RU2813094C1 - All-purpose antifouling and anti-corrosion coating composition for aerial and underwater application - Google Patents

Abstract

FIELD: antifouling coatings.

SUBSTANCE: means for protecting underwater parts of vessels, ships and hydraulic structures from fouling by marine organisms. The proposed antifouling material is environmentally friendly and has a net zero carbon. Universal antifouling and anti-corrosion coating composition for air and underwater application is described, including epoxy resin, active thinner, hardener, titanium dioxide, aerosil and additional components: grade 400 cement, epoxidized soybean oil, catamine, copper pyrithione, chlorinated paraffin and carbon black, with the following ratio of components, wt.%: epoxy resin 51.85-55.15; active diluent 3.0-6.0; titanium dioxide 10.0-12.0; soot 0.1-0.2; chlorinated paraffin 0.4-0.7; aerosil 0.2-0.4; cement grade 400 5.0-8.0; epoxidized soybean oil 0.05-0.1; catamine (alkyldimethylbenzylammonium chloride) 0.1-0.2; copper pyrithione 1.0-2.5; amine hardener 18.0-25.0.

EFFECT: creation of an antifouling coating for application to the surface to be protected directly under water using divers or special robotic equipment.

4 cl, 2 tbl, 6 ex

Description

The invention relates to means of protecting underwater parts of vessels, ships and hydraulic structures from fouling by marine organisms. The proposed anti-fouling material is environmentally friendly and has a zero carbon footprint.

Fouling agents quickly attach to the surface of the vessel, which leads to an increase in resistance to the vessel's movement and an increase in fuel consumption to maintain the required speed. Hydraulic structures also require antifouling and anti-corrosion protection in the underwater coating system.

A known antifouling agent in the marine environment is in the form of enamel based on a combination of rosin with a polymer film former (perchlorovinyl resin, pentaphthalic varnish) containing salicylic acid anilide and a copper-containing biocide - a spent copper-chrombarium catalyst. Antifouling paint XB-5295 is prepared in the usual way in a ball mill. The spent copper-chrombarium catalyst (MCC) is first fused with rosin at 160 - 185°C for 2 hours, the resulting alloy is broken into pieces, loaded into a ball mill, additives and part of the solvent are added. Grinding is carried out for 16 - 25 hours, after which PSH-LS resin is added in the remaining amount of solvent. Stir until a homogeneous solution is obtained in a ball mill to obtain paint of appropriate dispersion (RF patent for invention No. 2115680, published on July 20, 1998).

However, such enamel has insufficient service life of the coating, a high rate of leaching of cuprous oxide and high consumption, as well as low elasticity of the coating.

The enamel is also known according to the RF patent for invention 2394864, publ. 07/20/2010, consisting of the following components:

Rosin 11.9-13.0 Copolymer of vinyl chloride with vinyl acetate 2.4-3.7 Epoxy resin 0.48-1.9 Epoxy ester varnish 4.0-5.0 Biocide - cuprous oxide 45.0-50.0 Dibutyl phthalate 3.0-4.0 Zinc oxide 1.2-1.7 Salicylic acid 1.6-2.0 Salicylic acid anilide 1.5-2.1 Benzenesulfonic acid 0.3-0.9 Organic solvents Rest

To obtain anti-fouling enamel according to the specified patent, benzenesulfonic acid, cyclohexanone, a mixture of salicylic acid and salicylic acid anilide and acetone at their ratio, respectively, wt.%: 0.9-0.3: 3.2-2.6: 2.1 -1.5:10.6-9.0 is stirred at a temperature of 18-22°C for at least 1 hour, then a copper-containing biocide is loaded - cuprous oxide and the mixture is impregnated for 25-40 minutes, the resulting mass is treated with 50-60% - solution of rosin in a solvent at a temperature of 18-25 ° C, and then combined with the rest of the rosin, a film former - epoxy ester varnish, a copolymer of vinyl chloride with vinyl acetate, epoxy resin, a plasticizer - dibutyl phthalate, a pigment - zinc oxide, after which the mixture is dispersed until degree of grinding is 50-70 microns.

The resulting composition ensured a decrease in the rate of leaching of cuprous oxide and a reduction in its consumption, as well as an increase in the elasticity of the coating. The enamel is easily applied to horizontal and vertical surfaces, has good physical and mechanical properties (does not crack under the influence of various climatic factors), and high anti-fouling properties, that is, it has the necessary set of characteristics that ensure a long service life for the coating.

Improving the main technical characteristics of the coating and increasing the service life of the anti-corrosion coating system in conditions of highly mineralized / sea / water was also achieved in the enamel composition according to patent No. 2588225, publ. 06/27/2016 to protect the underwater part of ship hulls, ship equipment and mechanisms in contact with water, offshore drilling rigs, and port facilities from biofouling.

Anti-fouling enamel is a polymer coating based on epoxy resin, including an anti-fouling additive and an amine type hardener. An epoxy rubber adduct based on low molecular weight polysulfide and nitrile butadiene rubbers and an excess of low molecular weight epoxy resin is used as a polymer base; the coating additionally contains oligoester epoxide and pigments, and lanthanum, cobalt or manganese oxides or mixtures thereof are used as an antifouling additive, and an antifouling additive can be introduced into the coating, both together with other components, and by spraying after mixing all other components, including the hardener, and applying them to the surface to be protected in the following ratio of components, wt.%, based on 100 wt.% of the composition:

Epoxy rubber adduct (copolymer of epoxy resins with rubber) 61.0-62.0 Oligoester epoxide 8.0-8.5 Pigments 2.5-3.5 Antifouling additive 19.0-22.0 Hardener 6.5-7.0

The composition according to the Russian Federation patent for invention No. 2358998, publ. can be considered the closest to the proposed enamel in terms of the composition of components. dated June 20, 2009, composition, mass%:

epoxy-melamine-polyester varnish EP-074 with a content of non-volatile substances 55.4% 42.0-55.434 titanium dioxide 33.3-40.8 Aerosil A-175 1.4-5.8 microtalc 4.0-5.2 solvent R-189 4.7-19.0, hardener 8.0-13.5

The anti-corrosion coating system includes three layers: an upper, an intermediate and a lower layer, the upper and intermediate layers being made of the specified composition, and the lower layer being made of an epoxy paint and varnish material - VG-33 primer containing specularite pigment.

However, all of the listed enamels must be applied to the ship’s hull in a factory setting (dry dock), which requires significant material costs.

The technical result of the proposed solution is the creation of an anti-fouling coating for application to the surface to be protected directly under water using divers or special robotic equipment.

To achieve the stated technical result, a universal anti-fouling and anti-corrosion coating composition for air and underwater application was obtained, including epoxy resin, active thinner, hardener, titanium dioxide, Aerosil, grade 400 cement, epoxidized soybean oil, catamine, copper pyrithione, chlorinated paraffin and carbon black, with the following ratio of components, wt.%:

Epoxy resin 55.15-51.85 Active diluent 3.0-6.0 Titanium dioxide 10.0-12.0 Soot 0.1-0.2 Chlorinated paraffin 0.4-0.7 Aerosil 0.2-0.4 Cement grade 400 5.0-8.0 Epoxidized soybean oil 0.05-0.1 Katamine (alkyldimethylbenzylammonium chloride) 0.1-0.2 Copper pyrithione 1.0-2.5 Amine hardener 25.0-18.0

The proposed composition of the components of the anti-fouling and anti-corrosion coating composition (enamel) ensures its thixotropy, does not contain organic solvents, and is environmentally friendly. Thanks to thixotropy (the ability of a substance to reduce viscosity (liquefy) from mechanical action and increase viscosity (thicken) at rest), a composition that has a fairly thick consistency, reminiscent of jelly or gel, immediately becomes liquid. While a brush or roller with such enamel moves along the surface to be painted, the enamel remains liquid and is easy to apply, while it does not flow from a vertical surface, does not drip, and at rest it becomes thick and durable. This property of the proposed enamel composition allows it to be applied to the surface to be painted under water, outside of dry docks on land. This significantly simplifies and reduces the cost of protecting the underwater part of ship hulls, ship equipment and mechanisms in contact with water, offshore drilling rigs, and port facilities.

The proposed composition is prepared in two stages. At the first stage, epoxy resin, active diluent, titanium dioxide, soot, paraffin chlorine, aerosil are loaded into the mixer in the ratio wt.%: 55.15-51.85: 10.0-12.0: 10.0-12.0 :0.1-0.2:0.4-0.7:0.2-0.4 and stir for at least 1 hour.

At the second stage, the following are added to the reaction mass: cement grade 400, epoxidized soybean oil, catamine and copper perithione in a wt.% ratio of 5.0-8.0:0.05-0.1:0.1-0.2:1 -2.5. Dispersion is carried out to 70-80 microns for at least 1 hour. Dilute the mass with an active diluent (18.0-25).

The patented composition of components is thixotropic, but before use it requires thorough mixing and addition of the calculated amount of amine hardener (18.0-25.0 wt.%). The application of enamel is carried out with a brush, roller or spatula directly in water or using special equipment. The surface must be cleaned before application.

This enamel can also be applied in air using standard equipment.

Table 1 shows the various compositions of the proposed enamel in comparison with one of its analogues, and Table 2 compares their technological indicators.

Table 1 Components Content of components in the compositions of the analogue and the proposed enamel, wt.% RU 2394864 (analogue) 1 2 3 4 5 1. Biocide - a) copper oxide Cu ₂ O 50.0 - - - - - b) copper pyrithione - 1.0 1.5 1.5 2.0 2.5 c) katamine - 0.1 0.1 0.15 0.2 0.25 2. Titanium dioxide - 10.0 10.5 11.0 11.5 12.0 3. Soot - 0.1 0.12 0.15 0.18 0.2 4. Chlorinated paraffin - 0.4 0.5 0.6 0.65 0.7 5. Aerosil - 0.2 0.25 0.3 0.35 0.4 6. Cement grade 400 - 5.0 6.0 7.0 7.5 8.0 7. Rosin 13.0 - - - - - 8. Acetone 9.0 - - - - - 9. Benzenesulfonic acid 0.3 - - - - - 10. Epoxy ester varnish EF-0188 4.0 - - - - - 11. Copolymer of vinyl chloride with vinyl acetate A-15 3.0 - - - - - 12. Epoxidized soybean. oil - 0.05 0.06 0.07 0.09 0.10 13. Plasticizer dibutyl phthalate 3.0 - - - - - 14. Cyclohexanone 3.0 - - - - - 15. Salicylic acid anilide 2.0 - - - - - 16. Salicylic acid 1.8 - - - - - 17. Zinc oxide 1.2 - - - - - 18. Epoxy resin 1.4 55.15 52.97 52.23 52.03 51.85 19. Active diluent - 3.0 4.0 5.0 5.5 6.0 20. Amine hardener 0.3 25.0 24.0 22.0 20.0 18.0 21. Solvent 8.0 No

table 2 Technological indicator RU2394864 Examples of the Invention 1 2 3 4 5 1 Color Red-brown Grey 2 Mass fraction of non-volatile substances, % 75-78 100 100 100 100 100 3 Maximum thickness of non-draining wet layer from a vertical surface, mm, not less 0.3 0.3 0.4 0.5 0.5 0.5 4 Drying time to degree 3 at 20°C, hours, no more 8 5 5 5 5 5 5 Coating adhesion, points, no less 2 2 2 1 1 1 7 Coating system thickness, microns 320
(3 layers) 420
1 layer 450
1 layer 470
1 layer 480
1 layer 500
1 layer 8 Service life in the tropics (biocidal properties) 4 1 1.5 2 2 2 9 Anti-corrosion properties in a salt spray chamber 500 1000 1000 1000 1000 1000 10 Can be applied underwater No Yes Yes Yes Yes Yes

As can be seen from Table 2, the coating based on the proposed anti-fouling composition of components (enamel) is inferior in anti-fouling properties to its analogue, but has a greater thickness per applied layer (better technological indicators and protective physical and mechanical properties) and better anti-corrosion properties.

The main advantage of this composition (enamel): it can be applied directly in water without docking the vessel and does not contain harmful organic solvents, and has a zero carbon footprint.

Claims (5)

1. A universal anti-fouling and anti-corrosion coating composition for air and underwater application, including epoxy resin, active thinner, hardener, titanium dioxide, aerosil, characterized in that it additionally contains grade 400 cement, epoxidized soybean oil, catamine, copper pyrithione, chlorinated paraffin and carbon black, in the following ratio of components, wt. %: Epoxy resin 55.15-51.85 Active diluent 3.0-6.0 Titanium dioxide 10.0-12.0 Soot 0.1-0.2 Chlorinated paraffin 0.4-0.7 Aerosil 0.2-0.4 Cement grade 400 5.0-8.0 Epoxidized soybean oil 0.05-0.1 Katamine (alkyldimethylbenzylammonium chloride) 0.1-0.2 Copper pyrithione 1.0-2.5 Amine hardener 25.0-18.0 2. The composition according to claim 1, characterized in that the components of the composition are mixed in two stages, at the first stage epoxy resin, active diluent, titanium dioxide, carbon black, chlorinated paraffin, aerosil are mixed for 1 hour, at the second stage cement grade 400 is added , epoxidized soybean oil, catamine, copper pyrithione and the mixture are dispersed to 70-80 microns. 3. The composition according to claim 1, characterized in that it is diluted with an active diluent to technological viscosity. 4. The composition according to claim 1, characterized in that it is applied to the cleaned surface in 1 layer.