CN101967316A - Nontoxic antifouling paint for oceanographic ship and facilities and method for preparing paint - Google Patents

Abstract

A non-toxic antifouling coating for marine vessels and facilities and a preparation method thereof, which is composed of a base material, an antifouling agent, a filler, a pigment, an auxiliary agent and a solvent, wherein the antifouling agent has an average particle diameter of For silver particles of 1-200 nanometers, the weight percentage of each component is: base material 15-55%, antifouling agent 0.01-10%, filler 10-30%, pigment 0.3-25%, auxiliary agent 2- 8%, solvent 3-55%. While effectively inhibiting the corrosion of marine biological attachments, the invention does not contain toxic agents such as DDT, organotin, cuprous oxide, etc., conforms to the relevant regulations of the International Maritime Organization and the future development trend of antifouling coatings, and realizes the non-toxicity of marine antifouling technology. Poisoning and greening can be widely used in facilities and fields such as ships, floating docks, offshore oil platforms, submarine cables, cooling pipelines of coastal power plants, and seawater farming cages.

Description

A kind of non-toxic anti-fouling coating for marine ships and facilities and preparation method thereof

technical field

The invention belongs to the technical field of coatings, in particular to a non-toxic antifouling coating used for marine vessels and facilities.

Background technique

One of the most important problems encountered in offshore operations is the attachment and fouling of some marine organisms to various marine facilities such as ships, offshore drilling platforms, buoys, mariculture cages, and marine detection instruments. At present, more than 200,000 species of marine organisms have been preliminarily proven, including thousands of species of attached organisms. This kind of marine organisms mainly attach to the hull and the parts below the waterline of marine facilities, which will bring great harm and considerable economic losses to offshore operations. Preventing the harm and adverse effects of marine attached organisms on ships and marine facilities has always been is the focus of attention.

Statistics show that the damage and failure of materials related to the adhesion of marine organisms account for 70%-80% of the total amount of sea-related materials, and it is of great significance to effectively prevent the influence of microorganisms on the adhesion and corrosion of materials. Antifouling coating is an economical and efficient solution to prevent marine biofouling. It inhibits the attachment and growth of marine organisms by releasing the contained marine biotoxic agents at a certain rate, thereby maintaining The smoothness and integrity of the coating on the outer surface of ships and offshore facilities. In the middle and late part of last century, organotin compound antifouling agents such as tributyltin oxide, tributyltin and tin fluoride, triphenyltin chloride, and triphenyltin fluoride were widely used. Although organotin antifouling agents are low in dosage, high in efficiency and broad-spectrum, such organotin compounds are teratogenic and accumulate in marine organisms such as fish and shellfish, which will not only cause genetic variation in marine organisms , It will also enter the food chain and seriously affect the genetics and survival of humans and other organisms. Therefore, in the late last century, countries have legislated to ban organotin antifouling paints. The International Maritime Organization (IMO) has completely banned the use of such products on board ships from January 1, 2008. After the use of organotin antifouling coatings is banned, the substitutes are mainly products composed of cuprous oxide as the main antifouling agent and other auxiliary antifouling chemicals. Today, 80% of marine antifouling coatings use cuprous oxide as antifouling agent. Although its direct harm to the human body is not yet clear, the toxicity index for some fish and whales is greater than 24h. At the same time, it cannot be ignored that a large amount of copper compounds are precipitated and deposited on the seabed, which poses a great threat to the growth of algae and the downstream food chain, and will inevitably cause permanent damage and pollution to the marine environment. Therefore, the International Maritime Organization will begin to restrict the use of cuprous oxide in 2012, and the State Environmental Protection Administration of China will also list cuprous oxide as a high-risk and high-pollution list, and plans to ban it in 2012. In view of this, the development of new non-toxic antifouling coating materials is imminent.

Chinese Patent No. CN98812901 discloses a fluorine and/or siloxane low surface energy antifouling coating. The biggest disadvantage of low surface energy coatings is that the low surface free energy brings about poor adhesion of the coating to the substrate and between coating layers, and poor recoatability, which will cause difficulties in the construction and repair of the coating. Chinese Patent No. CN200510081683 discloses a zinc or copper acrylate resin containing capsaicin functional groups and a preparation method thereof. But unfortunately, this kind of coating is restricted by the process conditions, and there is still a considerable distance between it and the actual application, and its large-scale production is still difficult to realize. The suitable growth environment for marine fouling organisms is slightly alkaline seawater with a pH value of 7.5-8.0, and it is difficult to survive in a highly alkaline or strongly acidic environment. Chinese Patent No. CN97121813 discloses a non-toxic antifouling paint using silicate as an antifouling agent. However, studies have shown that the effective antifouling period of alkaline silicate antifouling coatings is not long, the physical and chemical properties are poor, and the practical application prospects are not clear.

Contents of the invention

The purpose of the present invention is to overcome the deficiencies of the existing antifouling coatings and provide a novel non-toxic marine antifouling coating; another purpose of the present invention is to provide a preparation method of this coating.

The purpose of the present invention is achieved through the following technical solutions:

A non-toxic antifouling coating for marine vessels and facilities, consisting of base material, antifouling agent, filler, pigment, auxiliary agent and solvent, the weight percentage of each component is:

Base material 15～55%,

Antifouling agent 0.01～10%,

Filler 10～30%,

Pigment 0.3～25%,

Auxiliary 2～8%,

Solvent 3～55%.

The antifouling agent is silver particles with an average particle diameter of 1-200 nm.

In the above-mentioned antifouling paint, the base material is acrylic resin, vinyl resin, vinyl chloride resin, vinyl acetate resin, chlorinated rubber, rosin, asphalt, polydivinyl acetylene resin, phenolic resin, urea-formaldehyde resin, melamine resin, polyurethane , epoxy resin, alkyd resin, silicone resin, organic fluorine resin or at least one of basic silicate.

In the above antifouling paint, the fillers are calcium carbonate, barium carbonate, silicon dioxide, talcum powder, graphite, zinc oxide, diatomaceous earth, glass microspheres, barite powder, bentonite, organoclay, china clay, zeolite powder or at least one of mica.

In the above antifouling paint, the pigments are iron oxide red, red clay, iron oxide yellow, carbon black, titanium dioxide, lithopone, magnesium oxide, iron blue, ultramarine blue, benzidine yellow, calcium phosphate, magnesium phosphate or metaboric acid at least one of barium.

In the above-mentioned antifouling coatings, the auxiliary agents are dispersants, defoamers, leveling agents, film-forming aids, wetting agents, plasticizers, drier, pH regulators, preservatives, anti-settling and at least one of thixotropic thickeners;

The above-mentioned additives can be selected from but not limited to the following varieties:

Dispersant: sodium hexametaphosphate, sodium dodecylbenzenesulfonate, zinc stearate, lecithin, Disper BYK series;

Defoamer: tributyl phosphate, dimethyl polysiloxane, polyether modified methyl polysiloxane, aluminum stearate;

Leveling agent: polymethyl acrylate, polymethylphenylsiloxane, polyester modified polydimethylsilane;

Coalescing aids: alcohol ester twelve, Texanol, ethylene glycol, petroleum ether, diisobutyl adipate;

Wetting agent: vinyltriethoxysilane, vinyltriacetoxysilane, dimethicone;

Plasticizers: tributyl phosphate, dibutyl phthalate, epoxy linseed oil, castor oil, chlorinated paraffin;

Drier: cobalt naphthenate, manganese naphthenate, calcium isooctanoate, zirconium isooctanoate, cobalt diethylate;

Preservatives: sodium benzoate, isothiazolinone, benzisothiazolinone (BIT);

pH regulator: ammonia water, sodium hydroxide aqueous solution, acetic acid;

Anti-settling and thixotropic thickeners: organic bentonite, aluminum octoate, calcium stearate, polyethylene wax, zinc ricinoleate.

In the above antifouling paint, the solvent is ketones, such as acetone, cyclohexanone, butanone or esters, such as ethyl acetate, butyl acetate or benzyl acetate; alcohols, such as methanol, ethanol, isopropyl Alcohols, isobutanol, ethylene glycol or propylene glycol; ethers such as ethylene glycol ethyl ether, ethylene glycol butyl ether or propylene glycol ethyl ether; aliphatic hydrocarbons such as n-hexane, cyclohexane, n-pentane, octane or heptane alkanes; aromatic hydrocarbons, such as at least one of toluene, xylene, trimethylbenzene or water.

A kind of method for preparing above-mentioned antifouling coating, it carries out as follows:

Under the condition of room temperature to 80°C, add the base material into the solvent to dissolve, then add antifouling agent, pigment, filler and auxiliary agent in sequence, and stir, disperse and grind at the speed of 1500-5000r/min for 2-6 hours , to produce antifouling coatings.

In the present invention, the non-toxic anti-fouling coating for marine ships and facilities is developed by utilizing the characteristics of silver particles having no toxic and side effects on the human body and other organisms, broad-spectrum antibacterial properties and environmental friendliness. It does not contain DDT, organotin (TBT), cuprous oxide and other toxic agents, conforms to the relevant regulations of the International Maritime Organization (IMO) and the future development trend of antifouling coatings, and realizes the non-toxic and green marine antifouling technology.

Compared with the prior art, the present invention has the following outstanding advantages:

1. Silver particles with a scale of 1 to 200 nanometers are used to prepare marine coatings, which have remarkable antifouling performance, have antifouling effects at low concentrations, and are cost-effective;

2. The antifouling paint of the present invention has a broad-spectrum antifouling effect on attached marine organisms;

3. The antifouling coating of the present invention will not release toxic substances into seawater during use, and is environmentally friendly;

4. The antifouling coating of the present invention can be widely used in facilities and fields such as ships, floating docks, offshore oil platforms, submarine cables, cooling pipes of coastal power plants, and seawater farming cages.

Detailed ways

The technology and features of the present invention will be further described below in combination with specific embodiments.

Example 1

Add each component into the batching tank of the multifunctional disperser according to the following formula, keep the mixture at 50°C, stir, disperse, and grind at a speed of 2000r/min for 4 hours to prepare 1kg of non-toxic marine antifouling paint finished product.

The weight of each component in the formula is respectively:

(1) Acrylic resin 500.00g,

(2) Zinc oxide 187.43g,

(3) Red iron oxide 124.95g,

(4) Talc powder 62.57g,

(5) Xylene 124.95g,

(6) Silver particles 0.10g,

The average particle diameter of the silver particles is 15 nm.

Example 2

(1) The water-soluble acrylic resin base material is mixed with water to form a water-soluble resin aqueous solution, and then organic silicon coupling agent vinyltriethoxysilane and dimethyl silicone oil additives are added to the water-soluble resin aqueous solution;

(2) Add ultra-fine silicon dioxide, titanium dioxide, zinc oxide, light magnesium oxide, sodium silicate and antifouling agent into the batching tank of the multifunctional disperser in sequence at 55°C; stir at a speed of 3500r/min , disperse, and grind for 2 hours to prepare 1 kg of non-toxic marine antifouling paint.

The weight of each component in the formula is respectively:

(1) Water-soluble acrylic resin 392.04g,

(2) Deionized water 417.00g,

(3) Vinyltriethoxysilane 6.58g,

(4)Simethicone oil 16.06g,

(5) Ultrafine silica 22.94g,

(6) Titanium dioxide 13.28g,

(7) Zinc oxide 45.96g,

(8) Light magnesium oxide 32.70g,

(9) Sodium silicate 52.44g,

(10) Silver particles 1.00g,

The average particle size of the silver particles is about 1 nm.

Example 3

Add each component into the batching tank of the multifunctional disperser according to the following formula, keep the mixture at room temperature, stir, disperse, and grind at a speed of 1500r/min for 6 hours to obtain 1 kg of non-toxic marine antifouling paint finished product.

The weight of each component in the formula is respectively:

(1) Coal tar pitch liquid 90.82g,

(2) Rosin 208.58g,

(3) Zinc oxide 159.68g,

(4) Laterite 211.58g,

(5) Talc powder 93.81g,

(6) Heavy benzene 233.53g,

(7) Silver particles 2.00g,

The average particle diameter of the silver particles is 22 nm.

Example 4

Add each component into the batching tank of the multifunctional disperser according to the following formula, keep the mixture at 40°C, stir, disperse, and grind at a speed of 5000r/min for 3 hours to prepare 1kg of non-toxic marine antifouling paint finished product.

The weight of each component in the formula is respectively:

(1) Vinyl resin 149.25g

(2) Tributyl phosphate 27.26g,

(3) Rosin 113.76g,

(4) Epoxy resin 3.28g,

(5) Laterite 236.91g,

(6) Zinc oxide 165.87g,

(7) Talc powder 94.72g,

(8) Organoclay 11.84g,

(9) Cyclohexanone 85.57g,

(10) Trimethylbenzene 106.57g,

(11) Silver particles 4.97g,

The average particle diameter of the silver particles is 45 nm.

Example 5

Add each component into the batching tank of a multifunctional disperser according to the following formula, keep the mixture at 80°C, stir, disperse, and grind at a speed of 4000r/min for 2 hours to prepare 1 kg of non-toxic marine antifouling paint product.

The weight of each component in the formula is respectively:

(1) 35% chlorinated rubber liquid 99.58g,

(2) Chlorinated paraffin 28.96g,

(3) 50% alkyd ester 34.77g,

(4) Rosin 104.32g,

(5) Laterite 231.77g,

(6) Zinc oxide 162.23g,

(7) Talc powder 92.69g,

(8) Organoclay 11.62g,

(9) Low barium carbonate 11.62g,

(10) Xylene 214.94g,

(11) Silver particles 7.50g,

The average particle diameter of the silver particles is 64 nm.

Example 6

Add each component into the batching tank of the multifunctional disperser according to the following formula, keep the mixture at 50°C, stir, disperse, and grind at a speed of 2500r/min for 4 hours, and adjust the pH value to 8 with sodium hydroxide . Prepare 1kg of non-toxic marine antifouling paint finished product.

The weight of each component in the formula is respectively:

(1) Silicone acrylic emulsion 554.26g,

(2) Sodium hexametaphosphate 27.74g,

(3) Zinc oxide 269.50g,

(4) Hydroxyethyl cellulose 13.77g,

(5) Tributyl phosphate 1.36g,

(6) Sodium benzoate 2.82g,

(7) Ethylene glycol 27.74g,

(8) Propylene glycol 2.81g,

(9) Silver particles 100.00g,

The average particle diameter of the silver particles is 78nm.

Example 7

Dissolve acrylic resin in a mixed solvent, add silver particles, dispersant, pigment, filler, etc. in sequence, keep at 35°C, stir, disperse, and grind at a speed of 3000r/min for 2.5 hours to prepare 1kg of non-toxic marine antifouling paint finished product.

The weight of each component in the formula is respectively:

(1) Acrylic resin 435.86g,

(2) Talc powder 43.51g,

(3) Zinc oxide 145.26g,

(4) Phthalocyanine blue 2.94g,

(5) Disper BYK 102 2.94g,

(6) Organic bentonite 32.07g,

(7) Xylene 226.84g,

(8) Butyl acetate 72.58g,

(9) Silver particles 38.00g,

The average particle diameter of the silver particles is 126 nm.

Example 8

Dissolve the modified silicone in an organic solvent, then add additives such as chlorinated paraffin, zinc oxide, dimethyl silicone oil, fluorocarbon surfactant, and silver particles in sequence, keep at 65°C, and rotate at 1800r/min Stir, disperse, and grind for 3.5 hours to become component A of low surface energy non-toxic marine antifouling paint. Dissolve low molecular weight polyamide in mixed solvent at room temperature to prepare component B of antifouling coating. Mix components A and B evenly before use.

The weight of each component in the formula is respectively:

Component A:

(1) Modified silicone 287.40g,

(2) Chlorinated paraffin 67.06g,

(3) Zinc oxide 38.32g,

(4) Fluorocarbon surfactant 2.50g,

(5) Simethicone oil 3.25g,

(5) Mixed solvent 496.24g,

(6) Silver particles 42.00g,

Component B:

(1) Low molecular weight polyamide 5.75g,

(2) Mixed solvent 57.48g,

The mixed solvent is a mixture of toluene, xylene, n-butanol, isobutanol and isopropanol.

The average particle size of the silver particles is 200nm.

The above is only a preferred embodiment of the present invention, it should be pointed out that for those of ordinary skill in the art, without departing from the concept of the present invention, some improvements and changes can also be made and should also be regarded as protection of the present invention within range.

Claims (7)

1. a kind of nontoxic antifouling paint for marine vessels and facilities, it is made up of base material, antifouling agent, filler, pigment, auxiliary agent and solvent, it is characterized in that, described antifouling agent is average particle diameter between Silver particles of 1 to 200 nanometers, the weight percentage of each component is: Base material 15～55%, Antifouling agent 0.01～10%, Filler 10～30%, Pigment 0.3～25%, Auxiliary 2～8%, Solvent 3～55%. 2. nontoxic antifouling paint according to claim 1, is characterized in that, described base material is acrylic resin, vinyl resin, vinyl chloride resin, vinyl acetate resin, chlorinated rubber, rosin, asphalt, polydiethylene At least one of acetylene resin, phenolic resin, urea-formaldehyde resin, melamine resin, polyurethane, epoxy resin, alkyd resin, silicone resin, organic fluorine resin or alkali silicate. 3. nontoxic antifouling paint according to claim 2, is characterized in that, described filler is calcium carbonate, barium carbonate, silicon dioxide, talcum powder, graphite, zinc oxide, diatomaceous earth, glass microsphere, At least one of barite powder, bentonite, organoclay, china clay, laterite, zeolite powder or mica. 4. nontoxic antifouling paint according to claim 3, is characterized in that, described pigment is iron oxide red, iron oxide yellow, carbon black, titanium oxide, lithopone, magnesium oxide, iron blue, ultramarine blue, At least one of benzidine yellow, calcium phosphate, magnesium phosphate or barium metaborate. 5. nontoxic antifouling paint according to claim 4, is characterized in that, described auxiliary agent is dispersant, defoamer, leveling agent, film-forming aid, wetting agent, plasticizer, catalyst At least one of dry agent, pH regulator, preservative or anti-sedimentation and thixotropic thickener; wherein, The dispersant is: sodium hexametaphosphate, sodium dodecylbenzenesulfonate, zinc stearate, lecithin; The defoamer is: tributyl phosphate, dimethyl polysiloxane, polyether modified methyl polysiloxane, aluminum stearate; The leveling agent is: polymethyl acrylate, polymethylphenylsiloxane, polyester modified polydimethylsilane; The film-forming aid is: alcohol ester dodeca, Texanol, ethylene glycol, sherwood oil, diisobutyl adipate; The wetting agent is: vinyltriethoxysilane, vinyltriacetoxysilane, dimethyl silicone oil; Described plasticizer is: tributyl phosphate, dibutyl phthalate, epoxy linseed oil, castor oil; The drier is: cobalt naphthenate, manganese naphthenate, calcium isooctanoate, zirconium isooctanoate, cobalt diethylhexanoate; The preservative is: sodium benzoate, isothiazolinone, benzisothiazolinone (BIT); The pH regulator is: ammonia water, sodium hydroxide aqueous solution, acetic acid; The anti-settling and thixotropic thickeners are: organic bentonite, aluminum octoate, calcium stearate, polyethylene wax, and zinc ricinoleate. 6. The non-toxic antifouling paint according to claim 5, characterized in that, the solvent is ketones, specifically: acetone, cyclohexanone, methyl ethyl ketone; esters, specifically: ethyl acetate, acetic acid Butyl ester, benzyl acetate; alcohols, specifically: methanol, ethanol, isopropanol, isobutanol, ethylene glycol, propylene glycol; ethers, specifically: ethylene glycol ethyl ether, ethylene glycol butyl ether, propylene glycol ethyl ether ; Aliphatic hydrocarbons, specifically: n-hexane, cyclohexane, n-pentane, octane, heptane; aromatic hydrocarbons, specifically: at least one of toluene, xylene, trimethylbenzene or water. 7. A method for preparing the nontoxic antifouling paint for marine vessels and facilities as claimed in claim 1, 2, 3, 4, 5 or 6, is characterized in that, it is carried out as follows: Under the condition of room temperature to 80°C, add the base material into the solvent to dissolve, then add antifouling agent, pigment, filler and auxiliary agent in sequence, and stir, disperse and grind at the speed of 1500-5000r/min for 2-6 hours , to prepare the non-toxic antifouling paint.