Chlorinated rubber antifouling paint and method of making same

Abstract

The application discloses chlorinated rubber antifouling paint and a preparation method thereof, and belongs to the technical field of antifouling paint. The chlorinated rubber antifouling paint comprises the following components in parts by weight: chlorinated rubber 20-30 parts, sorbitol polyglycidyl ether 3-6 parts, toughening agent 1-5 parts, cuprous oxide 30-40 parts, biological killing agent 4-7 parts, rosin 3-9 parts, defoaming agent 0.2-0.6 parts, pigment 2-5 parts, thixotropic agent 1-2 parts and solvent 5-10 parts. The biological killing agent is a compound of benzotriazole derivative and natural antifouling agent. The toughening agent is a compound of epoxy fatty acid methyl ester and full-acrylate core-shell impact modifier. The preparation method comprises the following steps: uniformly stirring the solvent, chlorinated rubber and sorbitol polyglycidyl ether, adding the defoaming agent, then adding the rosin, toughening agent and thixotropic agent, uniformly stirring the pigment, and then adding the cuprous oxide and biological killing agent to obtain the antifouling paint. The antifouling paint provided by the application guarantees the antifouling performance and improves the flexibility, adhesion and durability and the like.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of antifouling paint, and particularly relates to a chlorinated rubber antifouling paint and a preparation method thereof. BACKGROUND

[0002] As a protective coating material commonly used in the field of shipbuilding, chlorinated rubber antifouling paint occupies an important position in the protection of static and dynamic conditions of ships due to its high frequency of use. However, with the increasing demand for high-performance protection, the defects of chlorinated rubber antifouling paint in the actual use process have gradually become prominent.

[0003] At present, the chlorinated rubber antifouling paint circulating in the market has poor flexibility and impact resistance of the paint film, which is difficult to adapt to the deformation demand in complex environment, and the paint film is prone to damage during use, especially in low temperature environment, the paint film is prone to cracking, which seriously weakens the protection of the antifouling paint to the substrate; at the same time, the problem of burst release of antifouling agent is prominent, the durability of the paint film is insufficient, and the antifouling performance decays rapidly with time, frequent recoating operation is required, which greatly increases the maintenance cost. In addition, the adhesion of chlorinated rubber antifouling paint is insufficient, which leads to poor combination of the paint film and the substrate, and peeling phenomenon easily occurs, so that the long-acting protection function cannot be realized.

[0004] The above defects make it difficult for chlorinated rubber antifouling paint to meet the requirements of modern industry for high-performance protective coatings, and it is urgent to develop a chlorinated rubber antifouling paint technology which can effectively solve the above defects and improve the comprehensive performance. SUMMARY

[0005] In view of the poor flexibility and burst release of antifouling agent of chlorinated rubber antifouling paint in the background art, the present application develops a chlorinated rubber antifouling paint which can improve flexibility, low temperature resistance, adhesion and antifouling durability while ensuring antifouling performance, as follows:

[0006] A chlorinated rubber antifouling paint, comprising the following components by weight: chlorinated rubber 20-30 parts, sorbitol polyglycidyl ether 3-6 parts, toughening agent 1-5 parts, cuprous oxide 30-40 parts, biological killing agent 4-7 parts, rosin 3-9 parts, defoaming agent 0.2-0.6 parts, pigment 2-5 parts, thixotropic agent 1-2 parts, and solvent 5-10 parts; the biological killing agent is a compound of benzotriazole derivative and natural antifouling agent; the toughening agent is a compound of epoxy fatty acid methyl ester and full acrylate core-shell impact modifier.

[0007] As a preferred mode, the sorbitol polyglycidyl ether is at least one of Denacol EX-614 and Denacol EX-614B; the chlorinated rubber is at least one of Pergut S20 and ADEKA CR-5; the chlorine content of the chlorinated rubber is 64-65%.

[0008] As a preferred manner, the mass ratio of the epoxy fatty acid methyl ester to the full acrylate core-shell impact modifier is 4-5:1.

[0009] As a preferred manner, the epoxy fatty acid methyl ester is at least one of epoxy fatty acid methyl ester J107, epoxy fatty acid methyl ester TE-01, epoxy fatty acid methyl ester TE-02; the full acrylate core-shell impact modifier is at least one of Paraloid TM EXL-2330, Paraloid TM EXL-2388.

[0010] As a preferred manner, the mass ratio of the benzotriazole derivative to the natural antifouling agent is 1:3-6.

[0011] As a preferred manner, the benzotriazole derivative is 2-(2,4-dihydroxyphenyl)-2H-benzotriazole or 2-(5'-tert-butyl-2'-hydroxyphenyl) benzotriazole; the natural antifouling agent is at least one of chitosan, capsaicin, carotin, tannic acid, quercetin.

[0012] As a preferred manner, the defoaming agent is a silicone-based defoaming agent, the silicone-based defoaming agent is at least one of EFKA SI2038, EFKA SI 2722; the thixotropic agent is a polyamide thixotropic agent, the polyamide thixotropic agent is at least one of Akoma Ultra, Disperal 6650; the pigment is an iron-based pigment, the iron-based pigment is at least one of Yipin S190, Yipin S313, Huayuan 130A.

[0013] As a preferred manner, the rosin is first-class masson pine rosin, the resin acid content in the first-class masson pine rosin is 85-90%; the solvent is at least one of dimethylbenzene, methyl isobutyl ketone, methyl isoamyl ketone, n-butanol, butyl acetate, heavy benzene.

[0014] A preparation method of a chlorinated rubber antifouling paint, comprising the following steps:

[0015] Step S1: a part of the solvent, chlorinated rubber, sorbitol polyglycidyl ether are added into a dispersion tank, the rotating speed is controlled to be 1500-2000r / min, mixed stirring is carried out, after uniform stirring, the rotating speed is kept unchanged, the defoaming agent is added, after uniform stirring, a first mixture is obtained;

[0016] Step S2: rosin, toughening agent, thixotropic agent are added into the first mixture, the rotating speed is controlled to be 1500-2000r / min, mixed stirring is carried out, after uniform stirring, a second mixture is obtained;

[0017] Step S3: adding pigments to the second mixture, adjusting the rotation speed to 2000-3000 r / min, mixing and stirring to obtain a third mixture;

[0018] Step S4: adding cuprous oxide and a biological killing agent to the third mixture, controlling the rotation speed to 1500-2000 r / min, stirring until the fineness is less than 80 μm, and then filtering to obtain the chlorinated rubber antifouling paint.

[0019] As a preferred mode, in step S2, the toughening agent is obtained by first grinding the full acrylate core-shell impact modifier to below 0.1 μm by ball milling, then mixing with part of the solvent and the epoxy fatty acid methyl ester in a dispersion tank, controlling the rotation speed to 1000-1500 r / min, and stirring for 10-15 min to obtain the mixture, and the mass ratio of the epoxy fatty acid methyl ester to the full acrylate core-shell impact modifier is 4-5:1.

[0020] In step S4, the biological killing agent is obtained by first mixing the benzotriazole derivative, the natural antifouling agent, and part of the solvent in a dispersion tank, heating to 40-50 DEG C and stirring for 30 min to obtain the mixture, and the mass ratio of the benzotriazole derivative to the natural antifouling agent is 1:3-6.

[0021] Compared with the prior art, the present application has the following advantages:

[0022] 1. The chlorinated rubber antifouling paint provided by the present application uses a chlorinated rubber and sorbitol polyglycidyl ether compound system, which improves the flexibility and impact resistance of the paint film through physical and chemical dual action, effectively alleviates the cracking problem of the paint film in a low temperature environment, enhances the adhesion between the antifouling paint film and the substrate, and makes the antifouling paint film better resist the impact of seawater, friction and other external forces, thereby prolonging the service life of the paint film. The introduction of sorbitol polyglycidyl ether improves the dispersion stability of cuprous oxide in the system through steric hindrance effect and charge repulsion effect, and improves the uniformity and persistence of the antifouling effect. On the other hand, through micropore physical restraint and coordination complex release, the cuprous oxide is released at a stable rate, which not only ensures the antifouling effect, but also prolongs the service life of the antifouling paint and reduces the frequency of maintenance and re-painting.

[0023] ​2. The chlorinated rubber antifouling paint provided by the present application selects epoxy fatty acid methyl ester and full acrylate core-shell impact modifier as a toughening agent, strengthens the mechanical structure through molecular chain modification, constructs a multi-stage anti-damage mechanism of stress buffering and crack blocking, not only improves the flexibility and impact resistance of the paint film, but also endows the paint film with better environmental adaptability, and exhibits significant synergistic effect. The use of epoxy fatty acid methyl ester and full acrylate core-shell impact modifier strengthens the dispersibility of cuprous oxide and biological killing agent, avoids the release defects of traditional coating "burst release-attenuation", and further prolongs the effective antifouling period of the paint film. Through synergistic effect, the full acrylate core-shell impact modifier and the epoxy fatty acid methyl ester not only physically block the penetration of water in the environment, improve the corrosion resistance of the paint film, and further prolong the service life of the paint film, but also reduce the surface energy of the paint film, enhance the resistance to initial attachment of marine organisms, and improve the antifouling performance of the paint film. In addition, the epoxy fatty acid methyl ester and sorbitol polyglycidyl ether are chemically bonded, which enhances the intermolecular force of the paint film and improves the bonding strength between the paint film and the substrate, effectively improves the adhesion performance of the paint film, and reduces the problems of blistering and peeling caused by insufficient adhesion.

[0024] 3. The chlorinated rubber antifouling paint provided by the present application introduces benzotriazole derivatives and natural antifouling agent as biological killing agent, not only effectively inhibits the growth and attachment of organisms by interfering with the photosynthesis and respiration of algae and marine organisms, significantly improves the antifouling performance of the paint film, but also based on the slow-release effect of the natural antifouling agent and the chemical stability of the benzotriazole derivatives, constructs a double action mode of "sustained release-stable controlled release", prolongs the effective release period of the biological killing agent, at the same time, the introduction of benzotriazole derivatives effectively prevents the aging of the coating by absorbing ultraviolet rays, avoids the cracking and peeling of the coating, and prolongs the service life of the antifouling paint. In addition, the benzotriazole derivatives form a protective film on the surface of copper through complexation, realize the slow and controllable release of Cu²⁺, and further prolong the antifouling period. DETAILED DESCRIPTION

[0025] The technical solutions of the present application will be described below. Obviously, the described embodiments are part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0026] In addition, the technical features involved in different embodiments of the present application described below can be combined with each other as long as they do not conflict with each other.

[0027] The application aims to provide a chlorinated rubber antifouling paint and a preparation method thereof, which can improve flexibility, low temperature resistance, adhesion and antifouling durability while ensuring antifouling performance.

[0028] The application provides a chlorinated rubber antifouling paint, which comprises the following components in parts by weight: chlorinated rubber 20-30 parts, sorbitol polyglycidyl ether 3-6 parts, toughening agent 1-5 parts, cuprous oxide 30-40 parts, biological killing agent 4-7 parts, rosin 3-9 parts, defoaming agent 0.2-0.6 parts, pigment 2-5 parts, thixotropic agent 1-2 parts, and solvent 5-10 parts.

[0029] The chlorinated rubber is a weak polar substance, and the difference in polarity between the chlorinated rubber and the cuprous oxide leads to high interfacial tension, so that the cuprous oxide particles are aggregated to cause uneven dispersion of the cuprous oxide, and further affect the stable release of the cuprous oxide and the antifouling performance. The polar groups of the sorbitol polyglycidyl ether, i.e., the hydroxyl groups and the oxygen atoms in the ether, can be combined with the strong polar C-Cl bonds in the chlorinated rubber or the metal cations on the surface of the cuprous oxide particles (Cu²⁺ , surface hydroxyl groups and other active sites) to form stable adsorption through hydrogen bonds, van der Waals forces and the like, and after adsorption, a layer of “three-dimensional adsorption layer” is formed on the surface of the particles, thereby forming a steric hindrance effect; since the ether bond oxygen atoms in the sorbitol polyglycidyl ether chain segment can adsorb anions in the system through hydrogen bonds, when the cuprous oxide particles wrapped with the “sorbitol polyglycidyl ether adsorption layer” approach each other, a charge repulsion effect is formed. The steric hindrance effect and the charge repulsion effect synergistically improve the dispersion stability of the cuprous oxide in the system, and improve the uniformity and sustainability of the antifouling effect; on the other hand, on the basis of the formation of the rigid skeleton of the chlorinated rubber, the cuprous oxide is dispersed in the chlorinated rubber skeleton, and part of the particles are wrapped by the microporous channels to form a “particle-micropore” composite structure; at the same time , the cuprous oxide forms a coordination complex with the chlorine ions in the chlorinated rubber, and is “anchored” in the rubber skeleton and cannot freely diffuse; as the water medium continues to penetrate, water molecules in the system compete with ligands to bind , prompting part of the coordination bonds to break, releasing free . The maximum diffusion rate (physical upper limit) of the micropore constraint, and the effective release rate of the ion (chemical regulation) determined by the coordination complex. The dynamic dissociation of the coordination complex provides a continuous and stable ion source, and the microporous channel selects the appropriate diffusion rate through physical restriction, and the matching of the two keeps the Cu²⁺ release rate stable, which not only ensures the antifouling effect, but also prolongs the service life of the antifouling paint, reduces the frequency of maintenance and re-painting.

[0030] ​The present application introduces sorbitol polyglycidyl ether and chlorinated rubber as a synergistic film-forming material, the polar groups of sorbitol polyglycidyl ether and the molecular chains of chlorinated rubber increase the distance between molecular chains through intermolecular interaction, weaken the close packing of rigid structure, and absorb and disperse internal stress through the micro-elastic nodes formed by the branched structure of sorbitol polyglycidyl ether, the branched structure acts as a stress concentration point to effectively terminate crack propagation when impacted or bent, thereby improving the flexibility and impact resistance of the paint film, and by improving the compatibility of each component, reducing interface defects, and reducing the risk of cracking caused by uneven structure at low temperatures.

[0031] In addition, the introduced sorbitol polyglycidyl ether forms hydrogen bonds with water molecules through hydrophilic groups and is compatible with chlorinated rubber molecules through lipophilic groups, which is equivalent to building a "polar transition bridge" between "chlorinated rubber-water", reducing the difference in polarity and interfacial energy between the two phases, thereby reducing the surface tension. Deeply solidified in the micropores of the substrate, the multifunctional epoxy structure is "anchored" on the surface of the substrate through chemical bonds, and synergistically crosslinked with chlorinated rubber, enhancing the adhesion between the antifouling paint film and the substrate, making the antifouling paint film better resist the impact of seawater, friction and other external forces, thereby prolonging the service life of the paint film.

[0032] Preferably, the chlorine content of the chlorinated rubber is 64-65%, and further preferably, the chlorinated rubber is at least one of Pergut S20, ADEKA CR-5, and the sorbitol polyglycidyl ether is at least one of Denacol EX-614, Denacol EX-614B.

[0033] In the present application, the toughening agent is a combination of epoxy fatty acid methyl ester and full acrylic- core-shell impact modifier. The non-polar long carbon chain of epoxy fatty acid methyl ester can insert between the rubber molecular chains, and pull apart the molecular chain spacing through the steric hindrance effect. At the same time, the polar groups such as ester group and epoxy group of epoxy fatty acid methyl ester form weak hydrogen bonds or dipole-dipole interactions with the polar sites of rubber molecular chains (such as α-H beside double bond, residual hydroxyl group), which can shield the strong van der Waals force between rubber molecular chains, so that the originally closely intertwined molecular chains can be relaxed, the relative sliding resistance of chain segments is reduced, and the flexibility of rubber is improved. Epoxy fatty acid methyl ester relaxes the rubber molecular chains through interchain interaction, provides more sites for the interface combination of core-shell particles and molecular chains, and strengthens the interaction between shell layer and rubber matrix. The "point dispersion" of full acrylic-core-shell impact modifier core-shell particles forms "rigid support points" in the rubber molecular chain network, which not only maintains the flexibility by not hindering the normal activity of chain segments, but also absorbs energy through deformation when stressed, thereby improving the impact resistance. Through the combination of the two, the modification of chlorinated rubber molecular chains is realized, the mechanical structure is strengthened, and a multi-level anti-damage mechanism of stress buffering and crack blocking is constructed, which not only further improves the flexibility and impact resistance of the paint film, but also endows the paint film with better environmental adaptability, and exhibits significant synergistic effect.

[0034] The rosin acts as a "sacrificial component" in the paint film, forming a microporous channel network in the paint film by dissolving in seawater, allowing seawater to penetrate and contact the antifouling agent, so that the antifouling agent is released to the surface of the paint film, forming an effective toxic layer to prevent marine organisms from attaching, but it is easy to cause initial burst release and later failure. The compounding use of epoxy fatty acid methyl ester and full acrylate core-shell impact modifier, the epoxy group of epoxy fatty acid methyl ester can react with the active hydroxyl group on the surface of cuprous oxide to form a stable chemical bond; at the same time, the hydroxyl group generated after the ring opening of the epoxy group can further form a hydrogen bond network with the polar site of the biocide. This dual effect of "chemical anchoring + physical adsorption" allows the surface of the cuprous oxide particles to be firmly combined with a layer of polymer molecular chains, preventing them from re-aggregating during storage or use; at the same time, the dispersed core-shell particles act as "molecular spacers", uniformly distributed in the rubber matrix, physically separating cuprous oxide and biocide particles in different areas, preventing direct contact between particles and forming agglomerates. Through chemical anchoring and physical adsorption and physical separation, the dispersibility of cuprous oxide and biocide is further strengthened. This compound forms a chemical bond by embedding into the chlorinated rubber network, enhances the compactness of the paint film, forms multiple physical barriers, reduces the porosity of the paint film, and delays the penetration of water molecules and ions, thereby enhancing the uniformity of the antifouling effect and alleviating the problem of initial burst release of cuprous oxide. Under the synergistic effect of epoxy fatty acid methyl ester and full acrylate core-shell impact modifier, cuprous oxide and biocide are continuously and stably released through the slow erosion of rosin micropores, avoiding the release defects of traditional coatings "burst release-decay", thereby further prolonging the effective antifouling period of the paint film.

[0035] The introduction of full acrylate core-shell impact modifier and epoxy fatty acid methyl ester not only physically blocks the penetration of water in the environment through the core-shell structure, improves the corrosion resistance of the paint film, and further prolongs the service life of the paint film, but also reduces the surface energy of the paint film, enhances the resistance to initial attachment of marine organisms, and improves the antifouling performance of the paint film. In addition, epoxy fatty acid methyl ester and sorbitol polyglycidyl ether are chemically bonded, enhancing the intermolecular forces within the paint film. At the same time, epoxy fatty acid methyl ester and sorbitol polyglycidyl ether both contain multiple epoxy groups, which can cross-link to form a three-dimensional network structure, strengthening the internal toughness of the paint film. There are a large number of reactive active groups on the surface of the substrate, and the epoxy groups of the two can be chemically bonded to the active groups on the surface of the substrate. Due to the cross-linking reaction, the voids in the paint film are filled, making the paint film structure more compact, which can effectively block the invasion of water, oxygen and other substances into the interface. In combination with the chemical bonding formed by epoxy fatty acid methyl ester and sorbitol polyglycidyl ether and the surface of the substrate, the two synergistically improve the bonding strength of the paint film and the substrate interface, effectively improving the adhesion performance of the paint film, reducing the problems of blistering and peeling caused by insufficient adhesion.

[0036] Preferably, the mass ratio of the epoxy fatty acid methyl ester to the full acrylate core-shell impact modifier is 4-5:1. Further preferably, the epoxy fatty acid methyl ester is at least one of epoxy fatty acid methyl ester J107, epoxy fatty acid methyl ester TE-01, epoxy fatty acid methyl ester TE-02; the full acrylate core-shell impact modifier is at least one of Paraloid TM EXL-2330, Paraloid TM EXL-2388.

[0037] In the present application, the biocide is a combination of benzotriazole derivatives and natural antifouling agents. After combination, a "multi-target synergistic attack" can be formed, which can cover "microorganisms (bacteria, fungi) + large fouling organisms (barnacles, polychaetes)" at the same time. The microorganisms are killed by benzotriazole derivatives, and the attachment of new fouling organisms is prevented by natural antifouling agents. The target points of the two are different, which can avoid the problem of biological drug resistance caused by long-term use of a single antifouling agent. Not only can the growth and attachment of algae and marine organisms be effectively inhibited, but the antifouling performance of the paint film can be significantly improved. Based on the slow-release effect of natural antifouling agents and the chemical stability of benzotriazole derivatives, a "sustained release-stable controlled release" dual action mode is constructed, which prolongs the effective release period of the biocide. At the same time, the introduction of benzotriazole derivatives can effectively prevent the aging of the coating by absorbing ultraviolet rays, avoiding phenomena such as cracking and peeling of the coating, and prolonging the service life of the antifouling paint. In addition, benzotriazole derivatives form a protective film on the surface of copper through complexation to achieve slow and controllable release of Cu²⁺, further prolonging the antifouling period.

[0038] Preferably, the mass ratio of the benzotriazole derivative to the natural antifouling agent is 1:3-6. Further preferably, the benzotriazole derivative is 2-(2,4-dihydroxyphenyl)-2H-benzotriazole or 2-(5'-tert-butyl-2'-hydroxyphenyl) benzotriazole, and the natural antifouling agent is at least one of chitosan, capsaicin, carnosol, tannic acid, and quercetin.

[0039] In order to ensure that the antifouling paint has stable and durable antifouling performance, first-class Masson's pine rosin is selected as the key ingredient, with a resin acid content of 85-90%, which can effectively regulate the release rate of the antifouling agent, has excellent compatibility with chlorinated rubber and other film-forming materials, and improves the uniformity and long-acting antifouling of the coating.

[0040] In a preferred embodiment, the defoaming agent is an organic silicon-based defoaming agent, which can instantaneously break bubbles and long-acting suppress bubbles due to its low surface tension in the antifouling system provided by the present application. The shear resistance meets the needs of high viscosity systems. Preferably, the organic silicon-based defoaming agent is at least one of EFKA SI 2038 and EFKA SI 2722.

[0041] In a preferred embodiment, the thixotropic agent is a polyamide thixotropic agent, and the polyamide thixotropic agent is at least one of Arkon Ultra, Disparlon 6650.

[0042] In a preferred embodiment, the pigment is an iron-based pigment, which has high chemical stability and corrosion resistance in the antifouling system provided by the present application, and the iron-based pigment is at least one of Yinpins S190, Yinpins S313, Huayuan 130A.

[0043] In a preferred embodiment, the solvent is at least one of xylene, methyl isobutyl ketone, methyl isoamyl ketone, n-butanol, butyl acetate, and heavy benzene.

[0044] The present application also provides a preparation method of chlorinated rubber antifouling paint, comprising the following steps:

[0045] Step S1: A part of the solvent, chlorinated rubber, and sorbitol polyglycidyl ether are added to a dispersion tank, the rotation speed is controlled to be 1500-2000 r / min, and mixing and stirring are performed, after uniform stirring, the rotation speed is kept unchanged, a defoaming agent is added, and uniform stirring is performed, to obtain a first mixture;

[0046] Step S2: Rosin, a toughening agent, and a thixotropic agent are added to the first mixture, the rotation speed is controlled to be 1500-2000 r / min, and mixing and stirring are performed, after uniform stirring, a second mixture is obtained;

[0047] Step S3: A pigment is added to the second mixture, the rotation speed is adjusted to be 2000-3000 r / min, and mixing and stirring are performed, to obtain a third mixture;

[0048] Step S4: Cuprous oxide and a biological killing agent are added to the third mixture, the rotation speed is controlled to be 1500-2000 r / min, and stirring is performed until the fineness is less than 80 μm, and then the chlorinated rubber antifouling paint is obtained by filtration.

[0049] In a preferred embodiment, in step S2, the toughening agent is obtained by first grinding the full acrylate core-shell impact modifier to below 0.1 μm by ball milling, and then mixing the full acrylate core-shell impact modifier with a part of the solvent and the epoxy fatty acid methyl ester in the dispersion tank, controlling the rotation speed to be 1000-1500 r / min, and stirring for 10-15 min, and the mass ratio of the epoxy fatty acid methyl ester to the full acrylate core-shell impact modifier is 4-5:1;

[0050] In step S4, the biological killing agent is obtained by first mixing the benzotriazole derivative, the natural antifouling agent, and a part of the solvent in the dispersion tank, heating to 40-50℃ and stirring for 30 min, and the mass ratio of the benzotriazole derivative to the natural antifouling agent is 1:3-6. Example 1

[0051] The present embodiment provides a chlorinated rubber antifouling paint, comprising the following components by weight:

[0052] Chlorinated rubber 20 parts, sorbitol polyglycidyl ether 3 parts, toughening agent 1 part, cuprous oxide 30 parts, biocide 4 parts, rosin 3 parts, defoaming agent 0.2 parts, pigment 2 parts, thixotropic agent 1 part, solvent 5 parts.

[0053] Preparation of toughening agent: 0.2 parts of all-acrylate core-shell impact modifier Paraloid™ EXL-2330 is ground to below 0.1 μm by a ball mill, then mixed with 2 parts of xylene, 0.8 parts of epoxy fatty acid methyl ester J107 in a dispersion tank, the stirring speed is controlled at 1000 r / min, and stirring is carried out for 15 minutes to obtain the toughening agent.

[0054] Preparation of biocide: 1 part of 2-(2,4-dihydroxyphenyl)-2H-benzotriazole, 1 part of chitosan, 2 parts of carotan, and 1 part of n-butanol are mixed in a dispersion tank, heated to 40°C and stirred for 30 minutes to obtain the biocide.

[0055] Preparation of chlorinated rubber antifouling paint:

[0056] (1) 2 parts of n-butanol, 20 parts of chlorinated rubber ADEKA CR-5, and 3 parts of sorbitol polyglycidyl ether Denacol EX-614 are added to a dispersion tank, the stirring speed is controlled at 2000 r / min, and mixing and stirring are carried out, after uniform stirring, the stirring speed is kept unchanged, 0.2 parts of defoaming agent EFKA SI 2038 is added, and uniform stirring is carried out to obtain a first mixture;

[0057] (2) 3 parts of first masson pine rosin, the above-prepared toughening agent, and 1 part of thixotropic agent Akema Ultra are added to the first mixture, the stirring speed is controlled at 2000 r / min, and mixing and stirring are carried out, after uniform stirring, a second mixture is obtained;

[0058] (3) 2 parts of iron-based pigment Yipin S190 are added to the second mixture, the stirring speed is adjusted to 3000 r / min, and mixing and stirring are carried out to obtain a third mixture;

[0059] (4) 30 parts of cuprous oxide and the above-prepared biocide are added to the third mixture, the stirring speed is controlled at 2000 r / min, and stirring is carried out until the fineness is less than 80 μm, then the chlorinated rubber antifouling paint is obtained by filtration. Example 2

[0060] The present embodiment provides a chlorinated rubber antifouling paint, comprising the following components by weight:

[0061] Chlorinated rubber 25 parts, sorbitol polyglycidyl ether 4 parts, toughening agent 3 parts, cuprous oxide 35 parts, biocide 6 parts, rosin 6 parts, defoamer 0.4 parts, pigment 4 parts, thixotropic agent 1.5 parts, solvent 8 parts.

[0062] Preparation of toughening agent: 0.5 parts of all-acrylate core-shell impact modifier Paraloid™ EXL-2388 is ground to below 0.1 μm by a ball mill, then mixed with 3 parts of n-butanol and 2.5 parts of epoxy fatty acid methyl ester TE-02 in a dispersion tank, stirring at 1500 r / min for 10 minutes to obtain the toughening agent.

[0063] Preparation of biocide: 1 part of 2-(5'-tert-butyl-2'-hydroxyphenyl) benzotriazole, 5 parts of capsaicin, and 2 parts of n-butanol are mixed in a dispersion tank, heated to 45°C and stirred for 30 minutes to obtain the biocide.

[0064] Preparation of chlorinated rubber antifouling paint:

[0065] (1) 3 parts of butyl acetate, 25 parts of chlorinated rubber Pergut S20, 4 parts of sorbitol polyglycidyl ether Denacol EX-614B are added to a dispersion tank, the stirring speed is controlled at 2000 r / min, and the mixture is stirred uniformly. After stirring, the stirring speed is kept unchanged, 0.4 parts of defoamer EFKA SI 2722 is added, and the mixture is stirred uniformly to obtain a first mixture;

[0066] (2) 6 parts of first-class masson pine rosin, the above-prepared toughening agent, and 1.5 parts of thixotropic agent Akoma Ultra are added to the first mixture, the stirring speed is controlled at 2000 r / min, and the mixture is stirred uniformly to obtain a second mixture;

[0067] (3) 4 parts of iron-based pigment Yipin S313 is added to the second mixture, the stirring speed is adjusted to 3000 r / min, and the mixture is stirred to obtain a third mixture;

[0068] (4) 35 parts of cuprous oxide and the above-prepared biocide are added to the third mixture, the stirring speed is controlled at 2000 r / min, and the mixture is stirred until the fineness is less than 80 μm, and then filtered to obtain the chlorinated rubber antifouling paint. Example 3

[0069] The present example provides a chlorinated rubber antifouling paint, which comprises the following components by weight:

[0070] Chlorinated rubber 30 parts, sorbitol polyglycidyl ether 6 parts, toughening agent 5 parts, cuprous oxide 40 parts, biocide 7 parts, rosin 9 parts, defoamer 0.6 parts, pigment 5 parts, thixotropic agent 2 parts, solvent 10 parts.

[0071] Preparation of toughening agent: 0.4 parts of all-acrylate core-shell impact modifier Paraloid™ EXL-2330, 0.5 parts of all-acrylate core-shell impact modifier Paraloid™ EXL-2388 are ground to below 0.1 μm by a ball mill, and then mixed with 4 parts of methyl isobutyl ketone, 1.1 parts of epoxy fatty acid methyl ester TE-01, 3 parts of epoxy fatty acid methyl ester J107 in a dispersion tank, the rotating speed is controlled at 1500 r / min, and stirring is performed for 10 minutes to obtain the toughening agent.

[0072] Preparation of biocide: 0.5 parts of 2-(2,4-dihydroxyphenyl)-2H-benzotriazole, 0.5 parts of 2-(5'-tert-butyl-2'-hydroxyphenyl)benzotriazole, 3 parts of tannic acid, 3 parts of quercetin, 2 parts of methyl isopentyl ketone are mixed in a dispersion tank, heated to 50℃ and stirred for 30 minutes to obtain the biocide.

[0073] Preparation of chlorinated rubber antifouling paint:

[0074] (1) 4 parts of methyl isobutyl ketone, 20 parts of chlorinated rubber ADEKA CR-5, 10 parts of chlorinated rubber Pergut S20, 2 parts of sorbitol polyglycidyl ether Denacol EX-614, 4 parts of sorbitol polyglycidyl ether Denacol EX-614B are added into a dispersion tank, the rotating speed is controlled at 2000 r / min, and mixing and stirring are performed, after uniform stirring, the rotating speed is kept unchanged, 0.2 parts of defoamer EFKA SI 2038, 0.4 parts of defoamer EFKA SI 2722 are added, and uniform stirring is performed to obtain a first mixture;

[0075] (2) 9 parts of primary masson pine rosin, the above-prepared toughening agent, 1 part of thixotropic agent Akoma Ultra, and 1 part of Disparlon 6650 are added into the first mixture, the rotating speed is controlled at 2000 r / min, and mixing and stirring are performed, after uniform stirring, a second mixture is obtained;

[0076] (3) 2 parts of iron-based pigment Yipin S190, and 3 parts of iron-based pigment Yipin S313 are added into the second mixture, the rotating speed is adjusted to 3000 r / min, and mixing and stirring are performed to obtain a third mixture;

[0077] (4) 40 parts of cuprous oxide, and the above-prepared biocide are added into the third mixture, the rotating speed is controlled at 2000 r / min, and stirring is performed until the fineness is less than 80 μm, and then the chlorinated rubber antifouling paint is obtained by filtration.

[0078] The application also provides the following comparative examples:

[0079] Comparative Example 1

[0080] The preparation method of the comparative example is the same as that of Example 2, and the components thereof are different from those of Example 2 only in that an equal amount of chlorinated rubber Pergut S20 is used to replace sorbitol polyglycidyl ether.

[0081] Comparative Example 2

[0082] The preparation method of the comparative example is the same as that of Example 2, and the components thereof are different from those of Example 2 only in that an equal amount of chlorinated rubber Pergut S20 is used to replace sorbitol polyglycidyl ether.

[0083] The operation of preparing the toughening agent is: mixing 3 parts of n-butanol and 3 parts of epoxy fatty acid methyl ester TE-02 in a dispersion tank, controlling the rotating speed at 1500 r / min, and stirring for 10 minutes to obtain the toughening agent.

[0084] Comparative Example 3

[0085] The preparation method of the comparative example is the same as that of Example 2, and the components thereof are different from those of Example 2 only in that an equal amount of chlorinated rubber Pergut S20 is used to replace sorbitol polyglycidyl ether.

[0086] The step S2 of preparing the chlorinated rubber antifouling paint is: adding 6 parts of first masson pine rosin, 3 parts of full acrylate core-shell impact modifier Paraloid™ EXL-2388, 3 parts of n-butanol, and 1.5 parts of thixotropic agent Akoma Ultra to the first mixture, controlling the rotating speed at 2000 r / min, and mixing and stirring, to obtain a second mixture after uniform stirring.

[0087] Comparative Example 4

[0088] The preparation method of the comparative example is the same as that of Example 2, and the components thereof are different from those of Example 2 only in that an equal amount of natural antifouling agent capsaicin is used to replace 2-(5'-tert-butyl-2'-hydroxyphenyl) benzotriazole.

[0089] The operation of preparing the biocide is: mixing 6 parts of capsaicin and 2 parts of n-butanol in a dispersion tank, heating to 45°C and stirring for 30 minutes to prepare the biocide.

[0090] Comparative Example 5

[0091] The preparation method of the comparative example is the same as that of example 2, and the components thereof are different from those of example 2 only in that an equal amount of chlorinated rubber Pergut S20 is used to replace sorbitol polyglycidyl ether, an equal amount of dibutyl phthalate is used to replace epoxy fatty acid methyl ester TE-02, and an equal amount of natural antifouling agent chili is used to replace 2-(5'-tert-butyl-2'-hydroxyphenyl) benzotriazole.

[0092] Preparation of chlorinated rubber antifouling paint:

[0093] (1) 3 parts of butyl acetate and 29 parts of chlorinated rubber Pergut S20 were added to a dispersion tank, the rotation speed was controlled at 2000 r / min, and mixed stirring was carried out, after uniform stirring, the rotation speed was kept unchanged, 0.4 parts of defoaming agent EFKA SI 2722 was added, and uniform stirring was carried out, to obtain a first mixture;

[0094] (2) 6 parts of primary masson pine rosin, 3 parts of n-butanol, 3 parts of dibutyl phthalate and 1.5 parts of thixotropic agent Akoma Ultra were added to the first mixture, the rotation speed was controlled at 2000 r / min, and mixed stirring was carried out, after uniform stirring, a second mixture was obtained;

[0095] (3) 4 parts of iron-based pigment Yipin S313 were added to the second mixture, the rotation speed was adjusted to 3000 r / min, and mixed stirring was carried out, to obtain a third mixture;

[0096] (4) 35 parts of cuprous oxide, 6 parts of chili and 2 parts of n-butanol were added to the third mixture, the rotation speed was controlled at 2000 r / min, and stirring was carried out until the fineness was less than 80 μm, then the chlorinated rubber antifouling paint was obtained by filtration.

[0097] In the present application, the chlorinated rubber antifouling paints prepared in examples 1-3 and comparative examples 1-5 were respectively detected according to the performance indexes in table 1, and the detection results are shown in table 1.

[0098] Table 1: Performance detection indexes of paint and performance detection results of chlorinated rubber antifouling paint

[0099]

[0100] Through the comparison of the above examples and comparative examples, it can be seen that the chlorinated rubber antifouling paint provided by the present application can ensure the antifouling performance, and at the same time, the flexibility (bending radius ≤1 mm), impact strength (≥80 Kg•cm), low temperature resistance (-20℃ without cracking), adhesion (crosshatch method ≤1 grade) and antifouling durability (≥3 years) of the paint film are improved.

[0101] Compared with Comparative Example 1, the chlorinated rubber antifouling paint prepared in Examples 1-3 is better, which shows that the chlorinated rubber is compounded with sorbitol polyglycidyl ether, significantly improves the flexibility and impact resistance of the paint film, effectively relieves the cracking of the paint film in low temperature environment, enhances the adhesion between the paint film and the substrate, improves the antifouling effect, and prolongs the service life of the paint film.

[0102] Compared with Comparative Examples 2 and 3, the chlorinated rubber antifouling paint prepared in Examples 1-3 is better, which shows that the epoxy fatty acid methyl ester is compounded with the full acrylate core-shell impact modifier as a toughening agent, not only improves the flexibility and impact resistance of the paint film, but also improves the adhesion and antifouling performance of the paint film, and prolongs the antifouling period.

[0103] Compared with Comparative Example 4, the chlorinated rubber antifouling paint prepared in Examples 1-3 is better, which shows that the benzotriazole derivative is compounded with the natural antifouling agent as a biological killer, which improves the antifouling performance of the paint film and prolongs the service life of the antifouling paint.

[0104] Compared with Comparative Example 5, the chlorinated rubber antifouling paint prepared in Examples 1-3 is better, which shows that the chlorinated rubber is compounded with sorbitol polyglycidyl ether, the epoxy fatty acid methyl ester is compounded with the full acrylate core-shell impact modifier as a toughening agent, and the benzotriazole derivative is compounded with the natural antifouling agent as a biological killer, realizing the synergistic effect of multiple additives, while ensuring the flexibility, impact strength, low temperature resistance, adhesion, antifouling performance and antifouling durability of the paint film.

[0105] The above examples are only examples for clearly illustrating, but not limiting the embodiments. For those skilled in the art, other different forms of changes or variations can be made on the basis of the above description. Here, all the embodiments need not and cannot be exhausted. The obvious changes or variations derived therefrom are still within the protection scope of the present application.

Claims

1. A chlorinated rubber antifouling paint characterised in that, The composition comprises the following components by weight: chlorinated rubber 20-30 parts, sorbitol polyglycidyl ether 3-6 parts, toughening agent 1-5 parts, cuprous oxide 30-40 parts, biocide 4-7 parts, rosin 3-9 parts, defoamer 0.2-0.6 parts, pigment 2-5 parts, thixotropic agent 1-2 parts, solvent 5-10 parts; the biocide is a compound of benzotriazole derivative and natural antifouling agent; the mass ratio of the benzotriazole derivative to the natural antifouling agent is 1:3-6; the toughening agent is a compound of epoxy fatty acid methyl ester and full acrylate core-shell impact modifier; the mass ratio of the epoxy fatty acid methyl ester to the full acrylate core-shell impact modifier is 4-5:1; the toughening agent is obtained by first grinding the full acrylate core-shell impact modifier to below 0.1 μm by ball milling, then mixing it with part of the solvent and the epoxy fatty acid methyl ester in a dispersion tank, controlling the rotation speed at 1000-1500 r / min, and stirring for 10-15 min.

2. A chlorinated rubber antifouling paint according to claim 1 characterised in that, The sorbitol polyglycidyl ether is at least one of Denacol EX-614 and Denacol EX-614B; the chlorinated rubber is at least one of Pergut S20 and ADEKA CR-5; the chlorine content of the chlorinated rubber is 64-65%.

3. A chlorinated rubber antifouling paint according to claim 1 characterised in that, The epoxy fatty acid methyl ester is at least one of epoxy fatty acid methyl ester J107, epoxy fatty acid methyl ester TE-01, and epoxy fatty acid methyl ester TE-02; the full acrylate core-shell impact modifier is at least one of Paraloid™ EXL-2330 and Paraloid™ EXL-2388.

4. The chlorinated rubber antifouling paint according to claim 1, characterized in that, The benzotriazole derivative is 2-(2,4-dihydroxyphenyl)-2H-benzotriazole or 2-(5'-tert-butyl-2'-hydroxyphenyl)benzotriazole; the natural antifouling agent is at least one of chitosan, capsaicin, carotan, tannic acid, and quercetin.

5. A chlorinated rubber antifouling paint according to claim 1 characterised in that, The defoamer is a silicone-based defoamer, which is at least one of EFKA SI 2038 and EFKA SI 2722; the thixotropic agent is a polyamide-based thixotropic agent, which is at least one of Akema Ultra and Disparlon MT-6650; the pigment is an iron-based pigment, which is at least one of Yipin S190, Yipin S313, and Huayuan 130A.

6. The chlorinated rubber antifouling paint according to claim 1, characterized in that, The rosin is first-class masson pine rosin, and the resin acid content in the first-class masson pine rosin is 85-90%; the solvent is at least one of dimethylbenzene, methyl isobutyl ketone, methyl isoamyl ketone, n-butanol, butyl acetate, and heavy benzene.

7. The method of preparing a chlorinated rubber antifouling paint according to any one of claims 1 to 6, characterized in that, The method comprises the following steps: Step S1: part of the solvent, the chlorinated rubber, and the sorbitol polyglycidyl ether are added into a dispersion tank, the rotation speed is controlled at 1500-2000 r / min, and mixing and stirring are performed; after uniform stirring, the rotation speed is kept unchanged, the defoamer is added, and uniform stirring is performed to obtain a first mixture; Step S2: adding rosin, toughening agent and thixotropic agent to the first mixture, controlling the rotating speed at 1500-2000 r / min, mixing and stirring, and obtaining a second mixture after uniform stirring; Step S3: adding pigment to the second mixture, adjusting the rotating speed at 2000-3000 r / min, mixing and stirring, and obtaining a third mixture; Step S4: adding cuprous oxide and a biological killing agent to the third mixture, controlling the rotating speed at 1500-2000 r / min, stirring until the fineness is less than 80 μm, and filtering to obtain the chlorinated rubber antifouling paint.

8. The preparation method of the chlorinated rubber antifouling paint according to claim 7, characterized in that, in step S4, the biological killing agent is a mixture obtained by mixing benzotriazole derivatives, natural antifouling agents and part of the solvent in a dispersion tank, heating to 40-50 DEG C and stirring for 30 min, and the mass ratio of the benzotriazole derivatives to the natural antifouling agents is 1:3-6.

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