Application of a geraniol complex, environmentally friendly marine antifouling coating and its preparation method and application

Abstract

This invention belongs to the technical field of marine antifouling materials, and discloses the application of agrimonol complex, an environmentally friendly marine antifouling coating, and its preparation method and application. The agrimonol complex includes agrimonol, a carrier material, and a modifier, with a mass ratio of agrimonol, carrier material, and modifier of 1:2~5:0.1~0.5; the carrier material is chitosan; and the modifier is KH550. The environmentally friendly marine antifouling coating prepared using this agrimonol complex, by using a carrier to support the agrimonol and combining it with the reinforcing binding effect of the modifier, can achieve slow and controllable release of agrimonol, avoiding the rapid release of large amounts of free agrimonol that would lead to short-term failure, thus achieving long-term stable antifouling. Simultaneously, by utilizing the activity of agrimonol to inhibit biofilm formation, it effectively blocks the attachment of marine organisms, solving the pain point of natural antifouling agents that "difficult to balance antifouling and environmental protection."

Description

Technical Field

[0001] This invention belongs to the field of ship antifouling materials technology, and discloses the application of agrimonol compound, an environmentally friendly ship antifouling coating and its preparation method and application. Background Technology

[0002] When ships are navigating or anchored in the marine environment, their hull surfaces are easily fouled by marine organisms such as barnacles, mussels, algae, and bacteria. This not only increases the ship's drag, leading to a significant increase in fuel consumption and a decrease in speed, but also accelerates the corrosion of the hull metal, shortens the ship's service life, increases dry-dock maintenance costs and downtime losses, and seriously affects shipping efficiency and economy.

[0003] Traditional antifouling coatings for ships mainly rely on the release of toxic substances such as organotin and copper ions to inhibit biofouling. However, organotin antifouling agents have been completely banned by the International Maritime Organization due to their strong toxicity, persistence and bioaccumulation in marine ecosystems. Although copper-based antifouling coatings are widely used, the long-term release of copper ions can still have a negative impact on the ecosystem of nearshore waters, and the antifouling effect decays rapidly over time, usually requiring recoating after 2 to 3 years.

[0004] Therefore, natural antifouling agents have become a research hotspot due to their advantages such as good environmental compatibility and strong biodegradability. However, natural antifouling agents often suffer from problems such as uncontrolled release rates, insufficient stability, and difficulty in balancing antifouling and environmental protection. For example, although low surface energy coatings do not release toxic substances, they quickly lose their antifouling ability after the coating wears down and cannot be repaired. This is because the main application scenario for marine antifouling coatings is in seawater, where the coating matrix (such as self-peeling resin) is constantly washed away by seawater, causing peeling. This leads to the rapid release of natural antifouling agents in the coating matrix, resulting in a loss of antifouling ability in a short period of time and a short antifouling cycle.

[0005] Agrimonia pilosa is a natural phenolic compound extracted from Agrimonia pilosa. It has significant biological activity, can inhibit biofilm formation, and has certain toxic effects on various microorganisms and aquatic organisms, showing potential as an antifouling agent. However, when agrimony pilosa is directly applied to marine coatings, the aforementioned obvious drawbacks also exist, resulting in a shorter antifouling period.

[0006] Therefore, the technical problem to be solved by the present invention is: how to provide a geranium-based compound that can provide long-term stable antifouling properties, and apply it to antifouling coatings to achieve a long antifouling cycle. Summary of the Invention

[0007] The purpose of this invention is to provide an application of agrimonol complex in the preparation of environmentally friendly marine antifouling coatings. This agrimonol complex utilizes chitosan as a carrier material to support agrimonol, and through the reinforcing binding effect of the modifier KH550, the agrimonol is released slowly, thereby enabling the prepared environmentally friendly marine antifouling coating to have a longer antifouling cycle and achieve long-term stable antifouling.

[0008] Meanwhile, the present invention also provides an environmentally friendly antifouling coating for ships containing the agrimonol complex, as well as its preparation method and application.

[0009] To achieve the above objectives, the present invention provides the following technical solution:

[0010] The application of a geraniol complex in the preparation of environmentally friendly marine antifouling coatings, wherein the geraniol complex comprises geraniol, a carrier material and a modifier, and the mass ratio of geraniol, carrier material and modifier is 1:2~5:0.1~0.5;

[0011] The carrier material is chitosan;

[0012] The modifier mentioned is KH550.

[0013] An environmentally friendly antifouling coating for ships, comprising 20-40 parts of zinc acrylic resin and 5-15 parts of agrimonol complex per 100 parts by weight; wherein the agrimonol complex comprises agrimonol, a carrier material and a modifier, and the mass ratio of agrimonol, the carrier material and the modifier is 1:2-5:0.1-0.5.

[0014] The carrier material is chitosan;

[0015] The modifier mentioned is KH550.

[0016] The mechanism by which the environmentally friendly marine antifouling coating disclosed in this invention has a long-term stable antifouling effect may lie in:

[0017] The phenolic hydroxyl group (-OH) in the agrimonol molecule acts as a hydrogen bond donor, while the amino group (-NH2) on the chitosan molecular chain acts as an acceptor, forming a stable hydrogen bond network between them. Furthermore, the chitosan backbone provides a hydrophilic environment, and some hydrophobic groups of agrimonol may interact hydrophobically with the hydrophobic regions of the chitosan chain, further stabilizing the complex. This allows agrimonol to be tightly bound to chitosan. In addition, the addition of KH550 causes the silanol (-Si-OH) in the KH550 molecule to undergo an acetylation reaction with the hydroxyl group (-OH) on the chitosan molecular chain, generating a siloxane bond (Si-OC), chemically bonding KH550 to chitosan. The amino group (-NH2) at the other end of KH550 undergoes a phenolic condensation reaction with the phenolic hydroxyl group (-OH) in the agrimonol molecule, generating a phenolic ether bond (COC), firmly fixing agrimonol to the chitosan backbone. This further increases the binding strength between agrimonol and chitosan.

[0018] When the zinc acrylate resin (self-peeling resin) is washed away by seawater, chitosan comes into contact with the seawater and absorbs water to form a highly viscoelastic gel structure, which is a stable three-dimensional network with reduced porosity, further delaying the release of agrimonol. In addition, the water absorption and swelling of chitosan is usually accompanied by the softening and unfolding of the molecular chains. This softening leads to an increase in the contact area between the chitosan molecular chains and agrimonol, thereby forming more hydrogen bonds and electrostatic interactions. As the number of hydrogen bonds increases, the binding strength between agrimonol and chitosan is strengthened.

[0019] Based on the above possible mechanisms, the rapid release of agrimonol that could lead to short-term failure can be avoided, thereby achieving long-term stable antifouling.

[0020] Preferably, based on 100 parts by weight, the environmentally friendly marine antifouling coating further includes 5-10 parts of rosin, 3-8 parts of polyamide wax, 0.5-2 parts of stabilizer, 0.3-1 parts of silicone leveling agent, 20-40 parts of pigments and fillers, and the balance solvent.

[0021] In this invention, the addition of stabilizers can inhibit the oxidative degradation of agrimonyol, while the carrier material improves its compatibility and dispersibility in the coating system. Combined with high-performance film-forming resin, the coating has good resistance to seawater erosion and UV aging, thereby effectively extending the antifouling cycle.

[0022] More preferably, the solvent is a mixture of n-butanol and xylene, wherein the volume ratio of n-butanol to xylene is 1:1~3.

[0023] More preferably, the stabilizer is a compound of antioxidant 1010 and ultraviolet absorber UV-327, wherein the mass ratio of antioxidant 1010 to ultraviolet absorber UV-327 is 1:1.

[0024] More preferably, the pigments and fillers are one or more combinations of iron oxide red, barium sulfate and talc.

[0025] Furthermore, this invention discloses a method for preparing the environmentally friendly antifouling coating for ships as described above, the method being as follows:

[0026] Step 1: Add the carrier material to ethanol, ultrasonically disperse for 30-60 minutes until a uniform dispersion is formed, heat to 40-60℃, add agrimonol and modifier, stir and react for 2-4 hours, cool to room temperature, centrifuge, vacuum dry to constant weight, and pass through a 200-mesh sieve to obtain the agrimonol complex.

[0027] Step 2: Add zinc acrylate resin, rosin, solvent, polyamide wax, stabilizer and silicone leveling agent to the mixing tank in sequence, and stir at 500~800 r / min for 1~2 hours to form a uniform base material;

[0028] Step 3: Add the agrimonol complex obtained in Step 1 and pigments and fillers to the base material obtained in Step 2, stir and disperse at a speed of 1000~1500 r / min for 30~60 minutes, then cool to room temperature and filter to obtain the environmentally friendly marine antifouling coating.

[0029] Finally, the present invention also discloses the application of the environmentally friendly antifouling coating described above in the antifouling treatment of ship surfaces.

[0030] Compared with the prior art, the beneficial effects of the present invention are:

[0031] This invention relates to an environmentally friendly marine antifouling coating. By using a carrier to support agrimonyol and combining it with the reinforcing effect of a modifier, the slow and controlled release of agrimonyol can be achieved, avoiding the rapid release of large amounts of free agrimonyol that could lead to short-term failure, thus achieving long-term stable antifouling. Simultaneously, by utilizing agrimonyol's activity in inhibiting biofilm formation, it effectively blocks the attachment of marine organisms, solving the pain point of natural antifouling agents where "antifouling and environmental protection are difficult to achieve simultaneously." Attached Figure Description

[0032] Figure 1 This is a photograph of the coating tested in Example 1 after 9 months;

[0033] Figure 2 This is a photograph of the coating tested in Example 2 after 9 months;

[0034] Figure 3 This is a photograph of the coating tested in Example 3 after 9 months;

[0035] Figure 4 This is a photograph of the coating tested in Example 4 after 9 months;

[0036] Figure 5This is a photograph of the coating tested in Example 5 after 9 months;

[0037] Figure 6 A photograph of the paint used in Comparative Example 1 after 3 months of testing.

[0038] Figure 7 This is a photograph of the paint used in Comparative Example 2 after 0.5 months of testing.

[0039] Figure 8 This is a photograph of the paint used in Comparative Example 3 after 0.5 months of testing.

[0040] Figure 9 A photograph of the paint used in Comparative Example 4 after one month of testing.

[0041] Figure 10 This is a photo of the paint used in Comparative Example 5 after 6 months of testing. Detailed Implementation

[0042] The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0043] Product Information:

[0044] Zinc acrylate resin: purchased from Wuxi Yaodexin Chemical Products Co., Ltd., brand name SPZN-100;

[0045] Agrimonia pilosa: purchased from Delta Bio, brand name Delta-3363;

[0046] Chitosan: Purchased from Shanghai Aladdin Biochemical Technology Co., Ltd., brand name C105799;

[0047] KH550: Purchased from Nanjing Pinning Coupling Agent Co., Ltd.;

[0048] Iron oxide red: purchased from Changsha Zhonglong Chemical Co., Ltd., grade 110;

[0049] Barium sulfate: purchased from Qingdao Yili Special Chemical Technology Co., Ltd., grade G-065;

[0050] Talc powder: purchased from Quanzhou Xufeng Powder Raw Materials Co., Ltd., brand name BHS-8860;

[0051] Rosin: Purchased from Maclean's, brand name C832364;

[0052] Antioxidant 1010: Purchased from Tianjin Lianlong New Materials Co., Ltd.;

[0053] UV absorber UV-327: purchased from Guangdong Wengjiang Chemical Reagent Co., Ltd.;

[0054] Polyamide wax: purchased from Nanjing Tianshi New Material Technology Co., Ltd., brand name NEW-0455;

[0055] Silicone leveling agent: purchased from Shanghai Tiger Polymer Technology Co., Ltd., brand name Tech-2550.

[0056] It should be noted that the technical solution of this application can be achieved by purchasing other commercially available raw materials, and is not limited to the aforementioned raw material suppliers.

[0057] The coatings in each embodiment and comparative example were prepared according to the following method:

[0058] Step 1: Add the carrier material to ethanol, ultrasonically disperse for 45 minutes to form a uniform dispersion, heat to 50°C, add agrimonol and modifier, stir and react for 3 hours, cool to room temperature, centrifuge, vacuum dry at 60°C to constant weight, and pass through a 200-mesh sieve to obtain the agrimonol complex.

[0059] Step 2: Add zinc acrylate resin, rosin, solvent, polyamide wax, stabilizer and silicone leveling agent to the mixing tank in sequence, and stir at 600 r / min for 1.5 hours to form a uniform base material;

[0060] Step 3: Add the agrimonol complex obtained in Step 1 and pigments and fillers to the base material obtained in Step 2, stir and disperse at 1200 r / min for 45 minutes, then cool to room temperature and filter to obtain the environmentally friendly marine antifouling coating.

[0061] Example 1

[0062] An environmentally friendly antifouling coating for ships, comprising the following raw materials in 100 parts by weight:

[0063] 30 parts of zinc acrylate resin

[0064] 15 parts of agrimony-containing compound (agritoury-containing compound: chitosan: KH550 = 1:3:0.3, mass ratio);

[0065] 8 parts of iron oxide red;

[0066] 5 parts barium sulfate;

[0067] 10 parts talcum powder;

[0068] 8.5 parts rosin;

[0069] 5 parts polyamide wax;

[0070] 1 part stabilizer (antioxidant 1010: UV-327 = 1:1, by mass).

[0071] 0.5 parts of silicone leveling agent;

[0072] Add n-butanol / xylene mixed solvent to a total of 100 parts (n-butanol:xylene = 1:2, volume ratio).

[0073] Example 2

[0074] An environmentally friendly antifouling coating for ships, comprising the following raw materials in 100 parts by weight:

[0075] 20 parts of zinc acrylate resin

[0076] 10 parts of agrimony-containing compound (agritoury-containing compound: chitosan: KH550 = 1:3:0.3, mass ratio);

[0077] 5 parts of iron oxide red;

[0078] 5 parts barium sulfate;

[0079] 10 parts talcum powder;

[0080] 5 parts rosin;

[0081] 8 parts polyamide wax;

[0082] Stabilizer 0.5 parts (antioxidant 1010: UV-327 = 1:1, by mass);

[0083] 1 part silicone leveling agent;

[0084] Add n-butanol / xylene mixed solvent to a total of 100 parts (n-butanol:xylene = 1:1, volume ratio).

[0085] Example 3

[0086] An environmentally friendly antifouling coating for ships, comprising the following raw materials in 100 parts by weight:

[0087] 40 parts of zinc acrylate resin

[0088] Five parts of agrimony-containing compound (agritoury-containing compound: chitosan: KH550 = 1:3:0.3, mass ratio);

[0089] 10 parts of iron oxide red;

[0090] 10 parts barium sulfate;

[0091] 20 parts talcum powder;

[0092] 10 parts rosin;

[0093] 3 parts polyamide wax;

[0094] Stabilizer 2 parts (antioxidant 1010: UV-327 = 1:1, by mass);

[0095] 0.3 parts of silicone leveling agent;

[0096] Add n-butanol / xylene mixed solvent to a total of 100 parts (n-butanol:xylene = 1:3, volume ratio).

[0097] Example 4

[0098] It is largely the same as Example 1, except that the agrimonol complex has a mass ratio of agrimonol: chitosan: KH550 of 1:2:0.5.

[0099] Example 5

[0100] It is largely the same as Example 1, except that the agrimonol complex has a mass ratio of agrimonol: chitosan: KH550 of 1:5:0.1.

[0101] Comparative Example 1

[0102] It is largely the same as Example 1, except that the agrimonol complex contains only agrimonol and chitosan, and the mass ratio of agrimonol to chitosan is 1:3.

[0103] Comparative Example 2

[0104] It is largely the same as Example 1, except that an equal amount of agrimonol is used to replace the agrimonol compound.

[0105] Comparative Example 3

[0106] It is largely the same as Example 1, except that the carrier material is replaced with an equal amount of bentonite.

[0107] Comparative Example 4

[0108] It is largely the same as Example 1, except that the carrier material is replaced with an equal amount of microcrystalline cellulose.

[0109] Comparative Example 5

[0110] It is largely the same as Example 1, except that cuprous oxide is used in an equal amount to replace the agrimonol compound.

[0111] Performance testing

[0112] An epoxy primer was applied to a 3mm thick, polished steel plate, achieving a dry film thickness of 80µm. An intermediate coat was then applied, bringing the dry film thickness to 120µm. Finally, the finished coatings from the various embodiments and comparative examples were sprayed onto the plate. The plate was allowed to air dry at room temperature for 7 days until fully cured, achieving a dry film thickness of 100µm. Shallow sea immersion tests were conducted according to GB / T5370-2007. Observations were made at 0.25 months, 0.5 months, 1 month, 3 months, 6 months, and 9 months of immersion. If more than 5 barnacles adhered to the sample, it was considered an antifouling failure, indicating the end of the antifouling cycle. The antifouling cycle is the time between the antifouling failure and the last observation. Photos were taken and recorded at the time of antifouling failure.

[0113] Coating adhesion: Tested in accordance with GB / T5210-2006.

[0114] Test data

[0115] The test results are shown in Table 1. Figures 1-5 These are photos of examples 1-5 when the anti-fouling measures failed. Figures 6-10 These are photos of Comparative Examples 1-5 when the anti-fouling measures failed.

[0116] Table 1. Test Results Data

[0117] Pollution prevention cycle (months) Coating adhesion (MPa) Example 1 6~9 5.1 Example 2 6~9 5.0 Example 3 6~9 5.5 Example 4 6~9 5.2 Example 5 6~9 5.1 Comparative Example 1 1~3 4.8 Comparative Example 2 0.25~0.5 4.7 Comparative Example 3 0.25~0.5 5.2 Comparative Example 4 0.5~1 4.9 Comparative Example 5 3~6 5.0

[0118] Results analysis:

[0119] 1. As can be seen from Examples 1 to 5, the coatings of the present invention have excellent performance in terms of antifouling period and adhesion. Their antifouling period is as long as 9 to 12 months, and their adhesion is 4.8 to 5.5 MPa, indicating that the environmentally friendly marine antifouling coatings of the embodiments have excellent antifouling period.

[0120] 2. As can be seen from Example 1 and Comparative Example 1, when the modifier KH550 is missing in the agrimonol complex, the binding strength between agrimonol and chitosan decreases, and the antifouling cycle is significantly reduced.

[0121] 3. As can be seen from Example 1 and Comparative Example 2, when no agrimonol is loaded, its antifouling cycle is extremely short.

[0122] 4. As can be seen from Examples 1 and Comparative Examples 3 and 4, when bentonite and microcrystalline cellulose are used instead of chitosan, the antifouling cycle is significantly shortened. This may be because: bentonite mainly adsorbs agrimonol through physical adsorption, resulting in weak binding force. Once the resin is peeled off and comes into contact with seawater, it rapidly absorbs water and swells, increasing the interlayer spacing of the bentonite. The originally adsorbed agrimonol may be squeezed out or released due to volume expansion. While microcrystalline cellulose also forms hydrogen bonds with agrimonol, its binding is relatively simple, mainly relying on surface adsorption to load agrimonol. This binding force is usually single-point and weak, and it also absorbs water and swells, but unlike chitosan, it does not form a gel. Instead, it absorbs water and swells, leading to increased volume and thus loss of agrimonol. This demonstrates that the chitosan carrier selected in this invention is specific and cannot be substituted.

[0123] 5. As can be seen from Example 1 and Comparative Example 5, although cuprous oxide has a slightly better effect than agrimonol alone, it is still not as good as in Example 1, and cuprous oxide will pollute the marine environment.

[0124] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the invention can be implemented in other specific forms without departing from the spirit or essential characteristics of the invention. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description. Thus, it is intended that all variations falling within the meaning and scope of equivalents of the claims be included within the present invention.

Claims

1. The application of a geraniol complex in the preparation of environmentally friendly marine antifouling coatings, characterized in that, The agrimonol complex comprises agrimonol, a carrier material, and a modifier, wherein the mass ratio of agrimonol, the carrier material, and the modifier is 1:2~5:0.1~0.5; The carrier material is chitosan; The modifier mentioned is KH550.

2. An environmentally friendly antifouling coating for ships, characterized in that, Based on 100 parts by weight, the environmentally friendly marine antifouling coating comprises 20-40 parts of zinc acrylic resin and 5-15 parts of agrimony phenol compound; the agrimony phenol compound comprises agrimony phenol, carrier material and modifier, and the mass ratio of agrimony phenol, carrier material and modifier is 1:2-5:0.1-0.

5. The carrier material is chitosan; The modifier mentioned is KH550.

3. The environmentally friendly antifouling coating for ships according to claim 2, characterized in that, Based on 100 parts by weight, the environmentally friendly marine antifouling coating also includes 5-10 parts of rosin, 3-8 parts of polyamide wax, 0.5-2 parts of stabilizer, 0.3-1 parts of silicone leveling agent, 20-40 parts of pigments and fillers, and the balance solvent.

4. The environmentally friendly antifouling coating for ships according to claim 3, characterized in that, The solvent is a mixture of n-butanol and xylene, wherein the volume ratio of n-butanol to xylene is 1:1~3.

5. The environmentally friendly antifouling coating for ships according to claim 3, characterized in that, The stabilizer is a compound of antioxidant 1010 and ultraviolet absorber UV-327, wherein the mass ratio of antioxidant 1010 to ultraviolet absorber UV-327 is 1:

1.

6. The environmentally friendly antifouling coating for ships according to claim 3, characterized in that, The pigments and fillers are one or more combinations of iron oxide red, barium sulfate, and talc.

7. A method for preparing an environmentally friendly antifouling coating for ships as described in any one of claims 2 to 6, characterized in that, The preparation method is as follows: Step 1: Add the carrier material to ethanol, ultrasonically disperse for 30-60 minutes until a uniform dispersion is formed, heat to 40-60℃, add agrimonol and modifier, stir and react for 2-4 hours, cool to room temperature, centrifuge, vacuum dry to constant weight, and pass through a 200-mesh sieve to obtain the agrimonol complex. Step 2: Add zinc acrylate resin, rosin, solvent, polyamide wax, stabilizer and silicone leveling agent to the mixing tank in sequence, and stir at 500~800 r / min for 1~2 hours to form a uniform base material; Step 3: Add the agrimonol complex obtained in Step 1 and pigments and fillers to the base material obtained in Step 2, stir and disperse at a speed of 1000~1500 r / min for 30~60 minutes, then cool to room temperature and filter to obtain the environmentally friendly marine antifouling coating.

8. The application of the environmentally friendly antifouling coating as described in any one of claims 2 to 6 in the antifouling treatment of ship surfaces.

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