阅读说明：本技术 一种无铜海洋防污涂料及其制备方法 (Copper-free marine antifouling paint and preparation method thereof ) 是由 苏培 冯丹青 柯才焕 于 2020-06-23 设计创作，主要内容包括：本发明公开了一种无铜海洋防污涂料及其制备方法,防污涂料的原料包括氯醚树脂,松香,颜料,氧化锌,有机膨润土,滑石粉,复配防污剂和混合溶剂；其中复配防污剂包括鱼藤酮和4-溴-2-(4-氯苯基)-5-三氟甲基-1H-吡咯-3-甲腈。混合溶剂包括二甲苯和煤焦油。本发明的无铜海洋防污涂料不含重金属防污剂和国际禁用毒料,防污期效达1年以上,具有附着力强,不易脱落,环境友好等特点,可用于多种海洋设施表面的污损生物防除。(The invention discloses a copper-free marine antifouling paint and a preparation method thereof, wherein the raw materials of the antifouling paint comprise chlorinated polyether resin, rosin, pigment, zinc oxide, organic bentonite, talcum powder, a compound antifouling agent and a mixed solvent; wherein the compound antifouling agent comprises rotenone and 4-bromo-2- (4-chlorphenyl) -5-trifluoromethyl-1H-pyrrole-3-carbonitrile. The mixed solvent comprises xylene and coal tar. The copper-free marine antifouling paint disclosed by the invention does not contain heavy metal antifouling agents and internationally forbidden poisons, has the antifouling period of more than 1 year, has the characteristics of strong adhesion, difficulty in falling, environmental friendliness and the like, and can be used for preventing and removing fouling organisms on the surfaces of various marine facilities.)

1. A copper-free marine antifouling paint is characterized in that: the raw materials of the antifouling paint comprise: 10-20 parts of chlorinated polyether resin, 9-16 parts of rosin, 3-8 parts of pigment, 8-15 parts of zinc oxide, 0.8-1.2 parts of organic bentonite, 3-11 parts of talcum powder, 15-25 parts of compound antifouling agent and 20-30 parts of mixed solvent; the compound antifouling agent comprises 10-20 parts by weight of rotenone and 3-8 parts by weight of 4-bromo-2- (4-chlorophenyl) -5-trifluoromethyl-1H-pyrrole-3-carbonitrile.

2. The copper-free marine antifouling paint according to claim 1, wherein: the weight ratio of the rotenone to the 4-bromo-2- (4-chlorophenyl) -5-trifluoromethyl-1H-pyrrole-3-carbonitrile is 2.8-3.2: 1.

3. The copper-free marine antifouling paint according to claim 1, wherein: the mixed solvent comprises xylene and coal tar.

4. The copper-free marine antifouling paint according to claim 1, wherein: the mixed solvent comprises xylene and 200# coal tar in a ratio of 1.5-2.5: 1.

5. The copper-free marine antifouling paint according to claim 1, wherein: the pigment comprises at least one of titanium dioxide, iron oxide red, iron oxide green, medium chrome yellow, fast bright red, permanent red or lemon yellow.

6. The copper-free marine antifouling paint according to claim 1, wherein: the raw materials of the antifouling paint comprise: 12-14 parts of epichlorohydrin resin, 11-13 parts of rosin, 4-4.5 parts of pigment, 14-15 parts of zinc oxide, 0.9-1.1 parts of organic bentonite, 4.5-5 parts of talcum powder, 19-21 parts of compound antifouling agent and 29-30 parts of mixed solvent; the compound antifouling agent comprises 14-16 parts by weight of rotenone and 4-6 parts by weight of 4-bromo-2- (4-chlorophenyl) -5-trifluoromethyl-1H-pyrrole-3-carbonitrile.

7. The copper-free marine antifouling paint according to claim 1, wherein: the raw materials of the antifouling paint comprise: 15-17 parts of chlorinated polyether resin, 15-16 parts of rosin, 5-7 parts of pigment, 9-11 parts of zinc oxide, 0.9-1.1 parts of organic bentonite, 9-11 parts of talcum powder, 15-17 parts of a compound antifouling agent and 24-26 parts of a mixed solvent; the compound antifouling agent comprises 11-13 parts by weight of rotenone and 3-5 parts by weight of 4-bromo-2- (4-chlorophenyl) -5-trifluoromethyl-1H-pyrrole-3-carbonitrile.

8. A copper-free marine antifouling paint according to claim 6 or 7, wherein: the pigment is iron oxide red.

9. A copper-free marine antifouling paint according to claim 6 or 7, wherein: the mixed solvent comprises xylene and 200# coal tar in a ratio of 1.8-2.2: 1.

10. A method for preparing a copper-free marine antifouling paint according to any one of claims 1 to 9, wherein: firstly, completely dissolving rosin in a mixed solvent to prepare rosin liquid, then adding epichlorohydrin resin into the rosin liquid and dispersing until the epichlorohydrin resin is completely dissolved, sequentially adding pigment, zinc oxide, organic bentonite, talcum powder and a compound antifouling agent for dispersing, grinding until the fineness is below 60 mu m, and dispersing uniformly again to obtain the antifouling paint.

Technical Field

The invention belongs to the technical field of marine antifouling paints, and particularly relates to an antifouling paint which does not contain organic tin, DDT (dichlorodiphenyltrichloroethane), copper and other internationally forbidden antifouling agents.

Background

In marine environments, surfaces of ships, marine engineering, marine monitoring equipment, aquaculture facilities, and the like, are subject to attachment by marine organisms. The phenomenon of marine microorganisms, algae and animals attaching to and adversely affecting the surface of marine immersion equipment is known as marine biofouling (marine biofouling). Marine biofouling can pose a serious hazard to marine transportation, marine engineering, mariculture, and marine defense safety. Organisms are attached to the bottom surface of the ship, so that the surface roughness is increased, the speed is reduced, the fuel is increased suddenly, and the emission of greenhouse gases such as carbon dioxide is increased. It has been reported that an increase in biofouling for a tanker carrying 25 million tons of bio-oil by only 5% results in a 17% increase in fuel consumption. In addition, marine biofouling can increase the encumbrance of engineering equipment such as offshore oil exploitation platforms and the like, and metal corrosion is accelerated; blocking seawater conveying pipelines of factories such as coastal nuclear power stations and the like; the method has the advantages that signal transmission of ocean monitoring equipment is interfered, drift unbalance is caused, and the service life of the ocean monitoring equipment is shortened; blocking the aquaculture net, competing with the aquaculture organisms for food, and seriously reducing the production efficiency; attached organisms are brought into a new sea area along with the ship navigation to cause biological invasion. Therefore, prevention and control of marine biofouling (hereinafter referred to as antifouling) are of great significance in promoting marine economic development and protecting marine ecological environment.

The most economical and commonly used antifouling technology at present is the application of marine antifouling paints on the surface of marine equipment, which prevents fouling of marine organisms through the gradual release of antifouling agents, which are core components of the marine antifouling paints. The early antifouling paint contains organic tin, has excellent antifouling performance, but has high toxicity to many marine organisms, is slowly degraded, destroys the marine ecological environment, and is completely prohibited from being used in 1 month and 1 day in 2008. The bis-p-chlorophenyl trichloroethane (DDT) is also used for the production of antifouling paint in China in a large quantity, is applied to fishing boats for a large amount, and currently, China actively fulfills the Stockholm convention on persistent organic pollutants and prohibits the DDT from being used as a marine antifouling agent. Currently, cuprous oxide antifouling agents are mainly used at home and abroad, however, the marine ecological environment can be seriously damaged due to the continuous accumulation of copper in the marine environment, and partial port cities in Europe and America begin to limit the port berthing of ships using copper-based antifouling coatings. In the comprehensive records of environmental protection (2017), published by the ministry of environmental protection in China, the "organotin-containing antifouling paint", "DDT-containing ship bottom antifouling paint" and "cuprous oxide-containing antifouling paint" are listed as products with high pollution and high environmental risk. Under the situation, the research and development of novel environment-friendly antifouling paint is urgent.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provides a copper-free marine antifouling paint and a preparation method thereof, wherein the copper-free marine antifouling paint uses a low-content compound antifouling agent, has high antifouling performance, can be used for preventing and removing fouling organisms on the surfaces of marine facilities made of various materials, does not contain organic tin, DDT (dichlorodiphenyltrichloroethane) and copper antifouling agents, and solves the problem that the existing copper-containing antifouling paint and the like have increasingly serious environmental pollution.

One of the technical schemes adopted by the invention for solving the technical problems is as follows:

a copper-free marine antifouling paint, which comprises the following raw materials: 10-20 parts of chlorinated polyether resin, 9-16 parts of rosin, 3-8 parts of pigment, 8-15 parts of zinc oxide, 0.8-1.2 parts of organic bentonite, 3-11 parts of talcum powder, 15-25 parts of compound antifouling agent and 20-30 parts of mixed solvent; the compound antifouling agent comprises 10-20 parts by weight of rotenone and 3-8 parts by weight of 4-bromo-2- (4-chlorophenyl) -5-trifluoromethyl-1H-pyrrole-3-carbonitrile.

Furthermore, the weight ratio of the rotenone to the 4-bromo-2- (4-chlorophenyl) -5-trifluoromethyl-1H-pyrrole-3-carbonitrile is 2.8-3.2: 1. When the weight ratio of rotenone to 4-bromo-2- (4-chlorophenyl) -5-trifluoromethyl-1H-pyrrole-3-carbonitrile is less than the above ratio, for example, 2.5:1, a good antifouling effect cannot be achieved; when the weight ratio of rotenone to 4-bromo-2- (4-chlorophenyl) -5-trifluoromethyl-1H-pyrrole-3-carbonitrile is more than the above ratio, the cost of the antifouling paint increases. Therefore, the weight ratio of the rotenone to the 4-bromo-2- (4-chlorophenyl) -5-trifluoromethyl-1H-pyrrole-3-carbonitrile is 2.8-3.2: 1, and the balance between the antifouling effect and the cost is achieved.

Further, the mixed solvent comprises xylene and coal tar. The coal tar is 200# coal tar (200# coal tar is purchased from Hencai chemical industry materials sales Co., Ltd., Tianchang).

Preferably, the mixed solvent comprises xylene and 200# coal tar in a ratio of 1.5-2.5: 1.

The chlorinated polyether resin is a vinyl chloride-isobutyl vinyl ether resin, and is a polymer obtained by copolymerizing 75% of vinyl chloride and 25% of isobutyl vinyl ether. The chlorinated polyether resin contains more isobutyl ether long-chain groups, so that the antifouling paint has better flexibility after forming a film. The chlorinated polyether resin also has a large number of ether bonds, so that the antifouling paint has good adhesive force with various substrates.

The rosin is used as a film forming substance in a coating system, so that the coating is bright in color and luster, quick to dry and smooth and not easy to fall off after film forming.

The pigment has a covering function in a coating system and provides color matching for a coating, and the copper-free marine antifouling coating disclosed by the invention does not contain a cuprous oxide antifouling agent, so that the copper-free marine antifouling coating can be prepared into various colors. Further, the pigment comprises at least one of titanium white, iron oxide red, iron oxide green, medium chrome yellow, fast bright red, permanent red or lemon yellow.

The zinc oxide has certain antibacterial and mildewproof effects and can assist in improving the antifouling performance of the coating.

The organic bentonite is a compound of organic quaternary ammonium salt and natural bentonite, is used as an anti-settling agent and a thickening agent in a coating system, and has the functions of stabilization, thickening and dispersion.

The talcum powder has good suspension property and dispersibility, and can improve the hardness and increase the stability of the coating in a coating system.

The mixed solvent has the functions of dissolving resin and dispersing and stabilizing various components, and the advantage of compounding the xylene and the 200# coal tar is that the cost of the coating is reduced.

Preferably, the raw materials of the antifouling paint comprise: 12-14 parts of epichlorohydrin resin, 11-13 parts of rosin, 4-4.5 parts of pigment, 14-15 parts of zinc oxide, 0.9-1.1 parts of organic bentonite, 4.5-5 parts of talcum powder, 19-21 parts of compound antifouling agent and 29-30 parts of mixed solvent; the compound antifouling agent comprises 14-16 parts by weight of rotenone and 4-6 parts by weight of 4-bromo-2- (4-chlorophenyl) -5-trifluoromethyl-1H-pyrrole-3-carbonitrile.

Wherein the pigment is iron oxide red; the mixed solvent comprises xylene and 200# coal tar in a ratio of 1.8-2.2: 1.

In one embodiment, the raw materials of the antifouling paint comprise: 15-17 parts of chlorinated polyether resin, 15-16 parts of rosin, 5-7 parts of pigment, 9-11 parts of zinc oxide, 0.9-1.1 parts of organic bentonite, 9-11 parts of talcum powder, 15-17 parts of a compound antifouling agent and 24-26 parts of a mixed solvent; the compound antifouling agent comprises 11-13 parts by weight of rotenone and 3-5 parts by weight of 4-bromo-2- (4-chlorophenyl) -5-trifluoromethyl-1H-pyrrole-3-carbonitrile.

Wherein the pigment is iron oxide red; the mixed solvent comprises xylene and 200# coal tar in a ratio of 1.8-2.2: 1.

The second technical scheme adopted by the invention for solving the technical problems is as follows:

a preparation method of a copper-free marine antifouling paint comprises the steps of completely dissolving rosin in a mixed solvent to prepare rosin liquid, then adding epichlorohydrin resin into the rosin liquid and dispersing until the epichlorohydrin resin is completely dissolved, sequentially adding pigment, zinc oxide, organic bentonite, talcum powder and a compound antifouling agent for dispersing, grinding until the fineness is below 60 mu m, and dispersing uniformly again to obtain the antifouling paint.

The equipment, reagents, processes, parameters and the like related to the invention are conventional equipment, reagents, processes, parameters and the like except for special description, and no embodiment is needed.

All ranges recited herein include all point values within the range.

In the present invention, the proportions are by weight unless otherwise specified. The units of parts by weight are, for example, grams, kilograms or tons.

Compared with the background technology, the technical scheme has the following advantages:

(1) the copper-free marine antifouling paint contains epichlorohydrin resin, rosin, zinc oxide, organic bentonite and talcum powder, wherein film forming substances, namely the epichlorohydrin resin and the rosin, are matched for use, so that the antifouling paint can have good adhesive force on different base materials, and can slowly release an antifouling agent to the surface of a coating through the dissolution of the rosin to play an antifouling effect, the zinc oxide and the talcum powder can improve the strength of the coating, and the organic bentonite can be used as an anti-settling agent and a thickening agent to improve the storage stability of a paint system.

(2) The antifouling paint does not contain toxic materials such as organic tin, DDT (dichloro diphenyl trichloroethane) and cuprous oxide, uses the biological insecticide rotenone and is matched with the insecticide 4-bromo-2- (4-chlorphenyl) -5-trifluoromethyl-1H-pyrrole-3-formonitrile, can effectively prevent marine organisms from fouling marine facilities, and has low environmental risk.

(3) The antifouling paint of the present invention does not contain a deep-colored antifouling agent such as cuprous oxide, and therefore can be prepared into paints of various colors as required.

(4) The antifouling paint disclosed by the invention is simple to prepare, wide in application range and environment-friendly.

Detailed Description

The present invention will be described in detail with reference to the following examples: