Stain release type bionic marine antifouling paint with topological structure

Abstract

The invention discloses a fouling release type bionic marine antifouling paint with a topological structure. An anionic monomer, a hydrophilic amide monomer, a carboxyl curing agent and an organic solvent are subjected to an in-situ ester cross-linking reaction to prepare a modified curing agent with a soft and hard segment synergistic topological structure. In the final curing coating, the modified curing agent and the film-forming resin are subjected to a cross-linking reaction, the topological structure entropy of the coating is effectively improved through the soft and hard segment structure of the modified curing agent, and therefore coordination between cohesive force and adhesive force of the curing coating is achieved, and the curing coating is endowed with good adhesive performance through polar groups introduced by the modified curing agent; therefore, the adhesive can be excellently bonded on various base materials and intermediate paints. Meanwhile, a polar group introduced by the modified curing agent can drive the inert bionic mucus to migrate and release to the surface of the coating in the three-dimensional network structure, so that a good antifouling effect is achieved. The coating can be applied to antifouling of marine facilities, and is particularly suitable for various marine facilities immersed in a seawater environment for a long time.

Description

Technical Field

[0001] The invention belongs to the fields of marine antifouling coating technology and underwater coating protection technology, and relates to a fouling-releasing bionic marine antifouling coating with a topological structure. Background Art

[0002] Marine biofouling refers to the process by which marine fouling organisms non-selectively adhere to and grow on the surface of objects submerged in seawater. It is a major challenge currently faced by countries around the world in developing their ocean and maritime industries. Applying marine antifouling coatings is the most convenient and effective means to solve this problem.

[0003] Traditional marine antifouling coatings, while preventing marine fouling adhesion, bring a lot of pollution and harm, and are now gradually banned by countries around the world. New marine antifouling coatings based on environmentally friendly requirements, while preventing marine fouling organisms, will not threaten the marine environment, and are currently becoming the focus of development in countries around the world.

[0004] Silicone marine antifouling coatings belong to the field of environmentally friendly fouling-releasing antifouling coatings. Based on lower surface free energy and lower elastic modulus, they utilize the relative movement between the ship and the seawater to achieve the prevention and control of fouling organisms and the removal of loosely adhered fouling organisms, and have great application prospects.

[0005] However, silicone marine antifouling coatings currently have shortcomings such as poor adhesion to the substrate and inability to effectively prevent fouling in a static water environment, which urgently need to be improved. At present, bionic studies on large marine organisms such as fish and whales have shown that large marine organisms continuously secrete mucus from the inside out to moisten the skin surface, and use the secreted mucus to wrap and remove adherent fouling organisms. This related bionic mucus secretion type marine antifouling coating developed based on the bionic antifouling mechanism has made beneficial progress. However, this type of mucus secretion type marine antifouling coating generally has the problem of disordered migration and release of bionic mucus, which leads to reduced adhesion between the coating and the substrate. At present, the promotion and use of related coatings are greatly restricted. Summary of the invention

[0006] Purpose of the invention: The purpose of the present invention is to provide a topologically structured bionic marine antifouling coating with a fouling release structure to solve the defects of poor adhesion between the fouling release marine antifouling coating and the substrate, easy falling off, and the migration and release of bionic mucus will accelerate the falling off.

[0007] Technical solution: A topologically structured fouling-releasing bionic marine antifouling coating of the present invention comprises, by weight: (1) 80 to 100 parts of component A; (2) 20 to 35 parts of component B; (3) 5 to 10 parts of component C;

[0008] in,

[0009] Component A includes by weight:

[0010]

[0011]

[0012] Component B includes by weight:

[0013] Modified curing agent 10-20 parts

[0014] Solvent B 20-50 parts

[0015] Component C includes by weight:

[0016] Catalyst 5-10 parts

[0017] Solvent C 15-25 parts;

[0018] The modified curing agent is a modified polysiloxane polymer synthesized by anionic monomers, hydrophilic amide monomers, carboxyl curing agent and organic solvent through in-situ ester cross-linking reaction.

[0019] Furthermore, the hydrophobic silicone resin is selected from α,ω-dihydroxypolydimethylsiloxane having a viscosity of 2800-10000 mPa·s at room temperature.

[0020] Furthermore, the non-polar biomimetic mucus is selected from non-reactive inert silicone oil. Preferably, the non-reactive inert silicone oil is selected from methyl silicone oil with a kinematic viscosity of 10 to 50 cSt at room temperature, phenyl methyl silicone oil with a kinematic viscosity of 50 to 200 cSt at room temperature, and alkyl silicone oil with a kinematic viscosity of 70 to 100 cSt at room temperature.

[0021] Furthermore, the auxiliary agent is selected from at least one of a wetting and dispersing agent, a defoaming agent, and a leveling agent.

[0022] Specifically, the wetting and dispersing agent is selected from BYK116, BYK169 of BYK Company, and 901, 903 of Deqian Company.

[0023] Specifically, the defoaming agent is selected from BYK065, BYK066N of BYK Company, and EFKA2020 of Efka of the Netherlands.

[0024] Specifically, the leveling agent is selected from one of German BYK308, BYK310 and BYK373.

[0025] Furthermore, the pigment filler is common in the field and has no special requirements. As a preferred embodiment, it is selected from but not limited to one of calcium carbonate, ferric oxide, titanium dioxide, barium sulfate, kaolin, and zinc oxide.

[0026] Furthermore, the solvent A is selected from one of methanol, xylene and acetone; the solvent B is selected from one of acetone, butanone and acetylacetone; and the solvent C is selected from one of acetylacetone, cyclohexanone and toluene.

[0027] Furthermore, the catalyst is selected from one of dibutyltin dilaurate, stannous octoate and organic bismuth.

[0028] Furthermore, the weight ratio of the anionic monomer, the hydrophilic amide monomer, the carboxyl curing agent and the organic solvent is (5-10): (12-18): (20-35): (50-80).

[0029] Furthermore, the anionic monomer is selected from one of sodium 2-carboxyethyl acrylate, sodium acrylate, sodium indoleacrylate, and sodium alginate.

[0030] Furthermore, the hydrophilic amide monomer is selected from one of N-(2-hydroxyethyl) acrylamide, methacrylamide and dimethylaminopropyl acrylamide.

[0031] Furthermore, the carboxyl curing agent is selected from one of 3-carboxypropyltriethoxysilane, 2-carboxypropylmethyldimethoxysilane, 2-(triethoxysilyl)acetic acid and 3-carboxypropyltrimethoxysilane.

[0032] Furthermore, the organic solvent is selected from one of ethanol, acetone and toluene.

[0033] Furthermore, the modified curing agent is prepared by the following steps:

[0034] (1) In a reaction device protected by nitrogen and equipped with a stirring and reflux device, an anionic monomer, a hydrophilic amide monomer, a carboxyl curing agent and an organic solvent are added in sequence, and then the pH is adjusted to greater than 10 by a mixed solution of sodium hydroxide (1 g) / ethanol (10 g), and the reaction is stirred at 20 to 50 rpm at 40 to 50° C. for 12 to 24 hours;

[0035] (2) The precipitated product after the reaction is filtered, washed with deionized water for at least 3 times, and then dried in a vacuum device for 24 hours to obtain a modified polysiloxane polymer.

[0036] Furthermore, the coating of the present invention can be prepared according to conventional preparation methods. First, component A, component B, and component C are prepared separately and stored in a sealed manner. When coating, components A, B, and C are mixed in a conventional mixing manner and coated immediately.

[0037] Furthermore, the present invention provides a method for preparing a topologically structured fouling-releasing bionic marine antifouling coating:

[0038] (1) Adding a hydrophobic silicone resin, a nonpolar bionic mucus, and an additive to a dispersing and stirring device in sequence, and then dispersing at 100 rpm for 20 min, then adding a pigment and a filler and a solvent A to the dispersing and stirring device, and continuing to disperse at the same speed for 20 min, i.e., preparing component A, and then sealing and storing;

[0039] (2) using a dispersing and stirring device to disperse the modified curing agent and solvent B at 50 rpm for 10 min, i.e., preparing component B, and then sealing and storing;

[0040] (3) using a dispersing and stirring device to disperse the catalyst and solvent 3 at 50 rpm for 10 min, i.e., preparing component C, and then sealing and storing;

[0041] The present invention also provides a functional modified fouling-releasing marine antifouling coating, in which component A, component B and component C are uniformly mixed using conventional dispersion processes and equipment, and are applied by spraying, rolling, brushing or the like, and cured for at least 48 hours to prepare a coating with a film thickness of 150 to 250 um.

[0042] Beneficial effects: Compared with the prior art, the present invention has the following significant advantages: (1) Through an in-situ ester crosslinking reaction, the hard segment molecular chain segment (from anionic monomers and hydrophilic amide monomers) is introduced into the soft segment curing agent molecular structure (from carboxyl polysiloxane). This soft and hard segment synergy can effectively improve the topological structure entropy of the synthetic polymer, thereby achieving coordination between the cohesion and adhesion of the synthetic polymer, and achieving excellent bonding effect of the modified polymer. In the final cured coating, the modified curing agent undergoes a crosslinking reaction with the film-forming resin to form a three-dimensional network structure, and this topological structure is introduced into the cured coating, thereby coordinating the unity of the cohesion and adhesion of the cured coating polymer, ensuring that the cohesion and adhesion of the coating are close to each other, thereby achieving an energy dissipation factor of the cured coating close to tan=1, thereby ensuring that the coating has a good bonding effect with the substrate or the intermediate paint.

[0043] (2) The polar modified curing agent structure acts as an anchor point in the three-dimensional network molecular structure of the coating, thereby driving the active migration and release of the non-polar bionic mucus. The blocking effect produced by the modified curing agent anchor point makes the free non-polar bionic mucus in the coating only migrate spontaneously to the coating surface, achieving directional release of the mucus, and will not cause the coating to peel off due to the release of mucus at the coating-substrate interface. The prepared cured coating surface maintains the low surface energy characteristics of methylsiloxane. At the same time, the active release of bionic mucus creates a smooth environment for the coating surface, effectively inhibiting the adhesion of fouling organisms, thereby ensuring that the cured coating is firmly bonded while maintaining excellent anti-fouling effect. DETAILED DESCRIPTION

[0044] The present invention is described in detail below in conjunction with specific embodiments. The following embodiments will help those skilled in the art to further understand the present invention, but are not intended to limit the present invention in any form. It should be noted that, for those of ordinary skill in the art, without departing from the concept of the present invention, several variations and improvements can be made. These all belong to the protection scope of the present invention.

[0045] The coating of the present invention synthesizes a modified curing agent through an in-situ ester crosslinking reaction, introduces anionic monomers and hydrophilic amide monomers into the curing agent as hard segment structures, and uses the carboxyl siloxane structure of the curing agent itself as a soft segment structure to form a modified curing agent with a soft and hard segment synergistic topological structure. In the final cured coating, the modified curing agent undergoes a crosslinking reaction with a film-forming resin to form a three-dimensional network structure, and this topological structure is introduced into the cured coating, thereby coordinating the unity of the cohesion and adhesion of the cured coating polymer, ensuring that the cohesion and adhesion of the coating are close to each other, thereby achieving an energy dissipation factor close to tan=1 for the cured coating, thereby ensuring that the coating has a good bonding effect with the substrate or the intermediate paint. At the same time, the polar modified curing agent structure plays the role of an anchor point in the three-dimensional network molecular structure of the coating, thereby driving the non-polar bionic mucus to actively migrate and release, and the blocking effect generated by the modified curing agent anchor point makes the free non-polar bionic mucus in the coating only spontaneously migrate to the coating surface, realizing the directional release of the mucus, and will not cause the coating to peel off due to the release of the mucus at the coating-substrate interface. The surface of the prepared cured coating maintains the low surface energy characteristics of methylsiloxane. At the same time, the active release of biomimetic mucus creates a smooth environment for the coating surface, effectively inhibiting the adhesion of fouling organisms.

[0046] The modified curing agents involved in Examples 1-5 are prepared by the following Synthesis Examples 1-3 respectively. The raw materials used in Examples 1-5 and Synthesis Examples 1-3 are shown in Table 1. The specific implementation is not limited to the raw materials in Table 1, and the corresponding products can be selected according to the above. The other raw materials used in the examples are all commercially available chemical reagents.

[0047] Table 1

[0048]

[0049]

[0050] Synthesis example 1

[0051] The weight ratio of anionic monomer, hydrophilic amide monomer, carboxyl curing agent and organic solvent is 8:12:30:50. The specific preparation method is as follows:

[0052] (1) In a reaction device protected by nitrogen and equipped with a stirring and reflux device, anionic monomer 6-1, hydrophilic amide monomer 7-1, carboxyl curing agent 8-2 and organic solvent 9-1 are added in sequence, and then the pH is adjusted to greater than 10 by a sodium hydroxide (1 g) / ethanol (10 g) mixed solution, and the reaction is stirred at 40 rpm at 45° C. for 20 hours;

[0053] (2) The precipitated product after the reaction was filtered, washed with deionized water for at least 3 times, and then dried in a vacuum device for 24 hours to prepare a modified curing agent 1.

[0054] Synthesis example 2

[0055] The weight ratio of anionic monomer, hydrophilic amide monomer, carboxyl curing agent and organic solvent is 5:18:20:60. The specific preparation method is as follows:

[0056] (1) In a reaction device protected by nitrogen and equipped with a stirring reflux device, anionic monomer 6-2, hydrophilic amide monomer 7-2, carboxyl curing agent 8-1 and organic solvent 9-2 are added in sequence, and then the pH is adjusted to greater than 10 by a mixed solution of sodium hydroxide (1 g) / ethanol (10 g), and the reaction is stirred at 20 rpm at 40° C. for 24 hours;

[0057] (2) The precipitated product after the reaction was filtered, washed with deionized water for at least 3 times, and then dried in a vacuum device for 24 hours to prepare a modified curing agent 2.

[0058] Synthesis example 3

[0059] The weight ratio of anionic monomer, hydrophilic amide monomer, carboxyl curing agent and organic solvent is 10:15:35:80. The specific preparation method is as follows:

[0060] (1) In a reaction device protected by nitrogen and equipped with a stirring reflux device, anionic monomer 6-3, hydrophilic amide monomer 7-2, carboxyl curing agent 8-3 and organic solvent 9-1 are added in sequence, and then the pH is adjusted to greater than 10 by a mixed solution of sodium hydroxide (1 g) / ethanol (10 g), and the reaction is stirred at 50 rpm for 12 h at 50° C.;

[0061] (2) The precipitated product after the reaction was filtered, washed with deionized water for at least 3 times, and then dried in a vacuum device for 24 hours to prepare a modified curing agent 3.

[0062] Examples 1-5

[0063] The proportions of the three components A, B, and C of Examples 1-5 are shown in Table 2, and the specific proportions of the components of Examples 1-5 are shown in Table 3.

[0064] Table 2

[0065] Components Example 1 Example 2 Example 3 Example 4 Example 5 A 80 90 100 80 95 B 20 35 25 30 20 C 5 8 10 10 5

[0066] Table 3

[0067]

[0068]

[0069] According to Table 2 and Table 3, the preparation method of a fouling-releasing bionic marine antifouling coating of a topological structure of Examples 1-5 is shown in the following steps:

[0070] (1) Adding a hydrophobic silicone resin, a nonpolar bionic mucus, and an additive to a dispersing and stirring device in sequence, and then dispersing at 100 rpm for 20 min, then adding a pigment and a filler and a solvent A to the dispersing and stirring device, and continuing to disperse at the same speed for 20 min, i.e., preparing component A, and then sealing and storing;

[0071] (2) using a dispersing and stirring device to disperse the modified curing agent and solvent B at 50 rpm for 10 min, i.e., preparing component B, and then sealing and storing;

[0072] (3) using a dispersing and stirring device to disperse the catalyst and solvent 3 at 50 rpm for 10 min, i.e., preparing component C, and then sealing and storing;

[0073] (4) Component A, component B, and component C are mixed uniformly by conventional dispersion technology and equipment, and applied by spraying, rolling, brushing, etc. After curing for at least 48 hours, a coating with a film thickness of 150 to 250 μm is prepared.

[0074] In actual application, the antifouling coating can be prepared by conventional methods of marine antifouling coatings, and is not limited to the above preparation method.

[0075] Comparative Example 1 (Ordinary silicone low surface energy marine antifouling coating)

[0076] The common organosilicon low surface energy marine antifouling paint comprises the following raw materials in parts by weight: 90.0 parts of polysiloxane resin, 30.0 parts of pigments and fillers, 4.0 parts of cross-linking curing agent, 1.5 parts of catalyst, 0.5 parts of auxiliary agent and 10.0 parts of third solvent.

[0077] The polysiloxane resin is α, ω-dihydroxy polydimethylsiloxane with a viscosity of 10000 mPa·s; the pigment is zinc oxide; the cross-linking curing agent is tetraethyl orthosilicate; the catalyst is dibutyltin disilicate; the auxiliary agent is 0.5 parts of BYK161 dispersant from BYK; and the third solvent is xylene.

[0078] (1) 90.0 parts of α,ω-dihydroxy polydimethylsiloxane with a viscosity of 10000 mPa·s and 30.0 parts of micron-sized zinc oxide were added to a disperser and dispersed at 300 rpm for 30 min. Subsequently, 0.5 parts of BYK161 dispersant from BYK was added to the disperser at 200 rpm and dispersed for 30 min. The mixture was then ground with a sand mill to a fineness of less than 40 μm to prepare a pre-dispersed slurry and canned for standby use.

[0079] (2) 4.0 parts of tetraethyl orthosilicate and 10.0 parts of xylene were mixed evenly to prepare a crosslinking curing agent component, which was then canned for standby use; 1.5 parts of dibutyltin dioxysilicate and 20.0 parts of xylene were mixed evenly to prepare a catalyst component, which was then canned for standby use;

[0080] (3) Before use, the pre-dispersed slurry, the cross-linking curing agent component, and the catalyst component are stirred uniformly according to the ratio. After the obtained coating is applied and cured, a common organic silicon low surface energy marine antifouling coating with a thickness of 150 to 250 μm is obtained.

[0081] Comparative Example 2

[0082] Compared with Example 1, no anionic monomer is introduced into the prepared modified curing agent, and the remaining components and their weight parts are the same, and the preparation process is also the same as that of Example 1.

[0083] <Specific test experiments and conditions>

[0084] Test 1: Surface Free Energy

[0085] The contact angles of deionized water and diiodomethane on the surface of the cured coating were measured using the XG-CAMC3 fully automatic contact angle meter produced by Shanghai Xuanzhun Instrument Co., Ltd. Before the measurement, the coating surface needs to be cleaned with anhydrous ethanol and dried, and then the surface free energy of the coating is calculated according to the Owens two-liquid method.

[0086] Test 2: Pull-off method to measure adhesion after 100 days of seawater immersion (steel plate, epoxy intermediate paint)

[0087] The BGD500 digital semi-automatic adhesion tester produced by Guangzhou Biaogeda Precision Instrument Co., Ltd. was used to measure the adhesion of the coating applied on the corresponding substrate or epoxy intermediate paint. The steel plate needs to be polished with 800-grit sandpaper before use, and the epoxy intermediate paint used is the epoxy micaceous iron intermediate paint produced by Shanghai Jinsi Di. Before the test, it needs to be immersed in sterilized seawater for 100 days, and then taken out and dried for testing.

[0088] Test 3: Antifouling performance

[0089] A suspension containing at least 108 units of Streptococcus salivarius was dispersed in 20 ml of tryptic soy broth and incubated at 38°C, 5% CO2 for 2 hours. The suspension was then further diluted and inoculated in agar supplemented with 5% sheep blood and incubated at 38°C, 5% CO2 for 48 hours, and then the units containing six colonies were dispersed in 10 ml of tryptic soy broth. Subsequently, 20 ml of the above bacterial suspension was covered on the coating of 10×5 cm area and incubated at 38°C, 5% CO2 for 24 hours. After the incubation, each sample needed to be rotated and rinsed in 45 ml of distilled water for 30 seconds, and then rinsed with 50 ml of distilled water to remove non-sticky materials. The surface-adherent bacteria were observed using a Simga300 scanning electron microscope produced by Carl Zeiss, Germany.

[0090] The specific test results of Examples 1-5 and Comparative Examples 1-2 are shown in Table 4.

[0091] Table 4

[0092]

[0093] As can be seen from Table 4, the above test can confirm that the embodiment has excellent antifouling effect while having good adhesion. Therefore, the coating of the present invention can be excellently bonded to various substrates and intermediate paints. At the same time, the prepared coating has a good antifouling effect.

[0094] The above is a description of the specific embodiments of the present invention. It should be understood that the present invention is not limited to the above specific embodiments, and those skilled in the art may make various modifications or variations within the scope of the claims, which do not affect the essence of the present invention.

Claims

1. A topologically structured bionic marine antifouling coating with a fouling release property, characterized in that: In parts by weight, it comprises: (1) 80 to 100 parts of component A; (2) 20 to 35 parts of component B; (3) 5 to 10 parts of component C; in, Component A includes by weight: Component B includes by weight: Modified curing agent 10-20 parts Solvent B 20~50 parts Component C includes by weight: Catalyst 5-10 parts Solvent C 15-25 parts; The modified curing agent is a modified polysiloxane polymer synthesized by anionic monomers, hydrophilic amide monomers, carboxyl curing agent and organic solvent through in-situ ester cross-linking reaction.

2. The fouling-releasing bionic marine antifouling coating of topological structure according to claim 1, characterized in that: The hydrophobic silicone resin is selected from α,ω-dihydroxy polydimethylsiloxane with a viscosity of 2800-10000 mPa·s at room temperature.

3. The topologically structured fouling-releasing bionic marine antifouling coating according to claim 1, characterized in that: The non-polar bionic mucus is selected from one of methyl silicone oil with a kinematic viscosity of 10 to 50 cSt at room temperature, phenyl methyl silicone oil with a kinematic viscosity of 50 to 200 cSt at room temperature, and alkyl silicone oil with a kinematic viscosity of 70 to 100 cSt at room temperature.

4. The topologically structured bionic marine antifouling coating according to claim 1, characterized in that: The solvent A is selected from one of methanol, xylene and acetone; the solvent B is selected from one of acetone, butanone and acetylacetone; the solvent C is selected from one of acetylacetone, cyclohexanone and toluene.

5. The topologically structured fouling-releasing bionic marine antifouling coating according to claim 1, characterized in that: The catalyst is selected from dibutyltin diosilicate, stannous octoate and organic bismuth.

6. The topologically structured fouling-releasing bionic marine antifouling coating according to claim 1, characterized in that: The weight ratio of the anionic monomer, the hydrophilic amide monomer, the carboxyl curing agent and the organic solvent is (5-10): (12-18): (20-35): (50-80).

7. The topologically structured fouling-releasing bionic marine antifouling coating according to claim 1, characterized in that: The anionic monomer is selected from one of sodium 2-carboxyethyl acrylate, sodium acrylate, sodium indoleacrylate and sodium alginate.

8. The topologically structured fouling-releasing bionic marine antifouling coating according to claim 1, characterized in that: The hydrophilic amide monomer is selected from one of N-(2-hydroxyethyl) acrylamide, methacrylamide and dimethylaminopropyl acrylamide.

9. The topologically structured fouling-releasing bionic marine antifouling coating according to claim 1, characterized in that: The carboxyl curing agent is selected from one of 3-carboxypropyltriethoxysilane, 2-carboxypropylmethyldimethoxysilane, 2-(triethoxysilyl)acetic acid and 3-carboxypropyltrimethoxysilane.

10. The fouling-releasing bionic marine antifouling coating with a topological structure according to claim 1, characterized in that: The organic solvent is selected from one of ethanol, acetone and toluene.

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