Marine antifouling and antibacterial structure with adjustable release period and preparation process thereof

Abstract

The invention discloses a marine antifouling antibacterial structure with an adjustable release period and a preparation process thereof, and belongs to the technical field of marine antifouling structures. Comprising a nylon matrix, choline phosphate repellents and antibacterial agents are loaded in the nylon matrix in a soaking mode, and the choline phosphate repellents and the antibacterial agents form concentration gradient distribution in the nylon matrix to form nylon diffusion channels for releasing the repellents and the antibacterial agents; a nylon diffusion channel formed by a nylon matrix, a choline phosphate repellent and an antibacterial agent in a gradient distribution matching manner and an oil film distribution channel formed by an oil film layer construct a dual-channel synergistic slow-release system, and a dual-regulation mechanism of soaking duration and oil film layer thickness is combined; the release cycle of the choline phosphate repellent and the antibacterial agent is 120-1080 days, the 9-time wide range is precisely regulated and controlled, different antifouling requirements can be met, and the preparation process is simple and controllable; the choline phosphate repellent and the antibacterial agent do not release toxic and harmful substances, conform to marine environmental protection specifications and are good in environmental protection property.

Description

Technical Field

[0001] This invention relates to the field of marine antifouling structure technology, and in particular to a marine antifouling and antibacterial structure with adjustable release period and its preparation process. Background Technology

[0002] Marine antifouling technology is a core safeguard technology in marine engineering fields such as shipping, offshore oil and gas development, offshore wind power, and deep-sea equipment operation and maintenance. Its core function is to inhibit the attachment and growth of fouling organisms such as algae, shellfish, and marine microorganisms on the surface of marine equipment through physical barriers and biological repellency. This avoids problems caused by biofouling, such as increased flow resistance, accelerated structural corrosion, decreased equipment performance, and significantly increased operation and maintenance costs, thus ensuring the long-term, stable, and safe operation of marine equipment.

[0003] When using existing marine antifouling structures: Most existing marine antifouling structures adopt a single slow-release channel design. The release rate of the antifouling agent depends on the pore structure or degradation rate of the matrix. The release cycle is difficult to control precisely, making it difficult to meet the diverse needs of different sea areas, seasons, and ship types for the release cycle of antifouling agents, resulting in poor adaptability.

[0004] Therefore, a marine antifouling and antibacterial structure with an adjustable release period and its preparation process are provided to solve the problems mentioned above. Summary of the Invention

[0005] The purpose of this invention is to solve the problems mentioned in the background art, and to propose a marine antifouling and antibacterial structure with adjustable release period and its preparation process.

[0006] To achieve the above objectives, the present invention adopts the following technical solution: An adjustable release-cycle marine antifouling and antibacterial structure includes a nylon matrix. A choline phosphate repellent and an antibacterial agent are loaded within the nylon matrix via immersion. The choline phosphate repellent and antibacterial agent form a concentration gradient distribution within the nylon matrix, constituting a nylon diffusion channel for the release of the repellent and antibacterial agent. An oil film layer, comprising pentaerythritol ester and a complex lithium soap, covers the outer side of the nylon matrix, forming an oil film distribution channel for the release of the repellent and antibacterial agent. This oil film layer, superimposed with the nylon diffusion channels, forms a dual-channel slow-release system. The release cycle of the repellent and antibacterial agent can be freely adjusted by the immersion time and the oil film thickness, wherein the immersion time ranges from 4 to 24 hours, and the oil film thickness ranges from 0.2 to 0.8 mm.

[0007] To achieve precise adjustment of the release cycle, preferably, the nylon matrix is ​​a nylon series polymer material with water-absorbing characteristics; the loading depth and average concentration of choline phosphate repellent and antibacterial agent in the nylon matrix are both directly proportional to the immersion time; the diffusion resistance of the oil film layer is directly proportional to the oil film layer thickness, and the release rate of choline phosphate repellent and antibacterial agent is inversely proportional to the oil film layer thickness; the release cycle adjustment range of choline phosphate repellent and antibacterial agent is 120–1080 days, and the combination of immersion time and oil film layer thickness forms a release cycle adjustment range of 9 times.

[0008] To improve structural adaptability, preferably, the nylon matrix is ​​the body of a marine valve or marine pipe fitting, and the oil film layer covers the inner or outer wall of the valve or pipe fitting; the nylon matrix is ​​NC6 matrix material.

[0009] For the fabrication of the structure, preferably, the process includes cleaning and drying the nylon substrate surface, optional surface activation, immersion loading with a choline-phosphoric acid repellent and an antibacterial agent, and coating and curing an oil film layer. In the immersion loading step with the choline-phosphoric acid repellent and antibacterial agent, the choline-phosphoric acid aqueous solution has a mass percentage concentration of 10–20%, an immersion temperature of 25–30 degrees Celsius, and an immersion time of 4–24 hours. The oil film layer is coated using an airless spraying or dip coating process, with a target coating thickness of 0.2–0.8 mm. The curing process uses hot air or heating, and the curing time is positively correlated with the oil film layer thickness.

[0010] Compared with existing technologies, this invention provides a marine antifouling and antibacterial structure with adjustable release period and its preparation process, which has the following beneficial effects: By combining the gradient distribution of nylon matrix with choline phosphate repellent and antibacterial agent to form nylon diffusion channels and oil film distribution channels formed by oil film layer, a dual-channel synergistic slow-release system is constructed. Combined with the dual adjustment mechanism of immersion time and oil film layer thickness, the release period of choline phosphate repellent and antibacterial agent can be precisely controlled within a 9-fold wide range of 120-1080 days, which can be adapted to different antifouling needs. The preparation process is simple and controllable. The choline phosphate repellent and antibacterial agent do not release any toxic or harmful substances, comply with marine environmental protection regulations, and have good environmental performance. Attached Figure Description

[0011] Figure 1 This is a schematic diagram of the structure proposed in this invention; Figure 2 This is part A in the schematic diagram of the present invention.

[0012] In the diagram: 1. Nylon matrix; 2. Choline phosphate repellent; 3. Oil film layer. Detailed Implementation

[0013] The technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings of the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments.

[0014] Example 1

[0015] Reference Figure 1-2 A marine antifouling and antibacterial structure with adjustable release period includes a nylon matrix 1, a choline phosphate repellent 2, an antibacterial agent, and an oil film layer 3. The choline phosphate repellent 2 and the antibacterial agent are loaded into the nylon matrix 1 via immersion, forming a concentration gradient distribution within the nylon matrix 1, constituting nylon diffusion channels for repellent release. The molecular particle size of the choline phosphate repellent 2 and the antibacterial agent is smaller than the intermolecular gaps formed after the nylon matrix 1 absorbs water and swells, allowing for continuous diffusion and release through these channels, providing a basis for long-term sustained release. The oil film layer 3 covers the nylon matrix. On the outer side, pentaerythritol ester and complex lithium soap constitute the oil film distribution channel for repellent release. This channel overlaps with the nylon diffusion channel to form a dual-channel slow-release system. The surface oil film layer 3 serves as the slow-release layer for repellent release. The diffusion resistance of the repellent can be precisely controlled by its own thickness, achieving uniform and slow-release of the repellent and antibacterial agent and avoiding excessively rapid release in the initial stage. The release cycle of the repellent and antibacterial agent can be freely adjusted by the soaking time and the thickness of the oil film layer 3. The soaking time ranges from 4 to 24 hours, and the thickness of the oil film layer 3 ranges from 0.2 to 0.8 mm.

[0016] Nylon matrix 1 is a nylon material with water absorption characteristics. Nylon matrix 1 covers all nylon series polymer materials with water absorption characteristics. It can form internal channels through water absorption and swelling, which can allow repellent molecules and antibacterial agents to penetrate and diffuse. It can be directly used as the base material for marine valves and marine pipe fittings, realizing the integration of material and antifouling.

[0017] Choline phosphate repellent 2 and antibacterial agent are loaded into nylon matrix 1 by constant temperature immersion. Taking advantage of the water absorption and swelling properties of nylon matrix 1, choline phosphate repellent 2 and antibacterial agent molecules diffuse from the outer surface of the matrix to the inside, forming a concentration gradient distribution inside nylon matrix 1. This allows the repellent and antibacterial agent to be released over a long period of time, creating a concentration difference. The loading depth and average concentration of choline phosphate repellent 2 and antibacterial agent in nylon matrix 1 are directly proportional to the immersion time. The mass percentage concentration of choline phosphate aqueous solution is 10-20%, the immersion temperature is 25-30℃, and the immersion time is 4-24 hours.

[0018] The oil film layer 3 is uniformly coated and cured on the surface of the nylon substrate 1. The diffusion resistance of the oil film layer 3 is directly proportional to its thickness, while the release rates of the choline phosphate repellent 2 and the antibacterial agent are inversely proportional to the thickness of the oil film layer 3. The oil film layer 3 forms a synergistic effect with the concentration gradient of the substrate. The oil film layer 3 contains pentaerythritol ester, composite lithium soap, and antioxidant. The antioxidant is used to improve the adhesion, wear resistance, and anti-aging properties of the oil film layer 3. The coating process adopts airless spraying or dip coating, and the curing is carried out by hot air or heating. The curing time is positively correlated with the thickness of the oil film layer 3.

[0019] By combining the soaking time with the thickness of the oil film layer 3, the release cycle of the repellent and antibacterial agent can be adjusted within a range of 120–1080 days, and the combination of the two forms a release cycle adjustment range of 9 times.

[0020] A process for preparing a marine antifouling and antibacterial structure with an adjustable release period includes the following steps: 1. Cleaning and drying of nylon substrate 1: Clean the nylon substrate 1 to remove surface oil and impurities, and then dry it to ensure that there is no moisture residue on the substrate surface; 2. Optional surface activation: Depending on the requirements, the surface of the nylon matrix 1 can be activated after drying to improve the penetration efficiency of the matrix surface; 3. Choline-phosphate immersion loading: Prepare a choline-phosphate antibacterial aqueous solution of the corresponding concentration in advance, completely immerse the dried nylon matrix 1 in the solution, keep it at a constant temperature for the corresponding time, remove the matrix after immersion, rinse the surface liquid and air dry at room temperature. 4. Oil film coating and curing: Prepare the oil film coating according to the formula ratio, stir evenly, and apply it to the surface of the dried nylon substrate 1 using the corresponding process. Control the coating thickness to meet the design requirements. After coating, perform curing treatment and cool to room temperature to obtain a marine antifouling structure with adjustable release cycle.

[0021] During operation, the choline phosphate repellent 2 and the antibacterial agent rely on the concentration gradient inside the nylon matrix 1 to continuously diffuse through the nylon diffusion channels, and then release at a uniform speed into the seawater environment outside the matrix through the oil film distribution channels of the oil film layer 3. The oil film layer 3 precisely controls the diffusion resistance through its own thickness, and at the same time, in conjunction with the continuous concentration difference inside the matrix, it ensures the stable release of the repellent throughout the entire cycle, achieving a long-term and stable marine antifouling effect.

[0022] Example 2

[0023] Reference Figure 1-2A marine antifouling and antibacterial structure with adjustable release cycle and its preparation process are basically the same as in Example 1. However, the nylon matrix 1 is made of NC6 nylon material and is used as the body of the marine valve or marine pipe fitting to achieve the integration of material and antifouling. The oil film layer 3 is applied to the inner or outer wall of the valve or pipe fitting.

[0024] During operation, the NC6 nylon matrix 1 has excellent water absorption and swelling properties, which can achieve stable loading and diffusion of the repellent. The oil film layer 3 can be coated on the inner wall, outer wall or both sides simultaneously according to the actual working conditions.

[0025] Example 3

[0026] Reference Figure 1-2 A marine antifouling and antibacterial structure with adjustable release period and its preparation process are basically the same as those in Example 1, but with the following additional features: the maximum range of immersion time is 24 hours, and the maximum range of oil film layer 3 thickness is 0.8 mm, so as to meet the requirements of long-term antifouling.

[0027] The preparation process is basically the same as in Example 1, except that the soaking time and the thickness of the oil film coating are adjusted, and the curing time is extended accordingly as the thickness of the oil film layer 3 increases.

[0028] During operation, the thickness of the oil film layer 3 increases to the upper limit of the range, significantly increasing diffusion resistance and slowing down the release rate of repellents and antibacterial agents. The effective antifouling release cycle of repellents and antibacterial agents reaches 1080 days, achieving stable antifouling over a period of time and meeting the long-term antifouling needs of the deep sea.

[0029] Example 4

[0030] Reference Figure 1-2 A marine antifouling and antibacterial structure with adjustable release cycle and its preparation process are basically the same as those in Example 1, but with the following additional features: the lower limit of the immersion time is 4 hours, and the lower limit of the oil film layer 3 thickness is 0.2 mm, which is suitable for the antifouling requirements of short-term marine operation equipment.

[0031] The preparation process is basically the same as in Example 1, except that the oil film coating, curing parameters and soaking time are adjusted.

[0032] During operation, the soaking time is shortened to the lower limit of the range to meet the repellent load requirements for short-term antifouling. The thickness of the oil film layer 3 is reduced to the lower limit of the range, the diffusion resistance is reduced, the release rate of repellent and antibacterial agent is accelerated, and the effective antifouling release cycle of repellent and antibacterial agent is 120 days, which is suitable for the antifouling requirements of short-term marine operation equipment, shortens the preparation cycle and reduces raw material consumption.

[0033] A dual-channel synergistic sustained-release system is constructed by combining the gradient distribution of nylon matrix 1 with choline phosphate repellent 2 and antibacterial agent to form nylon diffusion channels and oil film distribution channels formed by oil film layer 3. Combined with the dual regulation mechanism of immersion time and oil film layer 3 thickness, the release cycle of choline phosphate repellent 2 and antibacterial agent can be precisely controlled within a 9-fold wide range of 120-1080 days, which can be adapted to different antifouling needs. The preparation process is simple and controllable. Choline phosphate repellent 2 and antibacterial agent do not release any toxic or harmful substances, comply with marine environmental protection regulations, and have good environmental performance.

[0034] The above description is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any equivalent substitutions or modifications made by those skilled in the art within the scope of the technology disclosed in the present invention, based on the technical solution and inventive concept of the present invention, should be covered within the scope of protection of the present invention.

Claims

1. A marine antifouling and antibacterial structure with adjustable release period, comprising a nylon matrix (1), characterized in that, The nylon matrix (1) is loaded with choline phosphate repellent (2) and antibacterial agent by immersion. The choline phosphate repellent (2) and antibacterial agent form a concentration gradient distribution inside the nylon matrix (1), which constitutes the nylon diffusion channel for the release of repellent and antibacterial agent. The outer side of the nylon matrix (1) is covered with an oil film layer (3). The oil film layer (3) contains pentaerythritol ester and complex lithium soap, which constitutes the oil film distribution channel for the release of repellent and antibacterial agent. It is superimposed with the nylon diffusion channel to form a dual-channel sustained-release system. The release cycle of repellent and antibacterial agent can be freely adjusted by the immersion time and the thickness of the oil film layer (3). The immersion time ranges from 4 to 24 hours, and the thickness of the oil film layer (3) ranges from 0.2 to 0.8 mm.

2. The marine antifouling and antibacterial structure with adjustable release period according to claim 1, characterized in that, The nylon matrix (1) is a nylon series polymer material with water absorption characteristics.

3. The marine antifouling and antibacterial structure with adjustable release period according to claim 1, characterized in that, The loading depth and average concentration of the choline phosphate repellent (2) and antibacterial agent in the nylon matrix (1) are both proportional to the soaking time.

4. The marine antifouling and antibacterial structure with adjustable release period according to claim 1, characterized in that, The diffusion resistance of the oil film layer (3) is directly proportional to the thickness of the oil film layer (3), while the release rates of the choline phosphate repellent (2) and the antibacterial agent are inversely proportional to the thickness of the oil film layer (3).

5. The marine antifouling and antibacterial structure with adjustable release period according to claim 1 and its preparation process, characterized in that, The release cycle adjustment range of the choline phosphate repellent (2) and the antibacterial agent is 120–1080 days, and the combination of the soaking time and the thickness of the oil film layer (3) forms a release cycle adjustment range of 9 times.

6. The marine antifouling and antibacterial structure with adjustable release period and its preparation process according to claim 2, characterized in that, The nylon matrix (1) is the body of the marine valve or marine pipe fitting, and the oil film layer (3) covers the inner or outer wall of the valve or pipe fitting.

7. The marine antifouling and antibacterial structure with adjustable release period according to claim 6 and its preparation process, characterized in that, The nylon matrix (1) is an NC6 matrix material.

8. The preparation process of a marine antifouling and antibacterial structure with adjustable release period according to claims 1-7, characterized in that, The steps are as follows: Nylon matrix (1) surface cleaning and drying, optional surface activation, choline phosphate repellent (2) and antibacterial agent immersion loading, oil film layer (3) coating and curing.

9. The preparation process of a marine antifouling and antibacterial structure with adjustable release period according to claim 8, characterized in that, In the choline phosphate repellent (2) and antibacterial agent soaking loading step, the choline phosphate aqueous solution has a mass percentage concentration of 10–20%, the soaking temperature is 25–30 degrees Celsius, and the soaking time is 4–24 hours.

10. The preparation process of a marine antifouling and antibacterial structure with adjustable release period according to claim 8, characterized in that, The oil film layer (3) is coated using an airless spraying or dip coating process, with a target coating thickness of 0.2–0.8 mm; the curing is performed using hot air or heating, and the curing time is positively correlated with the thickness of the oil film layer (3).

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