CN103160205A - Ionic liquid marine antifouling coating - Google Patents

Abstract

The invention discloses an ionic liquid marine antifouling coating. The ionic liquid marine antifouling coating is composed of 5 to 15 parts of ionic liquid, 30 to 45 parts of polyurethane, 0.1 to 1 part of titanium dioxide powder, 0.2 to 1 part of zinc oxide powder and 0.1 to 1 part of promoter and 40 to 55 parts of diluent. The ionic liquid marine antifouling coating can be used for marine organism pollution resistance on surfaces of ships and marine monitoring instruments.

Description

A kind of ionic liquid marine antifouling coating

technical field

The invention relates to an ionic liquid coating with the function of preventing marine biological pollution.

Background technique

In the historical process of developing and utilizing the ocean, human beings have always been faced with the problem of preventing and eradicating marine organisms. The marine organisms and microorganisms attached to the bottom of the ship and the surface of various facilities in the ocean have caused great harm to marine transportation and the exploration, development, and utilization of marine resources. In order to reduce the harm caused by marine fouling, save energy and expenditure, protect the environment and improve the operating efficiency of marine facilities such as ships, many effective measures have been taken internationally. Existing antifouling coatings include traditional antifouling coatings and non-toxic antifouling paint. Traditional antifouling paints use toxic materials such as copper, tin, mercury, and lead released from paints and organotins to kill marine organisms. However, although this material can reduce or eliminate the fouling of marine organisms, the release of harmful substances has also caused serious harm to the ecological environment and human health. Gao Junmin and others reported the pollution of organic tin to marine organisms in Marine Science, 2006, 30(5): 65-70, and later found that organic tin would accumulate in fish and shellfish, leading to genetic variation, and It may also enter the food chain. On January 1, 2008, ships were completely prohibited from using antifouling primers containing organotins. Therefore, the research and development of low-toxic, non-toxic or environmentally friendly antifouling coatings has become one of the important issues in the world to urgently solve marine biofouling.

A series of non-toxic, natural products with antifouling activity can be extracted from marine plants, marine animals (mainly marine invertebrates) and marine microorganisms, such as Denys R et al in Biofouling, 1995 (8): 259- 271 reported that a series of secondary metabolites halogenated furanones isolated and purified from red algae can effectively inhibit barnacles, macroalgae Ulva and marine bacteria, but the purification process is complicated and the production cost is high, which limits the promotion of its practical application .

Contents of the invention

The object of the present invention is to provide an ionic liquid marine antifouling coating.

The preparation method of ionic liquid is simple, and it is widely used in various fields of chemical research because of its advantages such as no pollution, low volatility, good thermal stability and chemical stability. In addition, our recent research has found that ionic liquid is a highly efficient antibacterial and anti-protein adsorption material, so the present invention adds it to the paint to obtain marine antifouling paint. The coating can be used to prevent marine biological pollution on the surface of ships and marine monitoring instruments.

An ionic liquid marine antifouling coating is characterized in that each component of the coating consists of 5-15 parts of ionic liquid, 30-45 parts of polyurethane, 0.1-1 part of titanium dioxide powder, and 0.2-1 part of zinc oxide powder in parts by weight. , 0.1-1 part of auxiliary agent and 40-55 parts of diluent; wherein the ionic liquid is selected from 1-methyl 3-hexylimidazolium hexafluorophosphoric acid, 1-methyl 3-dodecylimidazolium trifluoromethanesulfonic acid And one of 1-methyl 3-hexylimidazole bistrifluoromethylsulfonyl ammonium; the auxiliary agent is composed of a wetting and dispersing agent and an anti-sedimentation agent, wherein the wetting and dispersing agent is 0.05-0.5 parts, and the wetting and dispersing agent is selected Polyaminoamide solution of cationic unsaturated polybasic carboxylic acid; 0.05-0.5 parts of anti-settling agent, organic bentonite is selected as anti-settling agent; diluent is composed of mixed solvent of acetone, xylene or butyl acetate.

The synthetic method reference of ionic liquid of the present invention: Huddleston et al, Green Chemistry, 2001 (3): 156-164.

The polyurethane of the present invention is a polyurethane prepolymer modified by alcoholysis castor oil, the content of isocyanate is 5-8%, the number average molecular weight is 3500, and its structural formula is:

The titanium dioxide powder particle size of the present invention is 10nm-100nm.

The particle size of the zinc oxide powder in the present invention is 200nm-1μm.

The mass ratio of acetone and xylene or butyl acetate in the present invention is 1:0.5-3.

The wetting and dispersing agent of the present invention is selected from polyaminoamide solution of cationic unsaturated polycarboxylic acid, preferably BYK (130) type dispersant produced by German BYK company.

Coating of the present invention is prepared by following method:

First, polyurethane, ionic liquid, titanium dioxide, zinc oxide, and additives are added to the diluent, dispersed and ground until the fineness of the coating is less than 50 μm, and the marine antifouling coating is obtained.

The coating method of coating of the present invention has two kinds:

The first is spraying: under the pressure of 0.25-0.5MPa, the paint is sprayed onto the substrate.

The second is brushing: use a paintbrush to paint from left to right according to the painting direction first up and then down.

After spraying or brushing, the wet film is cured at room temperature for 24 hours.

The ionic liquid marine antifouling paint of the present invention is sprayed on the surface of the tinplate for coating performance testing. The performance is as follows:

Paint film drying time: GB1728-79, room temperature 16-25 ℃, surface dry 10 hours, hard dry 24 hours;

Adhesion: GB1720-79 (circle method), level 1;

Impact resistance: GB1732-79, 50Kg cm, positive and negative impact;

Flexibility: GB1731-79, 1mm;

The thickness of the coating is controlled at 30 μm-100 μm.

The ionic liquid marine antifouling coating of the present invention is sprayed onto sandblasted low-carbon steel plates for marine hanging panel experiments: the experimental samples and blank panels coated with various antifouling coatings are placed in the depth of 6 meters under the sea for actual sea Hanging board dynamic test. The test time is from June 2010 to June 2011, and the test location is Qingdao Marine Research Base, Shandong. One year after the coating sample was hanged in shallow sea, the paint film was intact, without blistering or falling off, and there was less marine fouling organisms attached to the surface of the sample, indicating that it had a good antifouling effect.

The coating of the invention can be used for preventing marine biological pollution on the surface of ships and marine monitoring instruments.

Detailed ways

Example 1

Coating formula: 40 parts of polyurethane, 5 parts of 1-methyl 3-hexylimidazolium hexafluorophosphate, 0.5 parts of titanium dioxide, 1 part of zinc oxide, 0.25 parts of BYK (130), 0.25 parts of organic bentonite, mixed solvent of acetone and xylene 53 parts (the mass ratio of acetone to xylene is 1:1).

Example 2

Coating formula: 40 parts of polyurethane, 10 parts of 1-methyl 3-hexylimidazolium hexafluorophosphate, 1 part of titanium dioxide, 0.5 part of zinc oxide, 0.25 part of BYK (130), 0.25 part of organic bentonite, mixed solvent of acetone and butyl acetate 48 parts (the mass ratio of acetone to butyl acetate is 1:3).

Example 3

Coating formula: 40 parts of polyurethane, 15 parts of 1-methyl 3-hexylimidazolium hexafluorophosphate, 0.5 parts of titanium dioxide, 1 part of zinc oxide, 0.25 parts of BYK (130), 0.25 parts of organic bentonite, a mixture of acetone and butyl acetate 43 parts of solvent (the mass ratio of acetone to butyl acetate is 1:0.5).

Example 4

Coating formula: 40 parts of polyurethane, 10 parts of 1-methyl 3-dodecyl imidazole trifluoromethanesulfonic acid, 0.5 parts of titanium dioxide, 0.5 parts of zinc oxide, 0.25 parts of BYK (130), 0.25 parts of organic bentonite, acetone and 48 parts of mixed solvents of xylene (the mass ratio of acetone to xylene is 1:0.5).

Example 5

Coating formula: 30 parts of polyurethane, 10 parts of 1-methyl 3-hexylimidazolium ditrifluoromethylsulfonyl ammonium, 1 part of zinc oxide, 0.25 part of BYK (130), 0.25 part of organic bentonite, mixed solvent of acetone and xylene 53 parts (the mass ratio of acetone to xylene is 1:3).

After the paint is formulated according to the above formula, the antifouling coating is obtained by spraying. Table 1 shows the antifouling performance of the coatings involved in the examples after hanging in the shallow sea of Qingdao for one year.

Table 1. Shallow sea coupon test of antifouling coating

*Blank sample: no ionic liquid was added to the coating, and other compositions were the same as in Example 1.

* Wuxi self-polishing antifouling paint produced by China Coating Chemical Co., Ltd.

Claims (6)

1. An ionic liquid marine antifouling coating is characterized in that each component of the coating is in parts by weight, consisting of 5-15 parts of ionic liquid, 30-45 parts of polyurethane, 0.1-1 part of titanium dioxide powder, and 0.2-1 part of zinc oxide powder. 1 part, 0.1-1 part of additive and 40-55 parts of diluent; wherein the ionic liquid is selected from 1-methyl 3-hexylimidazolium hexafluorophosphate, 1-methyl 3-dodecylimidazolium trifluoromethyl One of sulfonic acid and 1-methyl 3-hexylimidazolium bistrifluoromethylsulfonyl ammonium; the auxiliary agent is composed of wetting and dispersing agent and anti-sedimentation agent, of which 0.05-0.5 parts of wetting and dispersing agent, wetting and dispersing The polyaminoamide solution of cationic unsaturated polycarboxylic acid is selected as the agent; 0.05-0.5 parts of the anti-settling agent is selected, and the anti-settling agent is selected from organic bentonite; the diluent is composed of a mixed solvent of acetone, xylene or butyl acetate. 2. coating as claimed in claim 1 is characterized in that polyurethane is the polyurethane prepolymer of alcoholysis castor oil modification, and isocyanate content is 5-8%, and number average molecular weight is 3500, and its structural formula is:

3. The coating according to claim 1, characterized in that the titanium dioxide powder particle size is 10nm-100nm. 4. The coating according to claim 1, characterized in that the zinc oxide powder particle size is 200nm-1 μm. 5. coating as claimed in claim 1 is characterized in that the mass ratio of acetone and xylene or butyl acetate is 1: 0.5-3. 6. coating as claimed in claim 1 is characterized in that wetting and dispersing agent adopts the BYK (130) type dispersant that German BYK company produces.