 ten thousand SHU), is also called 8-methyl-N-vanillyl nonanamide, accounts for about 20-30% of the total extract, is a biological antifouling repellent, can play a good antifouling role, has a repellent effect on marine attached organisms only, does not generate injury, does not damage marine organism chains, does not pollute the environment, and has obvious ecological benefits. The dihydro capsaicin is added into antifouling paint as biological antifouling repellent for antifouling treatment of marine ship, marine culture facility, drilling platform, etc. to prevent marine organism adhesion, and has high efficiency, low power consumption, environment friendship, etc. (Peng Bixian, wang Junlian, peng Zhenghong, etc. capsaicin homolog synthesis, pungency and marine organism antifouling performance research [ J ]. Chinese science: chemistry, 2011, 41 (10): 1646-1654). The current biological antifouling repellent is used for ship antifouling paint, is coated on the contact part of ships and offshore structures with seawater, prevents the attachment of marine organisms such as algae, shellfish, mollusks and the like, can achieve the aim of preventing the aggregation of the marine organisms on the ship hull, and replaces toxic organotin and dribbling (DDT) antifouling agents. The coating produced by the spicy antifouling agent is mainly used for preventing fouling organisms of ships, offshore platforms and underwater facilities, can effectively remove the damage effect of aquatic fouling organisms on ship bodies, and has special effects on barnacles with the largest harm and obvious preventing and removing effects on other aquatic fouling organisms. However, if the biological antifouling repellent is prepared by using the non-coated dihydrocapsaicin, the release rate is too high in the early stage, the concentration of the antifouling agent is insufficient after the release rate is stable in the later stage, the utilization rate of the antifouling agent is low, and the phenomenon is called an 'burst release phenomenon' of the antifouling agent. The early excessive release of the biological anti-fouling agent not only shortens the effective period of the anti-fouling paint and increases the anti-fouling cost, therefore, the controllable release of the anti-fouling agent becomes a research hot spot of the novel marine anti-fouling paint, the capability of the anti-fouling paint for maintaining the controllable release of the anti-fouling agent for a long time becomes more and more important, and how to solve the problem of 'sudden release' of the anti-fouling agent in the coating to realize green long-acting anti-fouling is a technical problem focused by researchers at home and abroad, and becomes a focus of developing the green high-efficiency marine anti-fouling paint and a main development direction. The slow release technology is a substance controlled release technology, and the release speed of a target substance in the expected time is slowed down by specific measures, so that the target substance maintains a certain effective concentration in a system. Because the beta-cyclodextrin (beta-CD) is formed by connecting 7 glucopyranoses through alpha-1, 4 glycosidic bonds to form annular oligosaccharide which is in a cylindrical structure, and because the beta-cyclodextrin has a special structure of 'inner hydrophobic and outer hydrophilic', various organic compounds can be embedded into a hydrophobic cavity to form a molecular inclusion compound, so that the stability and the slow release performance of the compounds under the conditions of light, heat, oxygen, acid, alkali and the like are improved (Ma Xueyi, li Xiaoming, pan Huiping and the like).

Disclosure of Invention

Based on the technical problems, the slow-release of the biological anti-fouling agent is realized by utilizing the beta-cyclodextrin and dihydrocapsaicin inclusion technology, the inclusion compound is prepared by coating the beta-cyclodextrin and the dihydrocapsaicin, and the inclusion compound is used as the biological anti-fouling repellent for the anti-fouling paint of the ship, and the prepared paint can slowly release the anti-fouling agent for a long time and has good effects of repelling and inhibiting algae, barnacles, bacteria and other fouling organisms in the sea, so that the adhesion of the marine organisms is reduced, the anti-fouling paint has a broad-spectrum and efficient anti-fouling effect, and the problems of anti-fouling and marine environment pollution of the marine ship are effectively solved.

The marine antifouling paint containing the biological repellent and the preparation method thereof are characterized by comprising the following components in parts by weight:

10-20 parts of thermoplastic acrylic ester polymer, 6-16 parts of organosilicon modified acrylic resin, 6-9 parts of modified rosin resin, 5-10 parts of titanium pigment, 6-10 parts of wollastonite powder, 3-6 parts of precipitated barium sulfate, 6-10 parts of ferric oxide red, 6-10 parts of zinc oxide, 10-30 parts of organic solvent, 0.1-8 parts of biological repellent, 2-5 parts of adhesion promoter, 0.1-3 parts of defoamer, 2-5 parts of flatting agent and 1-6 parts of anti-settling agent;

The preparation method of the biological repellent comprises the following steps: weighing a certain amount of dihydrocapsaicin (purity is more than or equal to 98%) and dissolving the dihydrocapsaicin in quantitative ethanol for later use; weighing a certain amount of beta-cyclodextrin (the purity is more than or equal to 98 percent) and dissolving the beta-cyclodextrin in distilled water, and adjusting the solution to be alkaline by using 10 percent sodium hydroxide; transferring the dihydrocapsaicin ethanol solution into beta-cyclodextrin solution at a certain temperature, stirring for a certain time, distilling to remove ethanol solvent, placing the rest solution in 0-5 ℃ for cooling and placing for 24h ℃, filtering, discarding filtrate, and drying the filter cake at normal temperature to obtain a biological repellent-dihydrocapsaicin-beta-cyclodextrin inclusion compound (DHCAP-beta-CD);

The marine antifouling paint containing the biological repellent and the preparation method thereof are characterized in that the preferable preparation conditions of the biological repellent are as follows: the weight ratio of the dihydrocapsaicin to the beta-cyclodextrin is 1:2-5, and the reaction temperature is as follows: 20-70 ℃, and the reaction time is as follows: the pH value of the reaction system is 9-11 after 6-24 hours;

the marine antifouling paint containing the biological repellent and the preparation method thereof are characterized in that the preparation conditions of the biological repellent are as follows: the ratio of the amount of the dihydrocapsaicin to the amount of the beta-cyclodextrin material is 1:3; reaction temperature: 40 ℃; reaction time: 12 hours; the pH value of the reaction system is 10;

the adhesion promoter is as follows: dimethyl octadecyl [3- (trimethoxysilyl) propyl ] ammonium chloride;

the organic solvent is as follows: one or more of propylene glycol methyl ether ethyl ester, propylene glycol monoethyl ether, butyl acetate and xylene;

The marine antifouling paint containing the biological repellent and the preparation method thereof are characterized by comprising the following steps: adding 10-30 parts of organic solvent, 10-20 parts of thermoplastic acrylic polymer, 6-16 parts of organosilicon modified acrylic resin and 6-9 parts of modified rosin resin into a dissolution kettle respectively; after stirring and dissolving, transferring the materials to a multifunctional stirrer, sequentially adding 5-10 parts of titanium dioxide, 6-10 parts of wollastonite powder, 3-6 parts of precipitated barium sulfate, 6-10 parts of iron oxide red, 6-10 parts of zinc oxide and 0.1-3 parts of defoaming agent, stirring and dispersing for 30 minutes, grinding by a horizontal sand mill until the fineness is qualified, adding 0.1-8 parts of biological repellent, 1-6 parts of anti-settling agent, 2-5 parts of flatting agent and 2-5 parts of adhesion promoter, and filtering by a closed filter (120-mesh copper net) to obtain the ship antifouling paint containing the biological repellent.

The specific embodiments adopted by the invention are as follows:

The invention is further described below in connection with specific examples, without limiting the scope of protection. Meanwhile, the experimental methods described in the following embodiment examples are all conventional methods unless otherwise specified; the reagents and materials, unless otherwise specified, are commercially available. The present invention is described in detail below with reference to the embodiments, but it should be noted that the embodiments are not limited to the present invention, and functional, method, or structural equivalent changes or substitutions made by those skilled in the art according to the embodiments are included in the scope of the present invention.

Example 1:

Weighing 0.31 g of dihydrocapsaicin (purity is more than or equal to 98%) and dissolving in 150ml of ethanol for later use; then weighing 3.47 g of beta-cyclodextrin (the purity is more than or equal to 98 percent, the weight ratio of the dihydrocapsaicin to the beta-cyclodextrin is 1:3), dissolving in 200 ml of distilled water, and adjusting the pH value of the solution to 10 by using 10 percent sodium hydroxide; transferring the dihydrocapsaicin solution into beta-cyclodextrin solution at 40 ℃, stirring for 12 hours, distilling to remove ethanol solvent, placing the rest solution at 0-5 ℃ for cooling and standing for 24 hours, filtering, discarding filtrate, and drying the filter cake at normal temperature to obtain a biological repellent-dihydrocapsaicin-beta-cyclodextrin inclusion compound (DHCAP-beta-CD) (mark: DC); the analysis shows that: the dihydro capsaicin and the beta-cyclodextrin form inclusion compound according to the mass ratio of 1:1, and the dihydro capsaicin content is 21.31 percent.

Example 2:

27.7 parts of organic solvent, 18 parts of thermoplastic acrylic polymer, 11 parts of organosilicon modified acrylic resin and 7 parts of modified rosin resin are respectively added into a dissolution kettle; after stirring and dissolving, transferring the materials to a multifunctional stirrer, sequentially adding 7 parts of titanium dioxide, 5 parts of wollastonite powder, 5 parts of precipitated barium sulfate, 6 parts of ferric oxide red, 6 parts of zinc oxide and 0.2 part of defoamer, stirring and dispersing for 30 minutes, sanding with a horizontal sand mill until the fineness is qualified, adding 0.1 part of dihydrocapsaicin, 2 parts of anti-settling agent, 2 parts of flatting agent, 3 parts of adhesion promoter, and then filtering with a closed filter (120-mesh copper mesh), thereby obtaining the anti-fouling paint (number: FW-1) for the ship containing dihydrocapsaicin, wherein the anti-fouling performance is shown in Table 1.

Example 3:

27.33 parts of organic solvent, 18 parts of thermoplastic acrylic polymer, 11 parts of organosilicon modified acrylic resin and 7 parts of modified rosin resin are respectively added into a dissolution kettle; after stirring and dissolving, transferring the materials to a multifunctional stirrer, sequentially adding 7 parts of titanium dioxide, 5 parts of wollastonite powder, 5 parts of precipitated barium sulfate, 6 parts of iron oxide red, 6 parts of zinc oxide and 0.2 part of defoamer, stirring and dispersing for 30 minutes; and (3) sanding the mixture by a horizontal sand mill until the fineness is qualified, adding 0.47 part of biological repellent-dihydrocapsaicin-beta-cyclodextrin inclusion compound (DC), 2 parts of anti-settling agent, 2 parts of leveling agent and 3 parts of adhesion promoter, and filtering the mixture by a closed filter (120-mesh copper mesh) to obtain the marine antifouling paint (number: FW-2) containing the biological repellent, wherein the antifouling performance is shown in Table 1.

Example 4:

26.86 parts of organic solvent, 18 parts of thermoplastic acrylic polymer, 11 parts of organosilicon modified acrylic resin and 7 parts of modified rosin resin are respectively added into a dissolution kettle; after stirring and dissolving, transferring the materials to a multifunctional stirrer, sequentially adding 7 parts of titanium dioxide, 5 parts of wollastonite powder, 5 parts of precipitated barium sulfate, 6 parts of iron oxide red, 6 parts of zinc oxide and 0.2 part of defoamer, stirring and dispersing for 30 minutes; and (3) sanding the mixture by a horizontal sand mill until the fineness is qualified, adding 0.94 part of biological repellent-dihydrocapsaicin-beta-cyclodextrin inclusion compound (DC), 2 parts of anti-settling agent, 2 parts of leveling agent and 3 parts of adhesion promoter, and filtering the mixture by a closed filter (120-mesh copper mesh) to obtain the marine antifouling paint (number: FW-3) containing the biological repellent, wherein the antifouling performance is shown in Table 1.

Table 1. Comparison of antifouling properties of dihydrocapsaicin and dihydrocapsaicin-beta-cyclodextrin as repellent.

Note that: (1) the determination method is according to GB/T5370-2007; (2) intact: the paint film is not foamed, cracked and shed, and almost no marine organism adheres to the paint film; failure: the offset area is greater than 5%; (3) the surface marine organisms are mainly barnacles, seaweeds and the like; (4) blank 6 months offset area 78%.

As can be seen from table 1: the paint template was intact with only dihydrocapsaicin (FW-1) before 12 months, with an area of about 3% for 18 months of fouling, and had completely failed for 24 months; the adopted dihydro capsaicin-beta-cyclodextrin inclusion compound (FW-2, FW-3) is still intact in 18-24 months, has lasting release effect compared with the dihydro capsaicin in the ship antifouling paint, and shows high-efficiency antifouling activity. The biological repellent and the antifouling paint of the invention can not only improve the antifouling performance of the coating and prolong the service life of the coating, but also not destroy the marine ecological environment, and is an environment-friendly ship antifouling paint. The anti-fouling paint can be applied to marine ships, can be also applied to surface anti-fouling paint of marine engineering equipment such as nuclear power platforms, oil extraction platforms and the like, and has remarkable inhibition effect on the attachment of marine fouling organisms.

Furthermore, it should be understood that although the present disclosure describes embodiments, not every embodiment is provided with a separate embodiment, and that this description is provided for clarity only, and that the disclosure is not limited to the embodiments described in detail below, and that the embodiments described in the examples may be combined as appropriate to form other embodiments that will be apparent to those skilled in the art.

Claims (6)

1. The marine antifouling paint containing the biological repellent and the preparation method thereof are characterized by comprising the following components in parts by weight:

10-20 parts of thermoplastic acrylic ester polymer, 6-16 parts of organosilicon modified acrylic resin, 6-9 parts of modified rosin resin, 5-10 parts of titanium pigment, 6-10 parts of wollastonite powder, 3-6 parts of precipitated barium sulfate, 6-10 parts of ferric oxide red, 6-10 parts of zinc oxide, 10-30 parts of organic solvent, 0.1-8 parts of biological repellent, 2-5 parts of adhesion promoter, 0.1-3 parts of defoamer, 2-5 parts of flatting agent and 1-6 parts of anti-settling agent.

2. The biostimulant of claim 1 prepared by the method comprising: weighing a certain amount of dihydrocapsaicin (purity is more than or equal to 98%) and dissolving the dihydrocapsaicin in quantitative ethanol for later use; weighing a certain amount of beta-cyclodextrin (the purity is more than or equal to 98 percent) and dissolving the beta-cyclodextrin in distilled water, and adjusting the solution to be alkaline by using 10 percent sodium hydroxide; transferring the dihydrocapsaicin ethanol solution into beta-cyclodextrin solution at a certain temperature, stirring for a certain time, distilling to remove ethanol solvent, placing the rest solution in 0-5 ℃ for cooling and placing for 24 h ℃, filtering, discarding filtrate, and drying the filter cake at normal temperature to obtain the biological repellent-dihydrocapsaicin-beta-cyclodextrin clathrate (DHCAP-beta-CD).

3. The biostimulant of claim 2, preferably prepared under the following conditions: the weight ratio of the dihydrocapsaicin to the beta-cyclodextrin is 1:2-5, and the reaction temperature is as follows: 20-70 ℃, and the reaction time is as follows: the pH value of the reaction system is 9-11 after 6-24 hours.

4. The adhesion promoter of claim 1 which is: dimethyl octadecyl [3- (trimethoxysilyl) propyl ] ammonium chloride.

5. The organic solvent according to claim 1, which is one or a combination of several selected from propylene glycol methyl ether ethyl ester, propylene glycol monoethyl ether, butyl acetate, xylene and n-butanol.

6. The marine antifouling paint containing the biostimulant according to claim 1, wherein the preparation method comprises the following steps: adding 10-30 parts of organic solvent, 10-20 parts of thermoplastic acrylic polymer, 6-16 parts of organosilicon modified acrylic resin and 6-9 parts of modified rosin resin into a dissolution kettle respectively, stirring and dissolving, transferring the materials to a multifunctional stirrer, sequentially adding 5-10 parts of titanium white powder, 6-10 parts of wollastonite powder, 3-6 parts of precipitated barium sulfate, 6-8 parts of iron oxide red, 6-10 parts of zinc oxide and 0.1-3 parts of defoamer, stirring and dispersing for 30 minutes, grinding until the fineness is qualified by a horizontal sand mill, adding 0.1-8 parts of biological repellent, 1-6 parts of anti-settling agent, 2-5 parts of flatting agent and 2-5 parts of adhesion promoter, and filtering by a closed filter (120-mesh copper net) to obtain the marine anti-fouling paint containing the biological repellent.