CN112521783B

CN112521783B - Antifouling and anticorrosive marine coating

Info

Publication number: CN112521783B
Application number: CN202011371826.0A
Authority: CN
Inventors: 许旺发; 卻林; 张芳; 梁坤国
Original assignee: Beibu Gulf Marine New Materials Research Institute
Current assignee: Beibu Gulf Marine New Materials Research Institute
Priority date: 2020-11-30
Filing date: 2020-11-30
Publication date: 2022-03-18
Anticipated expiration: 2040-11-30
Also published as: CN112521783A

Abstract

The invention discloses an antifouling and anticorrosive marine coating, which is prepared from polymerized o-p-methylaniline, polychlorotrifluoroethylene, aldehyde ketone resin, alkyl succinic acid imide, eucalyptus oil, toosendanin, dicyclopentenyloxyethyl acrylate, hydroxypropyl methyl cellulose, coumarone-indene resin and aqueous chlorinated rubber according to the weight ratio of 7-19: 4.6-5.8: 7.7-9.4: 8-11.2: 6-14: 9-16: 6-8: 4-6: 4-6: 2.7-6.1 by mass ratio. The ship coating disclosed by the invention is excellent in performance, the effective components are obtained simply, conveniently and quickly, the ship body can be effectively protected from seawater erosion, and the adhesion of marine vegetation is effectively prevented.

Description

Antifouling and anticorrosive marine coating

[ technical field ] A method for producing a semiconductor device

The invention relates to the technical field of marine coatings, and particularly relates to an antifouling and anticorrosive marine coating.

[ background of the invention ]

Data show that the ocean plays a great role in the economic and social development of coastal areas in the east of China. Land area of 12 provinces, regions and cities along the sea accounts for only 14% of the land area, but GDP accounts for 60% of the country. The national ocean economic output value is 80 million yuan in 1980, 438 million yuan in 1990, 4133 million yuan in 2000, 1.3 trillion yuan in 2004, 3.8 trillion yuan in 2010, and the acceleration is as high as more than 20%. The development of marine economy cannot be kept away from the support of 'boat ships' and other marine facilities, and the marine corrosion prevention and pollution prevention are always the primary problems considered in the marine industries such as marine fishery, marine transportation, marine equipment and the like at any moment. The marine coating (marine anticorrosive coating) is a primary means for protecting marine equipment, and is a coating which is coated on the marine equipment to ensure long anticorrosive life of the marine equipment. The marine anticorrosive paint can ensure long anticorrosive life when being smeared on marine infrastructure, can react with iron atoms on the surface of a steel structure quickly to generate a material with physical and chemical double protection functions, and can resist chloride ion corrosion for a long time. With the rapid development of marine economy in China, the corrosion prevention of ships and marine engineering facilities becomes an important problem to be solved urgently in development, and the development prospect of marine coatings is more and more seen by people. In 2010, the ship building amount in China exceeds Korea for the first time, and the world is the first time to jump. The container manufacturing amount is stabilized in the world from the end of the 90 s of the 20 th century, and the current production and sales amount accounts for 95% of the world total amount. As the marine coating accounts for more than 90% of the total marine coating demand, China becomes the first country of world marine coating use with the leap of shipbuilding volume. In 2010, the market scale of the marine coating in China exceeds 350 billion yuan.

The marine coatings of the prior art generally employ epoxy resins as the film-forming substrate. However, the epoxy resin has poor heat resistance and hydrophobic property, so that the marine coating in the prior art is difficult to meet the marine environment with extreme humidity, high temperature and high salt fog. Compared with developed countries such as Enmeide, the ocean development and utilization level in China is not high generally, the traditional industry is mainly used, the proportion of the emerging industry is low, and the problems of slow conversion of scientific and technological achievements, difficulty in financing, difficulty in profit and the like still exist in part of the industry. In the process of developing marine resources, the marine organism attachment fouling problem severely limits the development of marine resource economy, and the loss of ships, marine ranches, marine facilities and the like caused by the marine organism attachment fouling problem is difficult to estimate every year.

In conclusion, the requirements of market demands and the development of pollution-free marine anticorrosion and antifouling technologies are met, and the development of an environment-friendly paint which is multifunctional, integrates antifouling, anticorrosion, low pollution and low cost is urgent.

[ summary of the invention ]

Aiming at the defects of the prior art, the invention aims to provide an antifouling and anticorrosive marine coating which is a bionic environment-friendly coating preparation with simple preparation, convenient preparation, no organic tin and no toxicity or pollution. The invention adopts the bionics principle, extracts alkaloid and peptide active antifouling agents from seaweeds and sponges by analyzing the marine organism antifouling mechanism, and prepares a bionic nontoxic biological antifouling preparation with broad-spectrum antifouling effect by adjusting the polarity, thus being an antifouling paint used for offshore undersea facilities and ships.

The antifouling anticorrosive marine coating is prepared from the following raw materials in parts by weight:

further, the antifouling and anticorrosive marine coating is prepared from the following raw materials in parts by weight:

furthermore, the antifouling and anticorrosive marine coating is prepared from the following raw materials in parts by weight:

in the antifouling and anticorrosive marine coating, the functions of the components are as follows:

toosendanin: through toxic and side effects of the toosendanin alkaloid, the nerve center conduction of the sucking organism is blocked, and the respiration and metabolism effects are destroyed, so that the effect of expelling the attachment of marine organisms is achieved.

Fast-growing eucalyptus: the eucalyptus oil is extracted from the leaves, and the terpene compounds in the eucalyptus oil have the functions of inhibiting biological activity and paralyzing central nerves, so that the side surface of the eucalyptus oil can achieve the effect of expelling marine organism attachment.

Polymerization of o-p-methylaniline: slightly soluble in water, and the coating organically synthesizes an intermediate, thereby accelerating the synthesis progress of the coating.

Polychlorotrifluoroethylene: the coating has good corrosion resistance, can be soaked in seawater for a long time without any corrosion, improves the waterproof performance of the coating, and is a low-cost and high-efficiency barrier polymer.

Aldehyde ketone resin: the cyclohexanone-formaldehyde resin has strong adhesive force, is non-saponifiable, has good quick-drying property and is insoluble in seawater.

Dicyclopentenyloxyethyl acrylate (DPOA): as the film forming auxiliary agent is unsaturated polymerizable organic matter, the film forming auxiliary agent is beneficial to improving the coalescence performance, promoting the plastic flow and elastic deformation of a macromolecular compound, increasing the hardness of a coating film, and causing no pollution to the marine environment, and is an active film forming auxiliary agent.

Hydroxypropyl methylcellulose: as a thickening agent, the viscosity of the material is increased.

Coumarone-indene resin: has aromatic heterocyclic structure, anti-cracking property, increased coating viscosity, excellent reinforcing effect and multiple functions.

Aqueous chlorinated rubber: the product is matched with coumarone-indene resin, has excellent creep resistance, improves the viscosity and the wear resistance of the product, has wide application range and excellent resistance effect on salt, alkali and corrosivity of seawater.

The invention also relates to a preparation method of the antifouling and anticorrosive marine coating, which comprises the following steps:

1) under the uniform stirring of 250-one-step stirring at 330r/min, adding aldehyde ketone resin, water-based chlorinated rubber, polymerized o-p-methylaniline, polychlorotrifluoroethylene and acrylic dicyclopentenyloxyethyl ester in sequence, and stirring uniformly;

2) continuously stirring at a constant speed of 330r/min under 250-;

3) adjusting the stirring speed from 250-600 r/min to 500-600r/min, maintaining for 5-10min, and stirring uniformly;

4) adjusting the stirring speed from 500-600r/min to 160-220r/min, adding eucalyptus oil, maintaining for 3-5min, and stirring uniformly;

5) adding hydroxypropyl methylcellulose to make the viscosity of the material reach 3400mpa.s, namely 125KU, and uniformly stirring to obtain a finished product;

the preparation method of the eucalyptus oil comprises the following steps: cleaning fast-growing folium Eucalypti Globueli, drying with a dryer, pulverizing into powder with a pulverizer, adding into a steam distillation kettle, distilling and extracting, separating oleum Eucalypti and water with an oil-water separator, recovering waste diethyl ether with a diethyl ether extractor and a diethyl ether recovery tower, passing through a fixed bed adsorption dryer, and removing impurity oil with a reduced pressure rectification tower to obtain oleum Eucalypti;

the preparation method of the toosendanin comprises the following steps: taking cortex Meliae, cortex Meliae and fructus Toosendan as raw materials, 60% (v/v) ethanol as extracting solution, and the liquid-material ratio is 1: 9, extracting for 80min at 60 deg.C for 4 times, mixing the 4 extractive solutions, and concentrating to 1/6.

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

1. the invention fully utilizes the special products of the chinaberry trees in south China, extracts the effective component of the chinaberry extract, and achieves the effect of preventing marine organisms from attaching through the stimulation effect of phytotoxin on the nervous system of the marine organisms on the premise of not using tin-containing self-polishing antifouling paint. The toosendanin is prepared by fully utilizing the special plants in Guangxi province, the different extraction modes are suitable for different chemical fields, and the extraction types are water extraction and supercritical CO₂The extraction efficiency reaches the highest by taking water as a solvent under the same operation steps, but in consideration of the problem of application range, ethanol with the same excellent polarity is selected as an extracting agent, the bacteriostatic effect is the best, and the effect is better when the toosendanin is added into the paint.

2. Due to the problem of limited extraction efficiency of the existing process, the eucalyptus oil in the market is expensive, and the content of 1, 8-cineole in the eucalyptus oil is low. The high-purity eucalyptus oil can be obtained at low cost by distilling with water vapor, extracting with diethyl ether, drying, removing impurity oil after the extract is distilled out synchronously with the vapor. The method extracts the eucalyptus oil by utilizing the fast-growing eucalyptus growing in the Guangxi territory, can fully utilize local resources of the Guangxi province, and can solve the problem of invasion of foreign species in the Guangxi province: the fast-growing eucalyptus trees can solve the problem that the fast-growing eucalyptus trees grow in high-altitude areas such as Guangxi XiLin and Happy industry due to the growth characteristics of the fast-growing eucalyptus trees; secondly, the problem of water resource shortage in important river catchment areas of Guangxi such as a white three forest and a river pool, Liuzhou and the like due to the fact that the fast-growing eucalyptus needs a large amount of water for growth can be solved, thirdly, the eucalyptus oil can be used as a terpene compound, has the effects of inhibiting biological activity, can paralyze central nerves of organisms, and further prevents marine organisms from attaching.

3. In the preparation process of the antifouling and anticorrosive marine coating, the components are added under the uniform stirring of 330r/min for 250-. Therefore, the invention fixes the rotating speed in a moderate range, and grasps the characteristics in a controllable range, thereby avoiding the condition.

4. The antifouling and anticorrosive marine coating obtained by the invention is particularly added with eucalyptus oil and toosendanin, and the safe biological extraction preparation is added to inhibit the attachment of marine organisms, so that the marine organisms are not fatally damaged, the local marine ecosphere is influenced, and the defects that artificial compounds and human beings poison the marine organisms for a long time by using toxic heavy metals such as self-polishing organic tin and the like are reduced; the obtained paint has excellent performances and high mechanical strength of a coating film, is manufactured by utilizing the bionics principle, is coated on a ship by a nanotechnology, and achieves long-acting antifouling by slowly releasing an inhibitor in the antifouling paint.

[ detailed description ] embodiments

The following examples are provided to further illustrate the embodiments of the present invention.

Example 1:

an antifouling and anticorrosive marine coating is prepared from the following raw materials in parts by weight:

polymerizing o-p-methylaniline	7.0g、
		Polychlorotrifluoroethylene	4.6g、
Aldehyde ketone resin	7.7g、
		Alkyl succinic acid imide	8.0g、
Eucalyptus oil	6.0g、
		Toosendanin	16.0g、
Acrylic acid dicyclopentenyloxyethyl ester	8.0g、
		Hydroxypropyl methylcellulose	6.0g、
Coumarone-indene resins	6.0g、
		Aqueous chlorinated rubber	6.1g。

Example 2:

example 3:

polymerizing o-p-methylaniline	15.0g、
		Polychlorotrifluoroethylene	5.5g、
Aldehyde ketone resin	8.6g、
		Alkyl succinic acid imide	9.7g、
Eucalyptus oil	11.3g、
		Toosendanin	13.4g、
Acrylic acid dicyclopentenyloxyethyl ester	7.2g、
		Hydroxypropyl methylcellulose	5.3g、
Coumarone-indene resins	5.5g、
		Aqueous chlorinated rubber	5.2g。

Example 4:

example 5:

polymerizing o-p-methylaniline	12.0g、
		Polychlorotrifluoroethylene	5.1g、
Aldehyde ketone treeFat and oil	8.2g、
		Alkyl succinic acid imide	10.1g、
Eucalyptus oil	8.9g、
		Toosendanin	12.7g、
Acrylic acid dicyclopentenyloxyethyl ester	7.6g、
		Hydroxypropyl methylcellulose	5.1g、
Coumarone-indene resins	5.7g、
		Aqueous chlorinated rubber	3.8g。

The preparation method of the antifouling and anticorrosive marine paint disclosed in the embodiment 1-5 comprises the following steps:

2) continuously stirring at a constant speed of 330r/min under 250-;

5) adding hydroxypropyl methylcellulose to make the viscosity of the material reach 3400mpa.s, namely 125KU, and uniformly stirring to obtain the finished product.

Comparative example 1:

a marine coating is prepared from the following raw materials in parts by weight (compared with example 5, eucalyptus oil is absent):

polymerizing o-p-methylaniline	12.0g、
		Polychlorotrifluoroethylene	5.1g、
Aldehyde ketone resin	8.2g、
		Alkyl succinic acid imide	10.1g、
Toosendanin	12.7g、
		Acrylic acid dicyclopentenyloxyethyl ester	7.6g、
Hydroxypropyl methylcellulose	5.1g、
		Coumarone-indene resins	5.7g、
Aqueous chlorinated rubber	3.8g。

Comparative example 2:

a marine coating is prepared from the following raw materials in parts by weight (compared with example 5, the raw materials lack of toosendanin):

polymerizing o-p-methylaniline	12.0g、
		Polychlorotrifluoroethylene	5.1g、
Aldehyde ketone resin	8.2g、
		Alkyl succinic acid imide	10.1g、
Eucalyptus oil	8.9g、
		Acrylic acid dicyclopentenyloxyethyl ester	7.6g、
Hydroxypropyl methylcellulose	5.1g、
		Coumarone-indene resins	5.7g、
Aqueous chlorinated rubber	3.8g。

Comparative example 3:

a marine coating is prepared from the following raw materials in parts by weight (compared with example 5, the marine coating lacks eucalyptus oil and toosendanin):

polymerizing o-p-methylaniline	12.0g、
		Polychlorotrifluoroethylene	5.1g、
Aldehyde ketone resin	8.2g、
		Alkyl succinic acid imide	10.1g、
Acrylic acid dicyclopentenyloxyethyl ester	7.6g、
		Hydroxypropyl methylcellulose	5.1g、
Coumarone-indene resins	5.7g、
		Aqueous chlorinated rubber	3.8g。

Comparative example 4:

a marine coating is prepared from the following raw materials in parts by weight (compared with example 5, the coating lacks coumarone-indene resin and waterborne chlorinated rubber):

polymerizing o-p-methylaniline	12.0g、
		Polychlorotrifluoroethylene	5.1g、
Aldehyde ketone resin	8.2g、
		Alkyl succinic acid imide	10.1g、
Toosendanin	12.7g、
		Acrylic acid dicyclopentenyloxyethyl ester	7.6g、
Hydroxypropyl methylcellulose	5.1g、
		Eucalyptus oil	8.9g。

Comparative example 5:

a marine coating is prepared from the following raw materials in parts by weight (compared with example 5, the marine coating lacks aqueous chlorinated rubber):

polymerizing o-p-methylaniline	12.0g、
		Polychlorotrifluoroethylene	5.1g、
Aldehyde ketone resin	8.2g、
		Alkyl succinic acid imide	10.1g、
Toosendanin	12.7g、
		Acrylic acid dicyclopentenyloxyethyl ester	7.6g、
Hydroxypropyl methylcellulose	5.1g、
		Coumarone-indene resins	5.7g、
Eucalyptus oil	8.9g。

Comparative example 6:

a marine coating is prepared from the following raw materials (compared with example 5, the extraction agent of toosendanin is replaced by water from ethanol):

polymerizing o-p-methylaniline	12.0g、
		Polychlorotrifluoroethylene	5.1g、
Aldehyde ketone resin	8.2g、
		Alkyl succinic acid imide	10.1g、
Toosendanin (water as extractant)	12.7g、
		Acrylic acid dicyclopentenyloxyethyl ester	7.6g、
Hydroxypropyl methylcellulose	5.1g、
		Coumarone-indene resins	5.7g、
Eucalyptus oil	8.9g、
		Aqueous chlorinated rubber	3.8g。

Experimental example:

the products prepared in the examples and comparative examples were tested for various properties with the following parameters:

table 1:

and (4) analyzing results:

1. as can be seen from comparative example 1, eucalyptus oil plays an important role in the coating, and the effect of expelling the oil cannot be achieved by using only toosendanin alone, and the effect of toosendanin is to destroy the conduction of the central nerves and to strip the oil from the marine facilities, which still causes the weight of the ship hull to increase and a great economic loss of the marine facilities to be caused.

2. It can be seen from comparative example 2 that absent the addition of toosendanin, the coating is still unable to resist attack by marine crustaceans, and compared to comparative example 1, toosendanin reduces the degree of adhesion of marine crustaceans but is not precluded or reduced on a large scale.

3. From comparative example 3, we can see that the mixture shows very poor performance in the seawater hanging plate experiment, has very many attachments and has no condition of separating from the coating plate due to no addition of two alkaloid components of the toosendanin and the eucalyptus oil, and can conclude that: as can be seen from the condition of the hanging plate of the coating plate, the toosendanin and the eucalyptus oil have good inhibiting and expelling effects on marine crustaceans.

4. As can be seen from comparative example 4, the absence of coumarone-indene resin and aqueous chlorinated rubber in the coating formulation reduces the resistance of the coating to salt and corrosion from seawater, and also loses the reinforcing effect of the resin, resulting in the coated panel showing poor resistance to salt and water, and having a corroded area exceeding 1/3.

5. By comparative example 5 we can see that the critical compounded aqueous chlorinated rubber is lacking. Although the coumarone-indene resin is added, the cracking resistance is improved, but the salt resistance is still not good under the condition of high saline-alkali property and high corrosivity of seawater, compared with the comparative example 4, the salt resistance is only improved by less than 8 percent, and the corrosion area is still as high as 27 percent after 90 days.

6. As can be seen from the comparative example 6 and the following table, under the condition of the same ingredients in the ingredient table, different solvents have different extraction effects on the cortex Meliae and the fruit, because the polarity of water and ethanol is stronger, the dissolving capacity on various polar ingredients is stronger, the extraction efficiency of the solvent on the cortex Meliae and the fruit is reduced along with the reduction of the polarity of the solvent, and in addition, the ethanol with the same excellent polarity is selected as an extracting agent in consideration of the organic performance of the coating.

Solvent(s)	The yield of the chinaberry bark extract is high	The yield of the chinaberry fruit extract is%
			Distilled water	13.18	29.55
Ethanol	12.67	27.75
			Ethyl acetate	4.02	9.76
Acetone (II)	3.64	8.05

7. It can be seen from the examples that the marine cladding test of example 5 has the best effect, the possibility of marine organisms attaching is reduced by adding two extracted natural substances, namely "toosendanin" and "eucalyptus oil", to stimulate the nervous system of the attached organisms, and the flexibility and the saline-alkali resistance of the marine organisms are improved by adding the water-based chlorinated rubber, so that the service life is prolonged, the maintenance cost of enterprises is reduced, the marine organisms can be naturally flushed away by using the water flow when a ship runs in the sea, and the weight of the marine organisms is reduced.

The above description is intended to describe in detail the preferred embodiments of the present invention, but the embodiments are not intended to limit the scope of the claims of the present invention, and all equivalent changes and modifications made within the technical spirit of the present invention should fall within the scope of the claims of the present invention.

Claims

1. An antifouling and anticorrosive marine coating is characterized in that: the feed is prepared from the following raw materials in parts by weight:

7.0 to 19.0 portions of polymerized o-methylaniline,

4.6 to 5.8 portions of polychlorotrifluoroethylene,

Aldehyde ketone resin 7.7-9.4,

Alkyl succinic acid imide 8.0-11.2,

Eucalyptus oil 6.0-14.0 wt%,

Toosendanin 9.0-16.0%,

6.0-8.0 parts of dicyclopentenyloxyethyl acrylate,

4.0 to 6.0 portions of hydroxypropyl methylcellulose,

4.0-6.0 g of coumarone-indene resin,

2.7-6.1 parts of water-based chlorinated rubber;

the preparation method of the antifouling and anticorrosive marine coating comprises the following steps:

2) continuously stirring at a constant speed of 330r/min under 250-;

5) adding hydroxypropyl methylcellulose to make the viscosity of the material reach 3400mpa.s, and uniformly stirring to obtain a finished product;

the preparation method of the toosendanin comprises the following steps: taking cortex Meliae, cortex Meliae and fructus Toosendan as raw materials, 60% v/v ethanol as extracting solution, and the liquid-material ratio is 1: 9, extracting for 80min at 60 deg.C for 4 times, mixing the 4 extractive solutions, and concentrating to 1/6.

2. The antifouling anticorrosive marine paint according to claim 1, wherein: the feed is prepared from the following raw materials in parts by weight:

9.0-15.0 portions of polymerized o-methylaniline,

4.9-5.5 portions of polychlorotrifluoroethylene,

8.1-8.6 parts of aldehyde ketone resin,

Alkyl succinic acid imide 8.8-9.7,

Eucalyptus oil 8.6-11.3 wt%,

11.3-11.6 portions of toosendanin,

6.4-7.2 parts of dicyclopentenyloxyethyl acrylate,

4.7 to 5.3 portions of hydroxypropyl methylcellulose,

4.0-5.5 parts of coumarone-indene resin,

2.7-5.2 parts of water-based chlorinated rubber.

3. The antifouling anticorrosive marine paint according to claim 1, wherein: the feed is prepared from the following raw materials in parts by weight:

polymerizing o-p-methylaniline 12.0,

5.1 portions of polychlorotrifluoroethylene,

8.2 parts of aldehyde ketone resin,

10.1 parts of alkyl succinimide,

8.9 portions of eucalyptus oil,

12.7 portions of toosendanin,

7.6 parts of dicyclopentenyloxyethyl acrylate,

5.1 portions of hydroxypropyl methyl cellulose,

5.7 parts of coumarone-indene resin,

3.8 parts of aqueous chlorinated rubber.