CN105482702A - Self-polishing antifouling paint and preparation method thereof - Google Patents

Abstract

The invention relates to a self-polishing antifouling paint and a preparation method thereof. In 100 parts by mass of the antifouling paint, there are 18 to 24 parts of resin in terms of solids, 50 to 55 parts of antifouling agent, and 0.5 to 1.5 parts of graphene microchips. 3 to 6 parts of pigment and filler, 1 to 2 parts of dispersant, 1 to 2 parts of organic bentonite, and the balance is organic solvent; among them, the resin is composed of hydroxyl acrylic resin, acrylic zinc resin and rosin; the antifouling agent is composed of copper pyrithione , 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, cuprous oxide and zinc oxide. The self-polishing antifouling paint is obtained by separately preparing graphene microchip-zinc oxide-hydroxyacrylic resin slurry and cuprous oxide-rosin-acrylic acid zinc slurry, and then mixing them. The obtained self-polishing antifouling paint product has stable quality, long antifouling period, good polishing, high strength, crack resistance and low VOC.

Description

A kind of self-polishing antifouling paint and preparation method thereof

technical field

The invention relates to a self-polishing antifouling paint and a preparation method thereof, which is especially suitable for ship bottom antifouling.

Background technique

The attachment and fouling of marine organisms to the bottom of the ship increases the roughness of the outer surface of the bottom of the ship, increases the navigation resistance, reduces the speed of the ship, and increases the fuel consumption. In addition, the adhesion and fouling of marine organisms to the hull also accelerates the corrosion of the hull, shortens the service life of the ship, and poses a hazard to navigation safety. According to incomplete estimates, the economic loss caused by marine biofouling in the world exceeds 1 billion US dollars every year. Therefore, preventing the attachment and fouling of marine organisms has always been an important task in naval defense construction, marine transportation and marine engineering development. In order to control the fouling of marine organisms on ships and marine engineering facilities, various technologies such as electrolytic seawater antifouling, low surface energy antifouling, ultrasonic antifouling, high-pressure water rinsing, and antifouling paint coating have been developed. However, no matter from the perspective of economy or application effect, coating antifouling coatings on the surface of ships and marine engineering facilities is still the most economical, effective and practical technology to prevent marine biofouling.

Since 1966, my country has conducted systematic research on antifouling paint for ship bottoms. We have successively developed asphalt-based, vinyl-based, acrylic-based, and chlorinated rubber-based antifouling paints, such as 72-19 long-term antifouling paint, 71-33 three-year antifouling paint, and 839 acrylic antifouling paint used in ships. etc., are still the main antifouling paint varieties in domestic paint manufacturers. According to the antifouling mechanism, these antifouling paints can be classified as controlled dissolution type. Early products of this type contain antifouling agents such as DDT/mercury/organotin, and have good antifouling effects. Such prohibited antifouling agents in the formula have been replaced, but this more or less reduces the antifouling ability of the paint.

In the late 1970s, a tin acrylate polymer self-polishing coating was developed. Under the action of alkaline seawater, the coating continuously hydrolyzes and slowly releases organotin groups to play an antifouling role. The content of tin-containing monomer components in organic tin self-polishing polymers reaches 30% to 50%, which seriously pollutes the ocean. The International Maritime Organization (IMO) required that the use of antifouling paint containing TBT (tributyltin) be completely banned in January 2003, and by January 2008, any antifouling paint containing TBT would no longer be applied to the surface of the hull.

At present, the mainstream product in the antifouling paint market is tin-free self-polishing paint. According to the self-polishing mechanism of tin acrylate polymer, an antifouling coating based on copper acrylate, zinc acrylate and acrylate alkylsiloxane self-polishing resin and cuprous oxide as biocide was developed. The self-polishing coating prepared by copper acrylate/zinc/silyl ester polymer and cuprous oxide can control the effective release of copper ions and has good polishing performance, but the solid content is low. CN101550305A Long-acting self-polishing antifouling paint discloses a long-acting self-polishing antifouling paint, which is composed of acrylic copper resin, composite antifouling agent, pigments and fillers, anti-settling agent, solvent, etc., and is suitable for ship bottoms as antifouling paint It can effectively prevent marine organisms from fouling the bottom of the ship within 3 to 5 years. The Intersmooth365 product of the International Coatings Company belonging to the same category as the above is prepared from copper acrylate self-polishing resin, cuprous oxide, and zinc zinc. Its volume solid content is 40%, and its VOC (volatile organic compound) content is high. current environmental requirements.

HJ2515 "Antifouling Paint Environmental Labeling Products" technical requirements: DDT/mercury/organotin should be banned, low-risk active substances should be used, copper ions in steady state are 25mg/cm ² /d, and VOC limit is 400g/L. It can be seen that there is an urgent need to develop high-efficiency and low-pollution antifouling paints to meet the higher requirements of environmental protection regulations.

Contents of the invention

The object of the present invention is: provide a kind of self-polishing antifouling paint, its antifouling high efficiency, antifouling agent toxicity controllable, low VOC.

The technical solution for realizing the object of the present invention is: a self-polishing antifouling paint, characterized in that, in 100 parts by mass of the self-polishing antifouling paint, 18-24 parts of solid resin, 50-55 parts of antifouling agent, graphite 0.5-1.5 parts of vinyl flakes, 3-6 parts of pigments and fillers, 1-2 parts of dispersants, 1-2 parts of organic bentonite, and the balance is organic solvents;

The 18-24 parts of solid-based resin is composed of 4 parts of solid-based hydroxyl acrylic resin, 4-6 parts of solid-based zinc acrylate resin, and the balance is rosin, wherein the zinc content of solid-based zinc acrylate resin is 12-15wt %, the hydroxyl content of the hydroxy acrylic resin in solids is 4 to 5wt%;

The 50-55 parts of antifouling agent is composed of 3 parts of copper pyrithione, 3 parts of 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, 30-35 parts of cuprous oxide , the balance is composed of zinc oxide;

The particle size (D ₅₀ ) of the graphene microflakes is ≤10 μm, and the specific surface area is 200-250 m ² /g; the zinc oxide and cuprous oxide are both spherical particles, the particle size of zinc oxide is ≤10 μm, and the particle size of cuprous oxide is ≤ 25 μm.

Another object of the present invention is: provide a kind of preparation method of self-polishing antifouling paint, simple and convenient, easy to operate, the product quality that makes is stable.

The technical solution for realizing another object of the present invention is: a kind of preparation method of above-mentioned self-polishing antifouling paint, it is characterized in that, concrete preparation steps are as follows:

① Prepare each component according to the dosage of the above components, and set aside;

②In the dispersion tank, add hydroxyacrylic resin, dispersant, and some organic solvents. After stirring evenly, add graphene microflakes and zinc oxide, stir evenly, and transfer to a horizontal sand mill for grinding until the fineness of the slurry is 20 μm. , stop grinding, obtain the graphene microchip-zinc oxide-hydroxyacrylic resin slurry, save it for later use;

③In the dispersion tank, add rosin and some organic solvents, fully dissolve the rosin under stirring, then add zinc acrylate resin and stir evenly, then add organic bentonite, pigments, copper pyrithione, 4,5-dichloro-2 - n-octyl-4-isothiazolin-3-one, cuprous oxide, stir evenly, transfer to a sand mill for grinding until the fineness is 40 μm, stop grinding, and save the obtained slurry for later use;

④In the batching tank, add the slurry prepared in step ② and step ③ and add the remaining organic solvent, stir and disperse evenly at a speed of 500-800rpm, filter, pack, and label to obtain a self-polishing antifouling paint.

Technical effect of the present invention is:

1. The self-polishing antifouling paint of the technical solution of the present invention has the following technical effects:

① The antifouling paint of the present invention is mixed with an appropriate amount of graphene microflakes, which strengthens the strength of the antifouling coating and improves hydrophobicity and hydrolysis controllability.

Because the particle size of the selected graphene microchips is suitable, and its dosage matches the consumption of the main antifouling agent cuprous oxide and zinc oxide, the number of graphene microchip particles can be equal to that of the main antifouling agent cuprous oxide and zinc oxide. 10 ² to 10 ³ times, so that the cuprous oxide and zinc oxide of the antifouling agent are effectively physically separated and wrapped by graphene microsheets, and the dissolution and release rates of cuprous oxide and zinc oxide are controlled and adjusted; the selected graphene microsheets The specific surface area is 200-250m ² /g, and the thickness-to-diameter ratio can reach tens to hundreds, so it provides excellent flexibility and strength for the coating, and the crack resistance of the coating is improved; due to the good hydrophobicity and lubricity of the graphene surface, The surface contact angle of the coating formed by the antifouling paint mixed with graphene is increased, and the affinity and friction coefficient between the coating surface and water are reduced, thereby reducing the resistance of the antifouling paint coating to navigation;

② The self-polishing antifouling paint of the present invention is mixed with an appropriate amount of rosin as a resin component, so that the solid content of the antifouling paint is increased, VOC is reduced, and environmental protection requirements are met;

3. the self-polishing antifouling paint of the present invention is mixed into an appropriate amount of metal oxides that have a good wetting and dispersing effect of hydroxyacrylic resin, so that the zinc oxide surface in the prepared graphene microchip-zinc oxide-hydroxyacrylic resin slurry Covered with organic resin and separated by graphene micro-sheets, it prevents the reaction of resin acid in rosin with zinc oxide to cause rapid increase in the viscosity of antifouling paint and improves the storage stability of antifouling paint;

4. in the antifouling agent of self-polishing antifouling paint of the present invention, join appropriate copper pyrithione and 4,5-dichloro-2-n-octyl-4 isothiazolin-3-ketone and cuprous oxide, to The inhibition of marine organisms, plants, and bacteria is improved, and it can effectively prevent marine organisms from fouling the bottom of the ship within 3 to 5 years;

2. The preparation method of the self-polishing antifouling paint of the technical solution of the present invention adopts to make slurry with hydroxyacrylic resin, graphene microflakes and zinc oxide respectively, and makes slurry with rosin, acrylic zinc resin and other components of antifouling paint Material, and then mix the two to ensure that the role of each component is fully exerted, and the storage of the product is more stable. The operation is simple and feasible.

detailed description

The present invention will be further described below in conjunction with the examples, but not limited thereto.

Unless otherwise specified, the raw materials used in the examples and comparative examples are commercially available industrial supplies, which can be purchased through commercial channels.

Embodiment 1 prepares self-polishing antifouling paint 1 and 2

In 100 parts by mass of the self-polishing antifouling paint of the present invention, there are 18 to 24 parts of resin in solids, 50 to 55 parts of antifouling agent, 0.5 to 1.5 parts of graphene microflakes, 3 to 6 parts of pigments and fillers, and 1 to 5 parts of dispersant. 2 parts, 1-2 parts of organic bentonite, and the balance is organic solvent;

The 18-24 parts of solid-based resin is composed of 4 parts of solid-based hydroxyl acrylic resin, 4-6 parts of solid-based zinc acrylate resin, and the balance is rosin, wherein the zinc content of solid-based zinc acrylate resin is 12-15wt %, the hydroxyl content of the hydroxy acrylic resin in solids is 4 to 5wt%;

The 50-55 parts of antifouling agent is composed of 3 parts of copper pyrithione, 3 parts of 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, 30-35 parts of cuprous oxide , the balance is composed of zinc oxide;

The particle size (D ₅₀ ) of the graphene microflakes is ≤10 μm, and the specific surface area is 200-250 m ² /g; the zinc oxide and cuprous oxide are both spherical particles, the particle size of zinc oxide is ≤10 μm, and the particle size of cuprous oxide is ≤ 25 μm.

The concrete formula of embodiment 1 and 2 is shown in table 1.

(1) The formula is shown in Table 1.

Table 1

In Table 1, MC-RA-01 is a product of CNOOC Changzhou Coating Chemical Research Institute Co., Ltd., its zinc acrylate copolymer content is 50wt%, its viscosity is 3000-8000mPa.s, and its zinc content accounts for 14wt% of the copolymer (solid);

CTY6278 is a product of CNOOC Changzhou Environmental Protection Coatings Co., Ltd. Its acrylate copolymer content is 70wt%, viscosity is 2000-6000mPa.s, and the hydroxyl content accounts for 4.2wt% of acrylate copolymer (solid);

SE1123 is a product of Changzhou Sixth Element Co., Ltd., with a particle size (D ₅₀ ) of 9.5 μm and a specific surface area of 205 m ² /g;

S130 is a product of Shanghai Yipin Pigment Co., Ltd.;

DC-30 is a product of Sanbo Biochemical Technology (Shanghai) Co., Ltd.;

S32500 is a product of lubrizol;

881-B is a product of Zhejiang Qinghong New Material Co., Ltd.

(2) Preparation method Concrete preparation steps are as follows:

① Prepare each component according to the dosage in Table 1, and set aside;

②In the dispersion tank, add hydroxyacrylic resin, dispersant, 4.0 parts of organic solvent, after stirring evenly, add graphene microflakes, zinc oxide and stir evenly, transfer to horizontal sand mill and grind until the slurry fineness is 20 μm, stop grinding to obtain graphene microflakes-zinc oxide-hydroxyacrylic resin slurry, which is stored for later use;

③In the dispersion tank, add rosin and 8.0 parts of organic solvent, fully dissolve the rosin under stirring, then add zinc acrylate resin and stir evenly, then add organic bentonite, pigments and fillers, copper pyrithione, 4,5-dichloro- Stir 2-n-octyl-4-isothiazolin-3-one and cuprous oxide evenly, transfer to a sand mill for grinding until the fineness is 40 μm, stop grinding, and save the obtained slurry for later use;

④In the batching tank, add the slurry prepared in step ② and step ③ and add the remaining organic solvent, stir and disperse evenly at a speed of 500-800rpm, filter, pack, and label to obtain self-polishing antifouling paint 1 and 2 .

Comparative example 1～5 prepares the comparative example antifouling paint 1～5 that is used for contrast

(1) The formula is shown in Table 2.

Table 2

In Table 2, Paraloid B66 is a product of ROHM & HAAS Company. It is a 50wt% xylene solution of MMA/BMA polymer, with a Tg°C of 50 and a viscosity of 5000-8500mPa.s. The rest are the same as in Table 1.

(2) The preparation method is basically the same as in Examples.

Carry out performance test to embodiment and comparative example

(1) Detection method

Pencil hardness is measured according to GB/T6739; paint film flexibility is measured according to GB/T1731;

Coating contact angle is measured by SL200B contact angle meter; storage stability is measured by GB/T6753.3; shallow sea hanging plate is measured by GB/T5370; dynamic simulation test is measured by GB/T7789.

(2) The test results are shown in Table 3.

table 3

It can be seen from the test results in Table 3 that:

(1) self-polishing antifouling paint of the present invention (embodiment 1 and embodiment 2), the flexibility of paint film and hardness are good, have passed through 3 years shallow sea immersion test and the dynamic simulation test of 8 cycles, have good Self-polishing performance and long-term antifouling;

(2) The composition of the antifouling paint of Comparative Example 1 is basically the same as that of Example 1, and the main difference is: Comparative Example 1 does not use graphene microsheets.

As can be seen from the test results in Table 3, the contact angle of the antifouling paint film surface of Comparative Example 1 without using graphene microplates is only 48 °, while the contact angle of the paint film surface of Example 1 using graphene microplates is only 48 °. Angle is increased to 74°, which proves that graphene microsheets have the function of increasing hydrophobicity, which can reduce the affinity between the coating surface and water and reduce navigation resistance; the antifouling paint test panel of Comparative Example 1 has small cracks in the shallow sea hanging plate, And embodiment 1 does not appear, proves graphene microplate, can improve the intensity of paint film, has overcome the partial brittle shortcoming of rosin physical property;

(3) The composition of the antifouling paint of Comparative Example 2 is basically the same as that of Example 1, the main difference being: Comparative Example 2 did not use 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one and Copper pyrithione is replaced by cuprous oxide and zinc oxide.

As can be seen from the test results in Table 3, the composition of the antifouling agent in the antifouling paint of Comparative Example 2 changed. The test panel was soaked in shallow sea for 24 months, and the antifouling evaluation was 83; after soaking for 36 months, the antifouling evaluation was 68. , are lower than that of Example 1, proving that the compounded antifouling agent of 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, copper pyrithione, cuprous oxide and zinc oxide, Its antifouling effect is better than that of antifouling paint only using cuprous oxide and zinc oxide;

(4) The composition of the antifouling paint of comparative example 3 is basically the same as that of Example 2, and the main difference is: zinc acrylic resin and hydroxyacrylic resin are replaced with Paraloid B66, and the total amount of resin components and the amount of antifouling agent are unchanged, which belongs to typical can Controlled dissolution antifouling paint.

It can be seen from the test results in Table 3 that the antifouling paint test panel of Comparative Example 3 was soaked in the shallow sea for 24 months, and the antifouling performance evaluation was 74 points, which was lower than the comprehensive evaluation score of 85 points required by the GB/T5370 standard. The dynamic simulation test has not passed, which proves that the self-polishing paint of the present invention has better long-term antifouling performance than Comparative Example 3;

(5) The composition of the antifouling paint of Comparative Example 4 is basically the same as that of Example 1, the main difference being that no hydroxyl acrylic resin is used, but zinc acrylate resin is used instead.

As can be seen from the test results in Table 3, the storage stability of the antifouling paint in Comparative Example 4 does not reach the technical index, which proves that the hydroxyacrylic resin has a good wetting and dispersing effect on metal oxides, and the surface of the zinc oxide is wrapped with the hydroxyacrylic resin , and are physically separated and wrapped by graphene microflakes, which reduces the contact and chemical interaction between resin acid and zinc oxide in rosin, and improves the storage stability of the paint;

(6) The composition of the antifouling paint of Comparative Example 5 is basically the same as that of Example 1, and the main difference is: no graphene microchips and only zinc acrylate resin are used as the resin component, which belongs to a typical zinc acrylate self-polishing antifouling paint.

As can be seen from the test results of Table 3, the contact angle of the surface of the antifouling paint film of Comparative Example 5 is only 51 °, which is far lower than the contact angle of the surface of the paint film of Example 1 and Example 2 using graphene microplates. It is further proved that graphene microflakes can reduce the affinity of the coating surface with water and reduce sailing resistance.

In addition, the resin of comparative example 5 antifouling paint is only acrylic acid zinc resin, and this resin solid content is 50wt%, and the comparative example 5 antifouling paint solid content of preparation is thus 68wt%; When the resin component used in embodiment 1 is adjusted to When the viscosity range is the same as that of Comparative Example 1, the solid content of the resin used in Example 1 reaches about 70wt%, so the solid content of the prepared antifouling paint of Example 1 is 78wt%, and the VOC is lower, which proves that the antifouling paint of the present invention uses rosin the positive effects brought about.

Claims (2)

1. a self-polishing antifouling paint, is characterized in that, in the self-polishing antifouling paint of 100 mass parts, and solid meter resin 18 ~ 24 parts, stain control agent 50 ~ 55 parts, graphene microchip 0.5 ~ 1.5 part, color stuffing 3 ~ 6 parts, dispersion agent 1 ~ 2 part, organobentonite 1 ~ 2 part, surplus is organic solvent;

Described 18 ~ 24 parts of solid meter resins are by solid meter Hydroxylated acrylic resin 4 parts, solid meter zinc acrylate resin, 4 ~ 6 parts, surplus be rosin composition, wherein, the Zn content of solid meter zinc acrylate resin is 12 ~ 15wt%, and the hydroxy radical content of solid meter Hydroxylated acrylic resin is 4 ~ 5wt%;

Described 50 ~ 55 parts of stain control agents are that zinc oxide forms by copper pyrithione 3 parts, 4,5-bis-chloro-Kathons 3 parts, 30 ~ 35 parts, Red copper oxide, surplus;

Described graphene microchip particle diameter (D ₅₀)≤10 μm, specific surface area 200 ~ 250m ²/ g; Described zinc oxide and Red copper oxide are spheroidal particle, zinc oxide particle diameter≤10 μm, Red copper oxide particle diameter≤25 μm.

2. a preparation method for self-polishing antifouling paint according to claim 1, is characterized in that, concrete preparation process is as follows:

1. each component is prepared by the consumption of claim 1, for subsequent use;

2. in dispersion tank, add Hydroxylated acrylic resin, dispersion agent, part organic solvent, after stirring, add graphene microchip, zinc oxide stirs, proceed in horizontal sand milling and grind, until slurry fineness is 20 μm, stop grinding, obtain graphene microchip-zinc oxide-Hydroxylated acrylic resin slurry, save backup;

3. in dispersion tank, add rosin and part organic solvent, under agitation make rosin fully dissolve, then add zinc acrylate resin and stir, then add organobentonite, color stuffing, copper pyrithione, 4, the chloro-Kathon of 5-bis-, Red copper oxide, stir, proceed in sand mill and grind, until fineness is 40 μm, stop grinding, preserve gained slurry for subsequent use;

4., in material-compound tank, add slurry that 3. 2. step obtain with step and add residue organic solvent, with the speed dispersed with stirring of 500 ~ 800rpm evenly after, to filter, packaging, label, obtain self-polishing antifouling paint.