CN113122042A

CN113122042A - Functional additive for marine coating and marine antifouling coating composition

Info

Publication number: CN113122042A
Application number: CN202110501865.6A
Authority: CN
Inventors: 唐新村; 唐攒浪; 李智华
Original assignee: Hunan Zhiyuan Environmental Protection Technology Co ltd
Current assignee: Hunan Zhiyuan Environmental Protection Technology Co ltd
Priority date: 2021-04-28
Filing date: 2021-05-08
Publication date: 2021-07-16
Anticipated expiration: 2041-05-08
Also published as: CN113122042B

Abstract

The invention discloses a functional additive of a ship coating and a ship antifouling coating composition, and relates to the technical field of ship coatings. The invention provides a ship antifouling paint using scorodite as a functional additive, which solves the problem that the ship antifouling paint using cuprous oxide as an antifouling agent brings adverse effects to marine environment. The scorodite-containing coating slurry prepared by adopting the epoxy resin and the polyamide as the adhesives and the ethanol as the solvent has excellent bonding performance to the steel plate, and the antifouling coating composition has the advantages of simple preparation process, stable performance, lower cost and environmental friendliness.

Description

Functional additive for marine coating and marine antifouling coating composition

Technical Field

The invention relates to the technical field of marine paint, in particular to a functional additive of marine paint and a marine antifouling paint composition.

Background

The ship navigation frictional resistance is 80% from the surface of the ship body, the ship generates fouling (marine organism attachment) which has great harm to the performance of the ship, and the fuel consumption is estimated to be increased by 0.3% -1% every time the ship fouling is increased by 10 mu m (Zhou Cheng Liang. history, current situation and future of ship antifouling paint [ J ]. Chinese paint, 1998(06): 3-5.); when the marine organism pollution loss rate is 5%, the frictional resistance is 2 times of that of a clean surface, the fuel oil is increased by 10% (Yangbeiping, etc. the development of the epoxy modified fluorocarbon nano composite ship coating [ J ], the research and development of Lanzhou university of science and technology, 2005,73-76.), and when the pollution is serious, the fuel oil consumption is increased by 30% at most (while still, the antifouling characteristic theoretical analysis of the low surface energy antifouling coating [ J ]. Chinese coating, 2000(05): 36-39). The marine organisms comprise microorganisms such as algae spores, bacteria and diatoms, and large fouling organisms such as barnacles, moss and mussels (Xieqing et al, marine antifouling material [ J ] science, 2017,69(1): 27-31.).

The attachment of marine organisms on the surface of a ship firstly secretes a mucus, moistens the surface of a ship body, disperses on the surface of the ship, and then attaches to the surface of the ship body in one or more ways of chemical bonding, electrostatic interaction, mechanical linkage and diffusion (development of epoxy modified fluorocarbon nano composite ship coatings, Yanbuping and the like, J)]The university of Ritussah university, Lanzhou, 2005, 73-76). The attachment of these marine organisms causes the increase of the ship's navigation resistance, the increase of fuel consumption, the increase of greenhouse effect, and the blockage of piping systemAnd safety accidents occur. Meanwhile, the marine organisms grow, reproduce and decompose a great deal of CO generated on the ship body₂And H₂Acidic gases such as S can acidify seawater and aggravate corrosion of ship hull (Huohuangsu, et al, Marine Ship antifouling coatings review [ J]Surface engineering and remanufacturing, 2017,17(2): 29-33.). Therefore, the ship antifouling significance is very important.

The coating of antifouling paint on the surface of ship hull is the most extensive and effective method for solving fouling problem. Antifouling paints are generally composed of a film-forming resin, an antifouling agent, a filler, an auxiliary agent, and the like (margaria and the like, antifouling paint and method for evaluating antifouling properties thereof [ J ] shanghai paint, 2010,48(1): 29-32.). The antifouling paint coated on the surface of the ship body can gradually release active ingredients (antifouling agents) of the antifouling paint into seawater to form an effective toxic layer, so that the aims of inhibiting the adhesion and growth of marine organisms on the outer surface of the ship body and reducing the fouling of the ship body are fulfilled. The antifouling agent of the traditional ship antifouling paint is generally cuprous oxide, and the base material is divided into a soluble type and an insoluble type.

The soluble type base material is rosin, and the insoluble type base material is acrylate, vinyl resin, chlorinated rubber, etc. With the development of science and technology, the polishable antifouling paint is widely applied. The paint is divided into organic tin self-polishing antifouling paint and tin-free self-polishing antifouling paint. The organotin has a broad spectrum and high antifouling effect at low concentration, but because the organotin substances are stable and easy to accumulate in organisms, can cause organism malformation, and can cause the organotin to enter a food chain, the marine environmental protection association (MEPC) determines that the final service life of the organotin antifouling agent is 2018, 1 and 1 (bigg.d M, et al. The base material of the tin-free self-polishing antifouling paint is divided into a common base material and a degradable base material. The common base material is acrylic acid copolymer, etc., and the degradable base material is mostly polyester. Because the antifouling agent of the tin-free self-polishing antifouling paint is lack of broad spectrum, cuprous oxide is often added to improve the sterilization effect of the antifouling agent.

In recent years, in order to protect the marine resource environment and realize sustainable development, low-toxicity or nontoxic antifouling paints such as low-surface-energy antifouling paints, nano antifouling paints, bionic antifouling paints, conductive antifouling paints, biological antifouling paints and the like have become research hotspots: (1) the low surface energy antifouling paint mainly refers to an antifouling paint based on fluorocarbon resin or organic silicon, accords with the modern antifouling concept of green and environmental protection, and has better application prospect as an environment-friendly antifouling technology. But the antifouling paint has the problems of difficult adhesion with other internal paints, poor recoatability and the like because of lower surface energy. Due to the limitation of antifouling effect, the coatings are mostly applied to small and medium-sized ships at present (the theoretical analysis on antifouling property of low-surface-energy antifouling coatings is static at the edge [ J ]. Chinese coatings, 2000(05):36-39+ 3.); (2) the nano antifouling paint has rapid development in recent years, opens up a new way for the development of antifouling paint, but the nano antifouling paint has the problems of high material cost, possible damage to marine environment and the like; (3) the bionic antifouling paint does not need to use an antifouling agent, has very important significance for protecting a marine ecosystem, and is one of research hotspots in the field of non-toxic antifouling. Biobiomimetic techniques, however, often require high costs and have great difficulty in achieving scale-up production applications of such antifouling coatings (Wohlgemuth R. the locks and keys to industrial bio-technology [ J ]. New Biotechnology, 2009,25(4): 204); (4) the conductive antifouling paint mainly focuses on improving the conductive capability and the electrolytic resistance of the coating, but has the defects of high cost and complex preparation process; (5) the biological antifouling paint is green, environment-friendly and pollution-free, but usually has a certain control effect only for specific fouling substances, and the antifouling objects are single and easy to dissolve in water environment (CN 106221353A), so that the antifouling time is limited, and therefore, in order to ensure the broad-spectrum and high-efficiency fouling control, the natural organic antifouling agent is usually used in cooperation with other antifouling agents. The marine antifouling paint is developing towards the environment-friendly and sustainable direction, cuprous oxide denatures protein by releasing heavy metal copper ions in seawater so as to achieve the aim of killing marine organisms, and although the cuprous oxide is low in cost and has a broad-spectrum sterilization effect, the marine environment is adversely affected by the accumulation of a large amount of copper ions (ocean environmental risk assessment of copper in domestic antifouling paint [ J ] ecological toxicology reports, 2016,11(1): 182-.

Disclosure of Invention

In order to solve the technical problem that the marine environment is adversely affected by cuprous oxide serving as an antifouling agent of the marine coating, the invention provides the functional additive of the marine coating, wherein scorodite is used as the functional additive of the marine coating, and the scorodite and various coatings can be uniformly mixed and have good coating property, so that the marine coating has the advantages of good antifouling effect, low cost, long time effect and environmental friendliness.

The second purpose of the invention is to provide a ship coating composition based on scorodite bioactivity, which can realize long-term and effective antifouling effect on the surface of a ship, utilizes unique and excellent bioactivity of scorodite, has high adhesion strength to a steel plate, has obvious antifouling advantage to water body organisms, and is environment-friendly.

In order to achieve the purpose, the invention provides the following technical scheme:

a functional additive for marine coatings, which is scorodite.

Preferably, the scorodite is synthesized by the following method:

the method comprises the steps of acidifying a sodium arsenate solution by using sulfuric acid, adding an iron source to carry out arsenic fixation reaction, preparing scorodite precipitate with low solubility, and sequentially carrying out filtering, washing and drying treatment to obtain the scorodite.

Preferably, the iron source is one or more of iron powder, ferrous sulfate, ferrous nitrate, ferrous chloride, ferrous oxide, ferric sulfate, ferric nitrate, ferric trichloride, rust, ferrihydrite, ferroferric oxide, polymeric ferric sulfate, polymeric ferric aluminum sulfate and polymeric ferric chloride.

Further, the scorodite is synthesized by the following method:

dissolving sodium arsenate into distilled water to obtain a sodium arsenate solution with the arsenic concentration of 5-70 g/L, adding concentrated sulfuric acid into the sodium arsenate solution according to the molar ratio of sulfuric acid to arsenic of 1: 1-7: 1 for acidification, transferring the acidified solution into a three-neck flask, adding an iron source according to the molar ratio of iron to arsenic of 5: 1-1: 1, placing the three-neck flask into an oil bath kettle with magnetic stirring, uniformly stirring at 50-100 ℃, and introducing oxygen at the flow rate of 0-10L/min for reaction for 4-12 hours; and (3) realizing liquid-solid separation by adopting vacuum filtration, wherein the liquid-solid ratio is 5-40: 1mL/g, mixing the precipitate in distilled water, washing, filtering, and drying the precipitate at 60-100 ℃ for 5-8 h to obtain light green scorodite powder.

Preferably, the scorodite can also utilize scorodite FeAsO in the nature₄·2H₂O。

The chemical formula of scorodite is FeAsO₄·2H₂O, is a stable compound, the crystal of the compound is mainly in an orthorhombic system or a bipyramid shape, the color of the compound is mostly green, the naturally generated scorodite contains arsenic not less than 30 wt%, and the molar ratio of iron to arsenic is 1: 1. Because scorodite mineral arsenic solubility is low, arsenic removal efficiency is high, arsenic content is high (25-32 wt%), iron dosage is small, and stability is relatively high under the conditions from weak acidity to neutrality, scorodite becomes the choice of fixing and treating arsenic commonly used by people at present. Furthermore, scorodite, depending on its crystal structure, shows suitable settling and filtration separation properties.

Through analyzing a large amount of experimental data, the inventor discovers for the first time that the scorodite has the biological driving effect and can be used as a nontoxic ship functional additive.

Based on the method, the scorodite is firstly used as a functional coating additive for the ship workshop primer, the ship bottom antirust paint, the ship bottom antifouling paint, the ship antirust paint, the waterline paint, the ship shell paint, the cargo compartment paint and the deck paint, and can be applied to the coating paints of different parts of the ship, wherein the mass ratio of the coating paint to the scorodite is (70-99.9): 30-0.1.

The invention also provides a ship antifouling paint composition which comprises epoxy resin, polyamide, ethanol and scorodite powder, wherein the mass ratio of the components is (20-60): (1-100): (1-10), the raw materials are added into a stirring tank according to a set proportion, and the raw materials are uniformly stirred at a preset rotating speed to obtain highly dispersed slurry.

Preferably, the mass ratio of the epoxy resin, the polyamide, the ethanol and the scorodite powder is (30-50): 10-30): 2-8; the stirring speed is 200-600 r/min, and the stirring time is 0.5-4 h.

Further, the mass ratio of the epoxy resin, the polyamide, the ethanol and the scorodite powder is 40:40:15: 5.

Further, the stirring speed is 400-600 r/min, and the stirring time is 1-1.5 h.

The essence of the invention is that the highly-dispersed and uniform coating is prepared by using the scorodite crystal powder with small solubility and no toxicity and other coating reagents, and finally the unique biological activity of the scorodite in the coating is utilized to repel the water organisms so as to realize the antifouling effect. The invention has the advantages of no toxicity of scorodite, low preparation cost, high adhesion strength of the coating slurry to a steel plate and good antifouling effect of the coating to water organisms.

Compared with the prior art, the invention has the beneficial technical effects that:

(1) the invention firstly proposes that the scorodite powder is used as a functional additive of the ship coating, the unique biological activity of the scorodite is utilized to realize the long-term adsorption and growth of microorganisms such as algae spores, bacteria and diatoms and large fouling organisms such as barnacles, mosses and mussels on a steel plate, the adhesion of marine organisms to a ship body is reduced, and the invention has strong innovation.

(2) The invention provides a method for using scorodite as a functional additive of a marine coating, which solves the problem that the marine coating takes cuprous oxide as an antifouling agent to bring adverse effects to marine environment.

(3) The scorodite-containing coating slurry prepared by adopting the epoxy resin and the polyamide as the adhesives and the ethanol as the solvent has excellent bonding performance to the steel plate, and the antifouling coating composition has the advantages of simple preparation process, stable performance, lower cost, environmental friendliness and capability of meeting the requirements of industrial production.

Drawings

Fig. 1 is a diagram showing a real object of scorodite powder in example 2.

FIG. 2 is a schematic representation of the marine antifouling paint of example 3.

Fig. 3 is an effect diagram of a control sample plate of a fresh water hanging plate experiment.

Fig. 4 is an effect diagram of a sample plate of a fresh water hanging plate experiment.

FIG. 5 is a diagram of the effect of the sea water hanging plate test.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Unless otherwise specified, the experimental procedures described in the following examples are conventional, and the reagents are all analytically pure and commercially available.

Example 1

Accurately weighing the base paint or the antirust paint of the ship and the scorodite powder according to the mass ratio of (70-99.9) to (30-0.1), sequentially adding the base paint or the antirust paint of the ship into a stirring tank, starting a stirrer at the rotating speed of 400r/min, and stirring for 60min to obtain highly dispersed slurry.

The scorodite powder in the embodiment is prepared by the following steps:

dissolving sodium arsenate into distilled water to obtain a sodium arsenate solution with the arsenic concentration of 65g/L, adding concentrated sulfuric acid into the sodium arsenate solution according to the molar ratio of sulfuric acid to arsenic of 2:1 for acidification, transferring the acidified solution into a three-neck flask, adding an iron source according to the molar ratio of iron to arsenic of 3:1, and placing the three-neck flask in an oil bath kettle with magnetic stirring to uniformly stir and react for 5 hours at 50-100 ℃; and (3) realizing liquid-solid separation by adopting vacuum filtration, wherein the ratio of liquid to solid is 30: 1mL/g, mixing the precipitate in distilled water, washing, filtering, and drying the precipitate at 60-100 ℃ for 5-8 h to obtain light green scorodite powder.

Example 2

Accurately weighing and sequentially adding the ship waterline paint or antifouling paint and scorodite powder according to the mass ratio of (80-99.5) to (20-0.5) into a stirring tank, starting a stirrer at the rotating speed of 600r/min, and stirring for 30min to obtain highly dispersed slurry.

The scorodite powder in the embodiment is prepared by the following steps:

dissolving sodium arsenate into distilled water to obtain a sodium arsenate solution with the arsenic concentration of 50g/L, adding concentrated sulfuric acid into the sodium arsenate solution according to the molar ratio of sulfuric acid to arsenic of 1:1 for acidification, transferring the acidified solution into a three-neck flask, adding an iron source according to the molar ratio of iron to arsenic of 4:1, placing the three-neck flask in an oil bath kettle with magnetic stirring, uniformly stirring at 70-100 ℃, and introducing oxygen according to 0.1-5L/min for reaction for 10 hours; and (3) realizing liquid-solid separation by adopting vacuum filtration, wherein the ratio of liquid to solid is 10: 1mL/g, mixing the precipitate with distilled water, washing, filtering, drying the precipitate at 60-100 ℃ for 5-8 h to obtain pale green scorodite powder, wherein the obtained scorodite is shown in figure 1.

Example 3

The ship antifouling paint composition comprises the following components in percentage by mass of epoxy resin, polyamide, ethanol and scorodite powder, wherein the mass ratio of the epoxy resin to the polyamide to the ethanol to the scorodite powder is 30: 30: 35: and 5, accurately weighing and sequentially adding the materials into a stirring tank, starting a stirrer at the rotating speed of 200r/min, and stirring for 4 hours to obtain highly dispersed slurry, wherein the highly dispersed slurry is shown in figure 2.

The scorodite powder in this embodiment adopts scorodite ore in nature.

Application example 1

Mixing scorodite and seawater or fresh water according to a liquid-solid ratio (the weight of the seawater or fresh water body: scorodite) of 10: 1mL/g, sampling, adding into a conical flask, oscillating for 18h at normal temperature, taking supernatant, filtering with a microporous membrane with the pore diameter of 0.4um, measuring filtrate by ICP-AES, and subtracting the concentration of arsenic in seawater or fresh water.

The experimental result shows that the toxicity of the scorodite is far lower than the national toxicity leaching standard by 5mg/L, which indicates that the scorodite has no toxicity in fresh water or seawater.

Group of	Example 1	Example 2	Example 3
				Seawater, its production and use	0.08mg/L	0.07mg/L	0.05mg/L
Fresh water	0.05mg/L	0.04mg/L	0.02mg/L

Application example 2

Guiding the ship coating slurry added with the scorodite into a material carrying groove of a coating machine, placing a stainless steel plate with a polished smooth surface at a coating position, starting the coating machine for coating to obtain a steel plate loaded with uniform slurry, and finally placing the steel plate at the temperature of 30-40 ℃ for drying to ensure that a test plate with a complete surface is obtained. At the same time, the reference plate was coated under the same conditions without adding scorodite powder.

And (3) carrying out a hanging plate test on the steel plate loaded with the coating in fresh water and seawater for 6-18 months respectively, and detecting the antifouling effect of the ship coating based on the biological activity of the scorodite on water organisms. The fresh water hanging plate test is a test which is carried out for 8 months by hanging the coating steel plate and the contrast steel plate in a river with aquatic organisms such as river snails and the like. The sea water hanging plate test is that a test plate and a control plate are selected according to the national standard GB5370-85, and the test is carried out in deeper sea water in a certain coastal sea area of Guangdong province for 8 months. And observing and recording the antifouling effect of the steel plate according to the requirements of the national standard.

FIG. 3 shows the adhesion growth of aquatic organisms such as river snails on the surface of the control plate in the fresh water hanging plate test; FIG. 4 shows that the steel plate coated with the marine coating (obtained in example 1) using scorodite as the functional additive has smooth surface and no adhesion of river snail and other aquatic organisms, and the scorodite with unique bioactivity has obvious repellent and antifouling effects on aquatic organisms in fresh water.

Fig. 5 shows that the steel plate coated with the ship paint containing 5 wt% of scorodite (obtained in example 3) after the plate hanging test in seawater shows that no marine aquatic organisms are attached and grow, and the scorodite paint with bioactivity has a dispelling effect on the marine organisms, and the antifouling effect of the steel plate is obvious.

The ship coating disclosed by the invention is integrated with the technologies of non-toxic scorodite preparation, high-efficiency coating of the coating and hanging plate test. The scorodite-containing coating has unique bioactivity, and can completely remove algae spores, bacteria, diatom and other microorganisms and barnacle, moss, mussel and other large fouling organisms from a steel plate for a long time to adsorb and grow.

The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above-described embodiments. Modifications and variations that may occur to those skilled in the art without departing from the spirit and scope of the invention are to be considered as within the scope of the invention.

Claims

1. A functional additive for marine coatings, which is characterized in that the functional additive for marine coatings is scorodite.

2. The marine paint functional additive of claim 1 wherein the scorodite is synthesized by: acidifying sodium arsenate solution with sulfuric acid, adding iron source for arsenic fixation reaction to obtain scorodite precipitate, and sequentially filtering, washing and drying.

3. The functional additive for marine coatings according to claim 2, wherein the iron source is one or more of iron powder, ferrous sulfate, ferrous nitrate, ferrous chloride, ferrous oxide, ferric sulfate, ferric nitrate, ferric trichloride, iron rust, ferrihydrite, ferriferrous oxide, polymeric ferric sulfate, polymeric ferric aluminum sulfate and polymeric ferric chloride.

4. The marine paint functional additive of claim 2 or 3 wherein the scorodite is synthesized by:

5. Marine paint function additive according to claim 1, characterized in that the scorodite can also utilize scorodite FeAsO in nature₄·2H₂O。

6. The application of the functional additive for the marine paint coating according to any one of claims 1 to 5, wherein scorodite is used as the functional additive for the paint coating of a marine workshop primer, a ship bottom antirust paint, a ship bottom antifouling paint, a ship antirust paint, a waterline paint, a ship shell paint, a cargo compartment paint and a deck paint, and is applied to the paint coating of different parts of a ship, wherein the mass ratio of the paint coating to the scorodite is (70-99.9): (30-0.1).

7. The antifouling ship coating composition is characterized by comprising epoxy resin, polyamide, ethanol and scorodite powder, wherein the mass ratio of the components is (20-60): 1-100): 1-10, the raw materials are added into a stirring tank according to a set proportion, and the raw materials are uniformly stirred at a preset rotating speed to obtain highly dispersed slurry.

8. The antifouling marine coating composition as claimed in claim 7, wherein the mass ratio of the epoxy resin to the polyamide to the alcohol to the scorodite powder is (30-50): (10-30): (2-8), the stirring speed is 200-600 r/min, and the stirring time is 0.5-4 h.

9. A marine antifouling paint composition according to claim 8, wherein the mass ratio of the epoxy resin, the polyamide, the ethanol, and the scorodite powder is 40:40:15: 5.

10. A marine antifouling paint composition according to claim 8, wherein the stirring speed is 400 to 600r/min, and the stirring time is 1 to 1.5 hours.