CN114907773A

CN114907773A - Environment-friendly marine antifouling paint and preparation method thereof

Info

Publication number: CN114907773A
Application number: CN202210690057.3A
Authority: CN
Inventors: 卢桂峰
Original assignee: Kaifeng Kuake New Materials Co ltd
Current assignee: Kaifeng Kuake New Materials Co ltd
Priority date: 2022-04-25
Filing date: 2022-06-17
Publication date: 2022-08-16
Also published as: CN114958199A; CN114921179A; CN114806406A; CN114836129B; CN114957668A; CN114836129A

Abstract

The application relates to the technical field of antifouling paint, and particularly discloses an environment-friendly marine antifouling paint and a preparation method thereof. An environment-friendly marine antifouling paint comprises the following raw materials in percentage by weight: 30-70% of modified siloxane polymer, 1.2-25% of bactericide, 1-10% of phthalate ester catalyst, 1-20% of graphite, 0.5-20% of dimethyl silicone oil and 5-17.3% of filler, wherein the dimethyl silicone oil contains monohydroxy or dihydroxy. The application discloses antifouling paint in environment-friendly ocean has excellent low surface energy, and surface energy is low, is difficult to bond other material, reduces the attached to of the marine fouling organism, has persistent anti fouling performance, and paint does not contain the solvent hardly simultaneously, has greatly reduced the pollution of volatile organic compounds to marine environment.

Description

Environment-friendly marine antifouling paint and preparation method thereof

The present invention is an invention application which is based on the priority including application No. 2022104422806 entitled "a Silicone Polymer and method for making same", application Ser. No. 2022, 04/25.

Technical Field

The application relates to the technical field of antifouling paint, in particular to environment-friendly marine antifouling paint and a preparation method thereof.

Background

Seawater is the most abundant and highly corrosive natural electrolyte in nature, and contains almost all chemical elements on earth, and the components are very complex. Seawater also contains marine organisms and putrefactive organic substances, which cause corrosion to metal components of various marine vehicles, oil platforms, and marine facilities.

Among them, some marine organisms adhere to marine facilities, which are also called marine fouling organisms, and are a general term for animals, plants and microorganisms growing on the surfaces of all facilities in the ship bottom and sea. These organisms are generally harmful, and these marine fouling organisms attach to marine facilities, which increases the sailing resistance of ships and affects the normal use of many marine facilities, and some secretions of these marine fouling organisms accelerate the corrosion of metal components of marine facilities and shorten the service life of marine facilities.

At present, for the phenomenon that marine fouling organisms are attached to marine facilities, a protective film is generally formed on a metal component of the marine facilities by spraying paint, so that the damage to the metal component is reduced, and the service life of the metal component on the sea is prolonged. In the related technology, the common high-end type marine coating is mainly FEVE type fluorocarbon, toxic bactericides are added into the FEVE type fluorocarbon, a large amount of volatile organic compounds (VOC >600g/l) are contained in the coating, the bactericides and the volatile organic compounds cause serious pollution to marine environment, and simultaneously cause great harm to marine organisms and influence the balance of marine ecological environment.

Accordingly, the inventors have recognized a need to provide an environmentally friendly and effective marine antifouling coating.

Disclosure of Invention

In order to reduce the pollution of the marine antifouling paint to the marine environment, the application provides the environment-friendly marine antifouling paint and the preparation method thereof.

In a first aspect, the application provides an environment-friendly marine antifouling paint, which adopts the following technical scheme:

an environment-friendly marine antifouling coating comprises the following raw materials in percentage by weight: 30-70% of modified siloxane polymer, 1.2-25% of bactericide, 1-10% of phthalate ester catalyst, 1-20% of graphite, 0.5-20% of dimethyl silicone oil and 5-17.3% of filler, wherein the dimethyl silicone oil contains monohydroxy or dihydroxy.

By adopting the technical scheme, the modified siloxane polymer adopted by the application contains a large amount of Si-O chemical bonds, the higher the content of the Si-O chemical bonds is, the lower the surface energy of the modified siloxane polymer is, and meanwhile, the stronger the ultraviolet resistance of the modified siloxane polymer is, the marine facilities often work at sea, the ultraviolet irradiation time is longer, and the coating prepared by adopting the modified siloxane polymer has the advantages that the ultraviolet irradiation coating is not broken, cracked, pulverized and discolored, and has stronger weather resistance; in addition, the modified siloxane polymer is non-toxic, and has the characteristics of environmental protection and safety compared with FEVE type fluorocarbon coating; the adopted copper pyrithione coordination compound mainly plays a role of a bacteriostatic agent, can reduce marine fouling organisms from being attached to metal components of marine facilities, and is non-toxic, so that the pollution to the marine environment is reduced; the adopted flake graphite and graphite fluoride mainly increase the lubricating property of the coating, so that marine fouling organisms are not firmly attached to the marine facilities, and the damage to marine facilities caused by the attachment of the marine fouling organisms can be reduced; the adopted catalyst is mainly used for accelerating resin curing and improving the workability of the coating, and in addition, the coating prepared by the method does not contain water, so that the pollution of volatile organic compounds to the marine environment is greatly reduced.

The coating prepared by the method has excellent low surface energy and low surface energy, is difficult to bond other substances, and reduces the adhesion of marine fouling organisms, so the coating has lasting anti-fouling performance; in addition, the silver ion powder has the sterilization and antibacterial performance, when marine microorganisms are attached to the surface of the coating, the silver ion powder can sterilize the marine microorganisms, and the attachment of more than 80% of organisms to marine facilities in the later period can be reduced; the raw materials adopted by the coating are nontoxic, so that the prepared coating has good pollution resistance and reduces the pollution phenomenon to the marine environment;

in addition, in the process of film formation of the coating, alkoxy in the modified siloxane polymer can generate hydrolysis reaction with water in the air to generate hydroxyl, and hydroxyl in the dimethyl silicone oil can perform condensation reaction with the hydroxyl generated by the alkoxy of the modified siloxane polymer, so that the film forming performance of the coating is better, the paint film of the coating is more compact, the stain resistance durability of the coating surface is remarkably improved, and the corrosion resistance and the impact resistance of the coating are further improved.

Preferably, the modified siloxane polymer is prepared from primary amino siloxane and acid anhydride, wherein the molar ratio of the acid anhydride to the primary amino siloxane is 0.3-0.6: 1;

the preparation method of the modified siloxane polymer comprises the following steps:

respectively weighing primary amino siloxane and anhydride, adding the primary amino siloxane and the anhydride into a reaction bottle, stirring, controlling the reaction temperature to be 0-10 ℃ and the stirring time to be 8-24 h, and preparing an imido acid-siloxane monomer; and then, putting the imido acid-siloxane monomer into a reaction bottle, stirring, controlling the temperature to be 70-100 ℃, and stirring for 4-8 hours to obtain the modified siloxane polymer.

Preferably, the modified siloxane polymer contains methoxy, ethoxy, or propoxy groups.

The preparation method comprises the following steps of preparing a primary amino siloxane, obtaining an imido acid-siloxane monomer, and polymerizing to obtain a modified siloxane polymer, wherein the primary amino siloxane is siloxane with amino on a side chain, and acid anhydride reacts with the primary amino on the side chain of the primary amino siloxane to obtain the imido acid-siloxane monomer, and the content of a siloxane bond in the prepared modified siloxane polymer is 30-60%.

Preferably, the imide linkage in the modified siloxane polymer is located on a polymer side chain.

By adopting the technical scheme, the acid anhydride and the primary amino group on the side chain of the primary amino siloxane are reacted, so that the finally prepared modified siloxane polymer is strong in stability and not easy to decompose, the molar ratio of the acid anhydride to the primary amino siloxane in reactants is 0.3-0.6: 1, the prepared imide siloxane polymer improves the adhesive force of the coating, the coating is not easy to fall off, and the effective protection period of the coating is favorably prolonged; the coating prepared by adding the modified siloxane polymer has strong adhesive force, can be more stably attached to the surface of a metal component of a marine facility, is not easy to fall off, and can also have the characteristic of good color, in addition, because the content of silicon-oxygen bonds contained in the modified siloxane polymer is 30-60%, the combination effect of the modified siloxane polymer and other raw materials is poor, and imide bonds in the modified siloxane polymer are positioned on a polymer side chain, the combination of the modified siloxane polymer and other materials can be improved, the film-forming toughness of the prepared coating can also be improved to be higher, the coating has the characteristic of cracking resistance, and meanwhile, the prepared coating also has the characteristic of high temperature resistance.

Preferably, the acid anhydride comprises one of trimellitic anhydride, 1,2, 4-cyclohexanetricarboxylic anhydride or phthalic anhydride.

Preferably, the primary amino siloxane is one or a combination of more of 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldiethoxysilane, N-2-aminoethyl-3-aminopropylmethyldiethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-divinyltriaminopropylmethyldimethoxysilane and 3-divinyltriaminopropyltrimethoxysilane.

By adopting the technical scheme, the acid anhydride substance adopts intramolecular acid anhydride, which is beneficial to replacing the-O-position with N to form imide; and the side chain containing imide group can be prolonged and the complexity of the side chain can be increased by adopting the reaction of the primary amino siloxane and the acid anhydride compound, thereby enriching the performance of the imidized siloxane polymer.

Preferably, the bactericide comprises one or both of a copper pyrithione complex and silver ion powder, and the pyrithione complex comprises one of copper pyrithione, zinc pyrithione, or silver pyrithione

The graphite includes one or both of flake graphite and graphite fluoride.

In a second aspect, the application provides a preparation method of an environment-friendly marine antifouling paint, which adopts the following technical scheme:

a preparation method of an environment-friendly marine antifouling paint comprises the following steps:

mixing the raw material modified siloxane polymer, the bactericide, the graphite and the dimethyl silicone oil, and dispersing at medium speed to prepare a mixture; adding a titanate catalyst into the mixture, and dispersing at medium speed to obtain a coating; wherein the rotation speed of the medium-speed dispersion is 300-600 rpm, and the time is 50-70 min.

In summary, the present application has the following beneficial effects:

1. the coating prepared by the method has excellent low surface energy and low surface energy, is difficult to bond other substances, and reduces the attachment of marine fouling organisms, so the coating has durable antifouling performance; in addition, the silver ion powder has the sterilization and antibacterial performance, when marine microorganisms are attached to the surface of the coating, the silver ion powder can sterilize the marine microorganisms, and the attachment of more than 80% of rattan and pitcher organisms to marine facilities in the later period can be reduced; the raw materials adopted by the coating are nontoxic, so that the prepared coating has good pollution resistance and reduces the pollution phenomenon to the marine environment;

2. according to the preparation method, the anhydride reacts with the primary amino group on the side chain of the primary amino siloxane, so that the finally prepared modified siloxane polymer is strong in stability and not easy to decompose, the coating prepared by adding the modified siloxane polymer is strong in adhesive force, can be more stably attached to the surface of a metal component of a marine facility and is not easy to fall off, and in addition, the prepared coating has the characteristic of good color;

3. in the film forming process of the coating, alkoxy in the modified siloxane polymer can be subjected to hydrolysis reaction with water in the air to generate hydroxyl, and hydroxyl in the dimethyl silicone oil can be subjected to condensation reaction with hydroxyl generated by the alkoxy of the siloxane polymer, so that the film forming performance of the coating is better, a paint film of the coating is more compact, and the corrosion resistance and the impact resistance of the coating are further improved.

Detailed Description

The present application will be described in further detail with reference to examples. The special description is as follows: the following examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer, and the starting materials used in the following examples were obtained from ordinary commercial sources unless otherwise specified.

Preparation example

Preparation examples 1 to 5

A modified siloxane polymer prepared by the following process:

respectively weighing primary amino siloxane and anhydride, adding the primary amino siloxane and the anhydride into a reaction bottle, stirring, controlling the reaction temperature to perform ice-bath reaction, and then stirring to obtain an imido acid-siloxane monomer;

and then putting the imido acid-siloxane monomer into a reaction bottle, stirring, and controlling the temperature to stir to obtain the modified siloxane polymer.

The kinds and molar ratios of the primary aminosilicone and the acid anhydride compound are shown in Table 1.

Table 1: types and molar ratios of raw materials in production examples 1 to 3 and comparative production examples 1 to 2

In other preparation examples, the primary aminosiloxane may be one or a combination of N-2-aminoethyl-3-aminopropylmethyldiethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane and 3-divinyltriaminopropylmethyldimethoxysilane.

Examples

Examples 1 to 3

respectively weighing the modified siloxane polymer, the bactericide zinc pyrithione and the flake graphite, mixing and adding the mixture into a reaction vessel, then placing the reaction vessel into a dispersion machine, starting the dispersion machine to stir at the rotating speed of 400rmp for 50 minutes at room temperature to prepare a mixture, then adding the phthalate catalyst into the mixture, starting the dispersion machine at the room temperature to stir at the rotating speed of 400rmp for 50 minutes to prepare the coating.

Modified siloxane Polymer the modified siloxane polymers prepared in preparation examples 1 to 3 were used as starting materials for the modified siloxane polymers in examples 1 to 3, respectively. The specific proportions of the raw materials of the coating materials of examples 1 to 3 are shown in Table 2.

Table 2: component proportion Table of Environment-friendly Marine antifouling paint in examples 1 to 3

Examples 4 to 5

Examples 4 to 5 differ from example 2 in that the modified silicone polymers in examples 4 to 5 were the modified silicone polymers prepared in comparative preparation examples 1 to 2, respectively.

Examples 6 to 7

Examples 6 to 7 differ from example 2 in that graphite fluoride was further added, and the specific ratios of the respective raw materials are shown in table 3.

Table 3: component proportion Table of Environment-friendly Marine antifouling paint in examples 6 to 7

Examples 8 to 10

Examples 8 to 10 are different from example 7 in that silver ion powder was further added, and the specific ratios of the respective raw materials are shown in table 4.

Table 4: component proportion Table of Environment-friendly Marine antifouling paint in examples 11 to 13

Example 11

Example 11 differs from example 10 in that the speed of the dispersion machine used was 600rmp and a mixture was obtained by stirring for 60 minutes; then adding the phthalate ester catalyst into the mixture, starting a dispersion machine at room temperature, and stirring at the rotating speed of 600rmp for 60 minutes to obtain the coating.

Example 12

Example 12 differs from example 10 in that the rotational speed of the dispersion machine used was 300rmp and a mixture was obtained by stirring for 70 minutes; then adding the phthalate ester catalyst into the mixture, starting a dispersion machine at room temperature, and stirring at the rotating speed of 300rmp for 70 minutes to prepare the coating.

Comparative example 1

The difference from example 10 is that the imide siloxane polymer of example 1 is replaced with the same amount of poly 3-aminopropyltriethoxysilane.

Comparative example 2

The difference from example 10 is that no dimethicone was added.

Comparative example 3

The difference from example 10 is that no silver ion powder was added.

Performance test

Detection method

Test No.)

The coatings obtained in examples 1-12 were subjected to a compression strength test and an antifouling performance test and evaluation by referring to test methods specified in SL 352-2006 and national standard GB/T7789-2007 respectively, the test period is 30 days, and the results are shown in Table 5:

table 5: antifouling test data for coatings prepared in examples 1-12

Referring to the above table, it can be seen that the coatings prepared in examples 1 to 12 have excellent low surface energy, are difficult to adhere to other substances, reduce the adhesion of marine fouling organisms, and thus, have durable antifouling properties. In addition, the imide bond in the modified siloxane polymer is positioned on the side chain of the polymer, so that the combination of the modified siloxane polymer and other materials can be improved, the film forming toughness of the prepared coating is improved, and the imide group-containing side chain can be prolonged and the complexity of the side chain is increased due to the reaction of the primary amino siloxane and the anhydride compound, so that the performance of the imide siloxane polymer is enriched, and the coatings prepared in examples 1 to 12 have strong anti-biological erosion performance.

The dimethyl silicone oil is added in each of the embodiments 1 to 12, and the dimethyl silicone oil can perform condensation reaction with hydroxyl generated by alkoxy of the modified siloxane polymer, so that paint films of the coatings prepared in the embodiments 1 to 12 are more compact, and the adhesion of marine organisms and the corrosion of biological secretion and alkaline seawater in marine environment to the coatings can be effectively reduced.

Wherein, only flake graphite is adopted in examples 1-5, while graphite fluoride and the compounding of the flake graphite are adopted in examples 6-7, and the addition ratio of the graphite fluoride to the flake graphite in example 7 is 1:1, and the graphite fluoride has more excellent lubricity and low surface energy, so that the adhesion of marine organisms can be well reduced; the flake graphite has good corrosion medium permeability resistance, and can reduce the erosion of biological secretion and alkaline seawater in marine environment to the coating. Therefore, the flake graphite and the graphite fluoride are mixed for use, so that the coatings prepared in examples 6 to 7 can not only further increase the low surface energy of the coating film of the coating, but also have good erosion resistance.

Compared with the example 7, the silver ion powder is added in the examples 8-10, and the silver ion powder can effectively kill the marine organisms attached to the coating and greatly reduce the attachment of the marine organisms. In addition, the lethality of the silver ion powder to marine microorganisms is high, and marine plants cannot be easily killed; the coating prepared by the modified siloxane polymer has very low surface energy, the surface of a coating film is smooth, and the force points of marine plants can be effectively reduced, so that the silver ion powder and the modified siloxane polymer are mutually synergistic, and the adhesion of marine microorganisms and marine plants can be effectively reduced.

Test No. two

The paint obtained in examples 1-12 and comparative examples 1-3 is subjected to adhesion performance test and antibacterial performance evaluation by referring to test methods specified in national standards GB/T9286-88 and GB/T1741-2007;

and (3) testing the ageing resistance: a metal substrate is taken, the coatings obtained in examples 1-12 and comparative examples 1-3 are sprayed on the metal substrate, then the metal substrate is placed under an ultraviolet lamp for irradiation for more than 5000 hours, the color change condition of the surface of the metal substrate is observed, and the ageing resistance of the coatings obtained in examples 1-12 and comparative examples 1-3 is tested;

and (3) pollution resistance performance test: a metal substrate is taken, the coatings obtained in the examples 1 to 12 and the comparative examples 1 to 3 are sprayed on the metal substrate, after the coatings are cured, the oily Mark pen is taken out and smeared on the surface of the metal substrate, then the metal substrate is wiped after being placed for 24 hours, and the coatings obtained in the examples 1 to 12 and the comparative examples 1 to 3 are tested for the stain resistance, wherein the stain resistance test is divided into three stages, namely, excellent, medium and poor.

Salt spray resistance test: JG/T224-.

The coatings obtained in examples 1 to 12 and comparative examples 1 to 3 were tested for adhesion, antibacterial properties, aging resistance, stain resistance and salt spray, the test methods are as above, and the specific test data are shown in table 6:

table 6: test data for coatings prepared in examples 1-12 and comparative examples 1-3

According to the examples 1-12 and the combination of Table 7, it can be seen that the modified siloxane polymer obtained by the reaction of the acid anhydride and the primary amino group on the side chain of the primary amino siloxane can improve the combination with other materials, and can also improve the film forming toughness of the prepared coating, and the prepared coating has the characteristic of cracking resistance, so that the prepared coating also has excellent characteristics of high temperature resistance, strong adhesive force, ultraviolet resistance and the like. In addition, the modified siloxane polymer with low surface energy and the nontoxic bactericide copper pyrithione coordination compound are adopted, so that the prepared coating has excellent low surface energy and low surface energy, is difficult to bond other substances, reduces the attachment of marine fouling organisms, and has durable pollution resistance. In addition, the coating prepared by the method does not contain water, and the pollution of volatile organic compounds to the marine environment and human bodies is greatly reduced.

The mole ratios of the acid anhydride of the modified siloxane polymer to the primary amino siloxane used in examples 4 and 5 were 0.2:1 and 0.8:1, respectively, so that the coatings prepared in examples 4 to 5 were reduced as compared to example 2, and the coating layers were easily released from the metal members of the marine facilities, which was disadvantageous in extending the effective protective period of the coatings. Therefore, the molar ratio of the acid anhydride to the primary amino siloxane is preferably 0.3-0.6: 1.

Comparative example 1 in which an equivalent amount of 3-aminopropyltrimethoxysilane polymer was used instead of the imide siloxane polymer in example 10, the 3-aminopropyltrimethoxysilane polymer was not imidized, and the difference was mainly that amino groups or carboxyl groups contained in the material were more hydrophilic and inferior in ultraviolet ray resistance and salt spray resistance.

Comparative example 2 is different from example 10 in that no dimethylsilicone oil is added, so that the coating prepared in comparative example 2 has a large surface tension of the coating film and cannot form a good antifouling surface on the surface, thereby causing the reduction of the fouling resistance and corrosion resistance of the coating surface.

The difference between comparative example 3 and example 10 is that the bactericidal performance of the paint prepared in comparative example 3 is lowered compared to example 10 without adding the silver ion powder.

The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.

Claims

1. The environment-friendly marine antifouling paint is characterized by comprising the following raw materials in percentage by weight: 30-70% of modified siloxane polymer, 1.2-25% of bactericide, 1-10% of phthalate ester catalyst, 1-20% of graphite, 0.5-20% of dimethyl silicone oil and 5-17.3% of filler, wherein the dimethyl silicone oil contains monohydroxy or dihydroxy.

2. The environmentally friendly marine antifouling paint of claim 1, wherein: the modified siloxane polymer is prepared from primary amino siloxane and acid anhydride, wherein the molar ratio of the acid anhydride to the primary amino siloxane is 0.3-0.6: 1;

respectively weighing primary amino siloxane and anhydride, adding the primary amino siloxane and the anhydride into a reaction bottle, stirring, controlling the reaction temperature to be 0-10 ℃ and the stirring time to be 8-24 h, and preparing an imido acid-siloxane monomer;

and then, putting the imido acid-siloxane monomer into a reaction bottle, stirring, controlling the temperature to be 70-100 ℃, and stirring for 4-8 hours to obtain the modified siloxane polymer.

3. The environmentally friendly marine antifouling paint of claim 2, wherein: the imide linkages in the modified siloxane polymer are located on polymer side chains.

4. The environmentally friendly marine antifouling paint of claim 2, wherein: the acid anhydride comprises one or more of trimellitic anhydride, 1,2, 4-cyclohexane tricarboxylic anhydride, or phthalic anhydride.

5. The environmentally friendly marine antifouling paint of claim 2, wherein: the primary amino siloxane is one or a combination of more of 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldiethoxysilane, N-2-aminoethyl-3-aminopropylmethyldiethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-diethylenetriaminopropylmethyldimethoxysilane and 3-diethylenetriaminopropyltrimethoxysilane.

6. The environmentally friendly marine antifouling paint of claim 1, wherein: the bactericide comprises one or two of a copper pyrithione coordination compound and silver ion powder, and the pyrithione coordination compound comprises one of copper pyrithione, zinc pyrithione or silver pyrithione.

7. The environment-friendly marine antifouling paint as claimed in claim 1, wherein: the graphite includes one or both of flake graphite and graphite fluoride.

8. A method for preparing the environment-friendly marine antifouling paint as claimed in any one of claims 1 to 7, wherein the method comprises the following steps: mixing the raw material modified siloxane polymer, the bactericide, the graphite and the dimethyl silicone oil, and dispersing at medium speed to prepare a mixture; adding a titanate catalyst into the mixture, and dispersing at a medium speed to obtain a coating; wherein the rotation speed of the medium-speed dispersion is 300-600 rpm, and the time is 50-70 min.