Intrinsic antifouling coating composition based on furan dioxime antibacterial crosslinker and application

Abstract

The application discloses an intrinsic antifouling coating composition based on furan dioxime antibacterial cross-linking agent and application. The intrinsic antifouling coating composition comprises an A component and a B component, the A component comprises a zwitterionic modified hydroxyl silicone oil, and the B component comprises a furan dioxime antibacterial cross-linking agent. After forming a coating, the organic silicon segment, the zwitterionic segment and the furan dioxime segment in the intrinsic antifouling coating composition can respectively endow the coating with dynamic antifouling performance, static antifouling performance and sterilization performance, meanwhile, the coating composition realizes intrinsic triple antifouling without any antifouling agent and related fillers, and is suitable for efficient antifouling of the surface of marine equipment.

Description

Technical Field

[0001] This invention belongs to the field of antifouling technology, specifically relating to an intrinsic antifouling coating composition based on furan dioxime antibacterial crosslinking agent and its application. Background Technology

[0002] Marine biofouling is currently one of the leading factors affecting ships and marine engineering equipment, causing significant economic losses to the ocean. Annually, the costs of transport delays, ship repair, maintenance, and cleaning due to the attachment and accumulation of marine microorganisms, flora, and fauna reach as high as $150 billion. Active antifouling strategies, such as applying antifouling coatings, are the simplest, most economical, and efficient way to address marine biofouling. However, the antifouling performance of most current antifouling coatings relies on antifouling agents with toxic properties, especially the widely used cuprous oxide and some zinc-containing antifouling agents. The release of these agents into seawater poses a significant risk and harm to the marine environment, ecological structure, and human health. Therefore, developing antifouling coatings with intrinsic antibacterial properties has become a crucial method for solving this problem. Furthermore, for stationary ships or engineering equipment in the ocean, the lack of high-speed water flow makes it difficult to remove fouling organisms adhering to the surface; therefore, it is necessary to improve the static defouling performance of the coating. Summary of the Invention

[0003] The main objective of this invention is to provide an intrinsic antifouling coating composition and its application based on furan dioxime antibacterial crosslinking agent, in order to overcome the shortcomings of the prior art.

[0004] To achieve the aforementioned objectives, the technical solution adopted by this invention includes:

[0005] This invention provides an intrinsic antifouling coating composition based on a furan dioxime antibacterial crosslinking agent, comprising component A and component B. Component A comprises zwitterionic modified hydroxyl silicone oil, and component B comprises a furan dioxime antibacterial crosslinking agent.

[0006] In some more specific embodiments, the zwitterionic modified hydroxyl silicone oil is selected from any one or a combination of two or more of the following structures:

[0007]

[0008] Wherein, n:m:p:q = 75~95:0.5~25:0.5~24.5:0.5~24.

[0009] In some more specific embodiments, the furan dioxime antibacterial crosslinking agent has a structure as shown in formula (I) and / or formula (II):

[0010]

[0011] This invention also provides an intrinsic antifouling coating, which is formed from the aforementioned intrinsic antifouling coating composition.

[0012] This invention also provides a method for preparing an intrinsic antifouling coating, comprising:

[0013] Provided the aforementioned intrinsic antifouling coating composition;

[0014] After mixing component A and component B of the intrinsic antifouling coating composition, the mixture is applied to the substrate surface by at least one of roller coating, brush coating or spray coating to form an intrinsic antifouling coating.

[0015] The present invention also provides the use of the aforementioned intrinsic antifouling coating composition or intrinsic antifouling coating in antifouling of marine equipment surfaces.

[0016] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0017] (1) Compared with traditional antifouling coatings, the intrinsic antifouling coating composition based on furan dioxime antibacterial crosslinking agent in this invention has intrinsic antifouling properties. The furan dioxime segments provided by the crosslinking agent can effectively kill the fouling organisms adhering to the surface.

[0018] (2) Compared with traditional antifouling coatings, the intrinsic antifouling coating composition based on furan dioxime antibacterial crosslinking agent in this invention has static decontamination performance, and achieves the removal of surface-adhered biofouling through the "hydration layer" formed by the zwitterionic chain segments provided by zwitterionic modified hydroxy silicone oil.

[0019] (3) Compared with traditional antifouling coatings, the intrinsic antifouling coating composition based on furan dioxime antibacterial crosslinking agent in this invention can impart dynamic defouling performance, static antifouling performance and bactericidal performance to the coating after the coating is formed by the organosilicon segment, zwitterionic segment and furan dioxime segment respectively. At the same time, the coating composition achieves intrinsic triple antifouling without the need for any antifouling agent and related filler, which is suitable for high-efficiency antifouling of marine equipment surfaces;

[0020] (4) Compared with traditional antifouling coatings, the intrinsic antifouling coating composition based on furan dioxime antibacterial crosslinking agent in this invention also has deep-sea pressure resistance and impermeability. Attached Figure Description

[0021] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments recorded in the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0022] Figure 1 This is the 1H NMR spectrum of the sulfobetaine-modified hydroxyl silicone oil in Example 1 of this invention;

[0023] Figures 2a-2k This is a graph showing the bactericidal performance of the coatings prepared from the samples in Comparative Examples 1-4 and Examples 1-7 of this invention. Detailed Implementation

[0024] In view of the deficiencies of the prior art, the inventors of this invention, through long-term research and extensive practice, have proposed the technical solution of this invention, which mainly involves crosslinking an amphoteric modified hydroxyl silicone oil component A with a furan dioxime antibacterial crosslinking agent component B to obtain an antifouling coating. The crosslinked coating acquires dynamic defouling properties through organosilicon segments, static antifouling properties through amphoteric segments, and bactericidal properties through furan dioxime segments, achieving intrinsic triple antifouling without the need for any antifouling agents or related fillers.

[0025] The technical solution of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0026] Specifically, as one aspect of the technical solution of the present invention, an intrinsic antifouling coating composition based on furan dioxime antibacterial crosslinking agent includes component A and component B, wherein component A includes zwitterionic modified hydroxyl silicone oil and component B includes furan dioxime antibacterial crosslinking agent.

[0027] In some preferred embodiments, the zwitterionic modified hydroxyl silicone oil is obtained by grafting zwitterionic compounds onto hydroxyl silicone oil.

[0028] Furthermore, the zwitterionic compound includes any one or a combination of two or more of sulfobetaine, carboxybetaine, and phosphorylcholine, but is not limited thereto.

[0029] Furthermore, the molecular weight of the hydroxyl silicone oil is 2000-20000 g / mol.

[0030] Furthermore, the zwitterionic modified hydroxyl silicone oil contains zwitterionic compound segments at a content of 2 wt% to 20 wt%.

[0031] Furthermore, the zwitterionic modified hydroxyl silicone oil is obtained by grafting the zwitterionic compound onto the hydroxyl silicone oil using at least one of free radical reaction, click chemistry reaction, and DA addition reaction.

[0032] Furthermore, the molar ratio of the zwitterionic compound to the hydroxyl silicone oil is 5–25:95–75.

[0033] In some preferred embodiments, the zwitterionic modified hydroxyl silicone oil is selected from any one or a combination of two or more of the following structures:

[0034]

[0035] Wherein, n:m:p:q = 75~95:0.5~25:0.5~24.5:0.5~24.

[0036] In some preferred embodiments, the furan dioxime antibacterial crosslinking agent has a structure as shown in formula (I) and / or formula (II):

[0037]

[0038]

[0039] In some preferred embodiments, the mass ratio of component A to component B is 10:0.5 to 10:1.5.

[0040] In some preferred embodiments, the intrinsic antifouling coating composition does not contain antifouling agents.

[0041] The intrinsic antifouling coating composition of this invention, after crosslinking, imparts dynamic defouling properties to the coating through organosilicon segments, static antifouling properties through zwitterionic segments, and bactericidal properties through furan dioxime segments. At the same time, this coating composition achieves intrinsic triple antifouling without the need for any antifouling agents and related fillers, making it suitable for highly efficient antifouling of marine equipment surfaces.

[0042] Another aspect of the present invention provides an intrinsic antifouling coating formed from the aforementioned intrinsic antifouling coating composition.

[0043] Another aspect of the present invention provides a method for preparing an intrinsic antifouling coating, comprising:

[0044] Provided the aforementioned intrinsic antifouling coating composition;

[0045] After mixing component A and component B of the intrinsic antifouling coating composition, the mixture is applied to the substrate surface by at least one of roller coating, brush coating or spray coating to form an intrinsic antifouling coating.

[0046] In some more specific embodiments, the method for preparing the intrinsic antifouling coating includes: uniformly mixing component A and component B in a certain proportion and then applying the mixture to an oil-free and dust-free solid surface by means of roller coating, brush coating, spraying, etc.

[0047] After the intrinsic antifouling coating composition of the present invention forms a coating, the organosilicon segments, zwitterionic segments and furan dioxime segments therein can respectively endow the coating with dynamic defouling properties, static antifouling properties and bactericidal properties. At the same time, the coating composition achieves intrinsic triple antifouling without the need for any antifouling agents and related fillers, making it suitable for highly efficient antifouling of marine equipment surfaces.

[0048] The intrinsic antifouling coating of this invention has excellent bactericidal effects against Escherichia coli, Pseudomonas, Vibrio, Achromobacterium, Flavobacterium, Spiril, Micrococcus, Micrococcus, Bacillus, Corynebacterium, Azotobacter, Nocardia, and Streptomyces.

[0049] Another aspect of the present invention provides the use of the aforementioned intrinsic antifouling coating composition or intrinsic antifouling coating in antifouling of marine equipment surfaces.

[0050] The technical solution of the present invention will be further described in detail below with reference to several preferred embodiments and accompanying drawings. This embodiment is implemented on the premise of the technical solution of the invention, and provides detailed implementation methods and specific operation processes. However, the protection scope of the present invention is not limited to the following embodiments.

[0051] Unless otherwise specified, the experimental materials used in the examples below can be purchased from conventional biochemical reagent companies.

[0052] Example 1

[0053] Preparation of antifouling coatings based on furan dioxime crosslinking agent and sulfobetaine modified hydroxyl silicone oil:

[0054] (1) The antifouling coating component A is sulfobetaine-modified hydroxy silicone oil, as shown in formula (1), and component B is furan dioxime antibacterial crosslinking agent, as shown in formula (2).

[0055] (2) 3g of vinyl-modified hydroxyl silicone oil was uniformly mixed with 0.3g of 3-dimethylamino-1-propanethiol and reacted at 60℃ for 24h. Then, 0.5g of 1,3-propylsulfonyl lactone was added dropwise to the system, and the reaction was carried out at room temperature for 24h to obtain sulfobetaine-modified hydroxyl silicone oil. The 1H NMR spectrum of the product is shown below. Figure 1 As shown.

[0056] (3) Mix component A and component B uniformly at a mass ratio of 10:1.

[0057] (4) Spray the coating onto the stainless steel plate to a thickness of 50μm.

[0058] (5) Dry the sprayed sample at room temperature for 1 hour.

[0059] (6) Conduct antibacterial tests on the samples.

[0060]

[0061] Example 2

[0062] Preparation of antifouling coatings based on furan dioxime crosslinking agents and carboxybetaine-modified hydroxyl silicone oil:

[0063] (1) The antifouling coating component A is carboxy betaine modified hydroxy silicone oil, as shown in formula (3), and component B is furan dioxime antibacterial crosslinking agent, as shown in formula (4).

[0064] (2) Mix 3g of vinyl-modified hydroxyl silicone oil with 0.3g of 3-dimethylamino-1-propanethiol and react at 60°C for 24h. Then add β-propiolactone dropwise to the system and react at room temperature for 24h to obtain carboxybetaine-modified hydroxyl silicone oil.

[0065] (3) Mix component A and component B uniformly at a mass ratio of 10:0.5.

[0066] (4) Spray the coating onto the stainless steel plate to a thickness of 50μm.

[0067] (5) Dry the sprayed sample at room temperature for 1 hour.

[0068] (6) Conduct antibacterial tests on the samples.

[0069]

[0070] Example 3

[0071] Preparation of antifouling coatings based on furan dioxime crosslinking agents and phosphorylated choline-modified hydroxyl silicone oil:

[0072] (1) The antifouling coating component A is phosphorylcholine modified hydroxy silicone oil, as shown in formula (5), and component B is furan dioxime antibacterial crosslinking agent, as shown in formula (6).

[0073] (2) Mix 3g of vinyl-modified hydroxy silicone oil with 0.3g of mercaptomethacryloyloxyethyl phosphocholine and react at 60°C for 24h to obtain phosphorylcholine-modified hydroxy silicone oil.

[0074] (3) Mix component A and component B uniformly at a mass ratio of 10:0.7.

[0075] (4) Spray the coating onto the stainless steel plate to a thickness of 50μm.

[0076] (5) Dry the sprayed sample at room temperature for 1 hour.

[0077] (6) Conduct antibacterial tests on the samples.

[0078]

[0079] Example 4

[0080] Preparation of antifouling coatings based on furan dioxime crosslinking agents and carboxybetaine / sulfobetaine / phosphorylcholine modified hydroxyl silicone oil:

[0081] (1) The antifouling coating component A is a carboxybetaine / sulfobetaine / phosphorylcholine modified hydroxy silicone oil, as shown in formula (7), and component B is a furan dioxime antibacterial crosslinking agent, as shown in formula (8).

[0082] (2) Mix 3g of vinyl-modified hydroxy silicone oil with 0.2g of 3-dimethylamino-1-propanethiol and 0.1g of mercaptomethacryloyloxyethyl phosphocholine uniformly and react at 60°C for 24h. Then add 0.3g of 1,3-propylsulfonyl lactone and 0.3g of β-propiolactone to the system and react at room temperature for 24h to obtain carboxybetaine / sulfobetaine / phosphocholine-modified hydroxy silicone oil.

[0083] (3) Mix component A and component B uniformly at a mass ratio of 10:1.2.

[0084] (4) Spray the coating onto the stainless steel plate to a thickness of 50μm.

[0085] (5) Dry the sprayed sample at room temperature for 1 hour.

[0086] (6) Conduct antibacterial tests on the samples.

[0087]

[0088] Example 5

[0089] Preparation of antifouling coatings based on furan dioxime crosslinking agents and carboxybetaine / sulfobetaine modified hydroxyl silicone oil:

[0090] (1) The antifouling coating component A is carboxybetaine / sulfobetaine modified hydroxy silicone oil, as shown in formula (9), and component B is furan dioxime antibacterial crosslinking agent, as shown in formula (10).

[0091] (2) Mix 3g of vinyl-modified hydroxyl silicone oil with 0.2g of 3-dimethylamino-1-propanethiol evenly and react at 60°C for 24h. Then add 0.3g of 1,3-propylsulfonyl lactone and 0.3g of β-propiolactone to the system and react at room temperature for 24h to obtain carboxybetaine / sulfobetaine modified polydimethylsiloxane.

[0092] (3) Mix component A and component B uniformly at a mass ratio of 10:1.

[0093] (4) Spray the coating onto the stainless steel plate to a thickness of 50μm.

[0094] (5) Dry the sprayed sample at room temperature for 1 hour.

[0095] (6) Conduct antibacterial tests on the samples.

[0096]

[0097] Example 6

[0098] Preparation of antifouling coatings based on furan dioxime crosslinking agent and sulfobetaine / phosphorylcholine modified hydroxyl silicone oil:

[0099] (1) The antifouling coating component A is sulfobetaine / phosphorylcholine modified hydroxy silicone oil, as shown in formula (11), and component B is furan dioxime antibacterial crosslinking agent, as shown in formula (12).

[0100] (2) Mix 3g of vinyl-modified hydroxy silicone oil with 0.2g of 3-dimethylamino-1-propanethiol and 0.3g of mercaptomethacryloyloxyethyl phosphocholine uniformly, react at 60°C for 24h, and then add 0.3g of 1,3-propylsulfonyl lactone dropwise to the system and react at room temperature for 24h to obtain sulfobetaine / phosphocholine-modified hydroxy silicone oil.

[0101] (3) Mix component A and component B uniformly at a mass ratio of 10:1.

[0102] (4) Spray the coating onto the stainless steel plate to a thickness of 50μm.

[0103] (5) Dry the sprayed sample at room temperature for 1 hour.

[0104] (6) Conduct antibacterial tests on the samples.

[0105]

[0106] Example 7

[0107] Preparation of antifouling coatings based on furan dioxime crosslinking agents and carboxybetaine / phosphatidylcholine modified hydroxyl silicone oil:

[0108] (1) The antifouling coating component A is carboxybetaine / phosphorylcholine modified hydroxy silicone oil, as shown in formula (13), and component B is furan dioxime antibacterial crosslinking agent, as shown in formula (14).

[0109] (2) Mix 3g of vinyl-modified hydroxy silicone oil with 0.2g of 3-dimethylamino-1-propanethiol and 0.3g of mercaptomethacryloyloxyethyl phosphocholine and react at 60°C for 24h. Then add 0.3g of β-propiolactone to the system and react at room temperature for 24h to obtain carboxybetaine / phosphocholine-modified hydroxy silicone oil.

[0110] (3) Mix components A and B uniformly at a mass ratio of 10:1.5.

[0111] (4) Spray the coating onto the stainless steel plate to a thickness of 50μm.

[0112] (5) Dry the sprayed sample at room temperature for 1 hour.

[0113] (6) Conduct antibacterial tests on the samples.

[0114]

[0115] Comparative Example 1

[0116] Preparation of antifouling coatings based on tetraethyl orthosilicate and hydroxyl silicone oil:

[0117] (1) The antifouling coating A component is hydroxyl silicone oil and B component is tetraethyl orthosilicate.

[0118] (2) Mix component A and component B uniformly at a mass ratio of 10:1.

[0119] (3) Spray the coating onto the stainless steel plate to a thickness of 50μm.

[0120] (4) Dry the sprayed sample at room temperature for 1 hour.

[0121] (5) Conduct antibacterial tests on the samples.

[0122] Comparative Example 2

[0123] Preparation of antifouling coatings based on methyltriacetoxysilane and hydroxyl silicone oil:

[0124] (1) The antifouling coating A component is hydroxy silicone oil and B component is methyltriacetoxysilane.

[0125] (2) Mix component A and component B uniformly at a mass ratio of 10:1.

[0126] (3) Spray the coating onto the stainless steel plate to a thickness of 50μm.

[0127] (4) Dry the sprayed sample at room temperature for 1 hour.

[0128] (5) Conduct antibacterial tests on the samples.

[0129] Comparative Example 3

[0130] Preparation of antifouling coatings based on furan dioxime crosslinking agents and hydroxyl silicone oil:

[0131] (1) The antifouling coating A component is hydroxyl silicone oil and B component is furan dioxime antibacterial crosslinking agent.

[0132] (2) Mix component A and component B uniformly at a mass ratio of 10:1.

[0133] (3) Spray the coating onto the stainless steel plate to a thickness of 50μm.

[0134] (4) Dry the sprayed sample at room temperature for 1 hour.

[0135] (5) Conduct antibacterial tests on the samples.

[0136] Comparative Example 4

[0137] Preparation of antifouling coatings based on aminopropyltriethoxysilane and sulfobetaine modified hydroxyl silicone oil:

[0138] (1) The antifouling coating component A is sulfobetaine-modified hydroxy silicone oil, and component B is aminopropyltriethoxysilane crosslinking agent.

[0139] (2) Mix component A and component B uniformly at a mass ratio of 10:1.

[0140] (3) Spray the coating onto the stainless steel plate to a thickness of 50μm.

[0141] (4) Dry the sprayed sample at room temperature for 1 hour.

[0142] (5) Conduct antibacterial tests on the samples.

[0143] The samples from Examples 1-7 and Comparative Examples 1-4 were prepared into coatings, and the antibacterial properties of the coating surface were tested according to the GB / T31402-2015 method to verify the intrinsic bactericidal properties of the coating.

[0144] like Figures 2a-2k As shown, compared to the coatings in Comparative Examples 1-4, the coatings in Examples 1-7 all have 100% sterilization (E. coli), which can effectively sterilize and prevent contamination.

[0145] In addition, the inventors of this case also conducted experiments with other raw materials, process operations, and process conditions described in this specification, referring to the aforementioned embodiments, and obtained relatively ideal results in all cases.

[0146] It should be understood that the technical solutions of the present invention are not limited to the specific embodiments described above. Any technical modifications made to the technical solutions of the present invention without departing from the spirit and scope of the claims are within the scope of protection of the present invention.

Claims

1. An intrinsic antifouling coating composition based on a furan dioxime antibacterial crosslinking agent, characterized in that, It includes component A and component B, wherein component A includes zwitterionic modified hydroxyl silicone oil and component B includes furan dioxime antibacterial crosslinking agent; The zwitterionic modified hydroxyl silicone oil is selected from any one or a combination of two or more of the following structures: ； Where, n:m:p:q = 75~95:0.5~25:0.5~24.5:0.5~24; The furan dioxime antibacterial crosslinking agent has a structure as shown in formula (I) and / or formula (II): ； Formula (I); ； Formula (II); The coating composition does not contain antifouling agents.

2. The intrinsic antifouling coating composition according to claim 1, characterized in that: The hydroxyl silicone oil used in the zwitterionic modified hydroxyl silicone oil has a molecular weight of 2000~20000 g / mol.

3. The intrinsic antifouling coating composition according to claim 1, characterized in that: The zwitterionic modified hydroxyl silicone oil contains zwitterionic compound segments ranging from 2 wt% to 20 wt%.

4. The intrinsic antifouling coating composition according to claim 1, characterized in that: The zwitterionic modified hydroxyl silicone oil is obtained by grafting a zwitterionic compound onto hydroxyl silicone oil using at least one of free radical reaction or click chemical reaction. The molar ratio of the zwitterionic compound to the hydroxyl silicone oil is 5~25:95~75.

5. The intrinsic antifouling coating composition according to claim 1, characterized in that: The mass ratio of component A to component B is 10:0.5 to 10:1.

5.

6. An intrinsic antifouling coating, characterized in that: The intrinsic antifouling coating is formed from the intrinsic antifouling coating composition according to any one of claims 1-5.

7. A method for preparing an intrinsic antifouling coating, characterized in that, include: Provide an intrinsic antifouling coating composition according to any one of claims 1-5; After mixing component A and component B of the intrinsic antifouling coating composition, the mixture is applied to the substrate surface by at least one of roller coating, brush coating or spray coating to form an intrinsic antifouling coating.

8. Use of the intrinsic antifouling coating composition of any one of claims 1-5 or the intrinsic antifouling coating of claim 6 in antifouling of marine equipment surfaces.

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