A capsaicin modified coating PE pipe

Abstract

The present invention belongs to the technical field of marine antifouling, and relates to a PE pipe coated with a capsaicin modified antifouling coating. The present invention provides a PE pipe coated with a capsaicin modified antifouling coating, comprising a polyethylene substrate and an antifouling coating coated on the surface of the polyethylene substrate, wherein the antifouling coating comprises waterproof paper printed with a capsaicin dot matrix and an eleostearic acid substance coated on the surface of the waterproof paper. The present invention prints a pungent capsaicin dot matrix on waterproof paper, coats the waterproof paper on the surface of a PE pipe, and then coats the eleostearic acid substance on the surface of the waterproof paper, thereby improving the hydrophobicity of the coating surface and the adhesion between the coating and the PE substrate, and achieving the effect of preventing marine organisms from attaching.

Description

Technical Field

[0001] The present invention relates to the technical field of marine antifouling, and more specifically, to a PE pipe coated with a capsaicin-modified antifouling coating, and a preparation method and application thereof. Background Art

[0002] HDPE is often used in pipes that form the main frame structure of marine aquaculture cages due to its excellent toughness, low price and easy processing. However, the substances secreted by marine shellfish and other organisms through the ducts are replaced by the water layer, then combined with the surface and solidified to achieve attachment to the underwater interface. The attached marine fouling will increase the load on the platform frame and reduce the service life of the aquaculture cage.

[0003] In the past few decades, major research results have been invested in the modification of HDPE, and more new antifouling coatings have been studied to improve the ability to prevent the attachment of marine shellfish. For example, tributyltin was grafted onto acrylate through an ester bond to prepare tin acrylate polymer, and then antifouling agents such as Cu2O were added to develop organic tin self-polishing (TBT-SPC) antifouling coatings. However, tributyltin accumulates in oysters, causing organopathic lesions and deformities in oysters, and Cu2O produces Cu 2+ It will cause great damage to the marine ecological environment and may even endanger human health. Researchers have also studied various methods for modifying the polarity of polyethylene, mainly aimed at introducing suitable polar sites into and on the polymer chain. For example, plasma modification, followed by alkoxy grafting to form a new surface containing polar functional groups, is used to increase the surface functional groups of polyethylene and improve their adhesion properties. HDPE is also modified by electron beam radiation cross-linking, which gives the polymer excellent processability and chemical resistance, but the antifouling effect is not obvious.

[0004] Therefore, the development of environmentally friendly, non-toxic or low-toxic antifouling coatings is the mainstream of future development. Natural products isolated and extracted from organisms are promising sources of antifouling agents. Compared with heavy metals, they are biodegradable, widely anti-fouling and low toxic, and will not pollute the environment. Summary of the invention

[0005] The primary purpose of the present invention is to overcome the shortcomings and deficiencies in the above-mentioned prior art and provide a PE pipe coated with a capsaicin modified anti-fouling layer.

[0006] Another object of the present invention is to provide a method for preparing the above-mentioned PE pipe.

[0007] Another object of the present invention is to provide application of the above PE pipe.

[0008] The above-mentioned object of the present invention is achieved by the following technical solutions:

[0009] The present invention protects a PE pipe coated with a capsaicin-modified antifouling coating, comprising a polyethylene substrate and an antifouling coating coated on the surface of the polyethylene substrate, wherein the antifouling coating comprises waterproof paper printed with a capsaicin dot matrix and tung oil acid substances coated on the surface of the waterproof paper.

[0010] The present invention prints irritating capsaicin dot matrix on waterproof paper, which, on the one hand, utilizes the irritation of capsaicin to achieve the expulsion of marine organisms, and on the other hand, makes the distribution of capsaicin on the waterproof paper more uniform, and also saves the amount of capsaicin. At the same time, the present invention coats a sufficient amount of eleostearic acid substances on the surface of waterproof paper, which, on the one hand, can improve the hydrophobicity of the coating, so that marine organisms are not easy to adhere to the surface of the coating; on the other hand, after the eleostearic acid substances are cured in the air, they can improve the adhesion between the coating and the PE substrate, and significantly improve the antifouling effect; in addition, the raw materials of the eleostearic acid substances are cheap and easy to obtain, and can quickly realize large-scale production and practical application.

[0011] Preferably, the number of layers of the waterproof paper is greater than or equal to 2.

[0012] Preferably, the waterproof paper is a nautical chart.

[0013] The present invention arranges more than two layers of waterproof paper in the antifouling coating, and realizes the long-term effectiveness of preventing the attachment of marine organisms by utilizing the form of the waterproof paper falling off layer by layer.

[0014] Preferably, the spacing between the capsaicin lattices is 1 to 100 μm.

[0015] In the marine environment, shellfish attached to marine aquaculture cages mainly include organisms such as barnacles. The arm span of the barnacle's byssus is about 100μm. Setting the spacing of the capsaicin dot matrix to less than 100μm can effectively prevent marine shellfish such as barnacles from attaching to the waterproof paper.

[0016] Preferably, every 100 cm 2 The surface of waterproof paper of area contains the following components by mass:

[0017] Ink 0.8~8.3g

[0018] Capsaicin 0.8~4.1g

[0019] Eleuropein acid substances: 74.4-82.6g.

[0020] Preferably, the mass of the ink is 4.1-8.3 g.

[0021] Preferably, the mass of the capsaicin is 2.5-4.1 g.

[0022] Preferably, the mass of the eleostearic acid substance is 78.5-82.6 g.

[0023] The amount of tung oil acid added will affect the anti-fouling coating. The smaller the amount, the less tung oil acid will be needed to completely cure the waterproof paper at the same curing temperature and curing time, causing the waterproof paper to fall off prematurely. The greater the amount, the more tung oil acid will remain after curing, resulting in poor anti-fouling effect of the PE pipe.

[0024] Preferably, the capsaicin is selected from one or more of trans-8-methyl-N-vanillyl-6-nonenamide, dihydrocapsaicin, nordihydrocapsaicin, homodihydrocapsaicin or homocapsaicin.

[0025] Preferably, the elaeuric acid-based substance is selected from one or more of α-elaeuric acid triglyceride, α-elaeuric acid or β-elaeuric acid.

[0026] The ink is a conventional printing ink that can make the printer work to print out patterns. The main components of the ink used in the present invention include blue-black ink, stabilizer, phenol, arsenic anhydride, glycerol, ethylene glycol, solvent and the like.

[0027] The pattern of the capsaicin dot matrix includes, but is not limited to, circular, rectangular, diamond, trapezoidal and other shapes.

[0028] The present invention further provides a method for preparing a PE pipe coated with a capsaicin-modified antifouling coating, comprising the following steps:

[0029] S1. Dissolve capsaicin in ink and print it on waterproof paper;

[0030] S2. The surface of the PE pipe is coated with the waterproof paper, and the surface of each layer of waterproof paper is coated with a tung oil acid substance, and cured in air to obtain the PE pipe.

[0031] Preferably, the number of layers of the wrapped waterproof paper is at least two.

[0032] Preferably, the curing is carried out at room temperature; the curing time is 12 to 36 hours, preferably 24 hours.

[0033] The present invention creatively prints capsaicin dot matrix on waterproof paper, utilizing the irritation of capsaicin to marine shellfish and the hydrophobicity of eleostearic acid substances, and achieves an anti-fouling effect by wrapping three layers of waterproof paper on the surface of HDPE and coating eleostearic acid substances and capsaicin, and using the gradual shedding of the waterproof paper to prevent marine organisms from adhering to its surface.

[0034] The present invention further protects the use of the above-mentioned PE pipe coated with the capsaicin modified antifouling coating in the preparation of marine antifouling pipes.

[0035] The present invention also protects the use of the PE pipe coated with the capsaicin-modified antifouling coating in preventing barnacle attachment.

[0036] Compared with the prior art, the present invention has the following beneficial effects:

[0037] 1. The present invention utilizes the irritating effect of capsaicin on marine shellfish, prints the irritating capsaicin dot matrix on waterproof paper, makes the capsaicin adhere to the surface of the waterproof paper, and then wraps the waterproof paper on the surface of the PE pipe to achieve the effect of preventing marine organisms from attaching.

[0038] 2. The present invention designs the spacing of the capsaicin lattice according to the arm span of the barnacle's byssus, thereby effectively preventing the barnacle from adhering to the surface of the antifouling coating.

[0039] 3. The present invention coats the surface of waterproof paper with eleostearic acid substances. On the one hand, the hydrophobic effect of eleostearic acid substances is utilized to prevent marine organisms from adhering to the surface of waterproof paper. On the other hand, the curing effect of eleostearic acid substances in the air can improve the adhesion between the coating and the PE substrate.

[0040] 4. The present invention coats the surface of the PE pipe with multiple layers of waterproof paper, and uses the waterproof paper to fall off layer by layer to prevent marine organisms from adhering to the surface, thereby achieving an anti-fouling effect. BRIEF DESCRIPTION OF THE DRAWINGS

[0041] Figure 1 This is a 40× microscope image of the surface of a PE pipe having a capsaicin-modified antifouling coating prepared in Example 1 of the present invention.

[0042] Figure 2 This is an infrared spectrum of the navigation paper, capsaicin, eleostearic acid substances and capsaicin-modified antifouling coating prepared in Example 2 of the present invention.

[0043] Figure 3 This is an energy dispersive spectrum (EDS) diagram of the capsaicin-modified antifouling coating prepared in Example 3 of the present invention.

[0044] Figure 4 The PE pipe coated with the capsaicin modified antifouling coating and the HDPE pipe without the coating prepared in Example 1 of the present invention are in the state of being immersed in real sea. DETAILED DESCRIPTION

[0045] In order to more clearly and completely describe the technical solution of the present invention, the present invention is further described in detail through specific embodiments below. It should be understood that the specific embodiments described herein are only used to explain the present invention, and are not used to limit the present invention. Various changes can be made within the scope of the rights of the present invention.

[0046] Example 1

[0047] A PE pipe coated with a capsaicin-modified antifouling coating, comprising a polyethylene substrate and an antifouling coating coated on the surface of the polyethylene substrate, wherein the antifouling coating comprises waterproof paper printed with a capsaicin dot matrix and an eleostearic acid substance coated on the surface of the waterproof paper;

[0048] The number of layers of the waterproof paper is 3;

[0049] The waterproof paper is a marine navigation drawing;

[0050] The spacing of the capsaicin lattice is 60 μm;

[0051] Every 100cm 2 The surface of the waterproof paper contains the following components by mass:

[0052] Ink 8.3g;

[0053] Capsaicin 4.1g;

[0054] Eleuropein acid substances 82.6g;

[0055] The capsaicin is trans-8-methyl-N-vanillyl-6-nonenamide;

[0056] The eleostearic acid substance is α-eleostearic acid triglyceride.

[0057] The preparation method of the above PE pipe comprises the following steps:

[0058] S1. Dissolve 5g of capsaicin in 10g of ink, set the dot pattern, and print the capsaicin dot matrix to an area of ​​121cm 2 On the navigation drawings;

[0059] S2. The surface of the HDPE pipe is coated with three layers of the HNA blueprint, 100 g of eleostearic acid is applied on the surface of the HNA blueprint, and the mixture is cured for 24 hours in an outdoor environment at room temperature to obtain the PE pipe.

[0060] Example 2

[0061] A PE pipe coated with a capsaicin modified antifouling coating, which differs from Example 1 only in that: every 100cm 2 The surface area of ​​the waterproof paper contains 2.5g of capsaicin.

[0062] Example 3

[0063] A PE pipe coated with a capsaicin modified antifouling coating, which differs from Example 1 only in that: every 100cm 2 The surface of the waterproof paper contains 74.3 g of eleostearic acid substances.

[0064] Example 4

[0065] A PE pipe coated with a capsaicin-modified antifouling coating, which is different from Example 1 only in that the capsaicin is dihydrocapsaicin.

[0066] Example 5

[0067] A PE pipe coated with a capsaicin-modified antifouling coating, which is different from Example 1 only in that the capsaicin is high capsaicin.

[0068] Example 6

[0069] A PE pipe coated with a capsaicin-modified antifouling coating, which is different from Example 1 only in that the eleostearic acid substance is α-eleostearic acid.

[0070] Example 7

[0071] A PE pipe coated with a capsaicin-modified antifouling coating, which is different from Example 1 only in that the eleostearic acid substance is β-eleostearic acid.

[0072] Comparative Example 1

[0073] A PE pipe coated with a capsaicin modified antifouling coating, which differs from Example 1 only in that: every 100cm 2 The surface area of ​​the waterproof paper contains 0.4g of capsaicin.

[0074] Comparative Example 2

[0075] A PE pipe coated with a capsaicin modified antifouling coating, which differs from Example 1 only in that: every 100cm 2 The surface of the waterproof paper contains 49.6 g of eleostearic acid substances.

[0076] Comparative Example 3

[0077] A PE pipe coated with a capsaicin modified antifouling coating, which differs from Example 1 only in that: every 100cm 2 The surface of the waterproof paper contains 99.2g of eleostearic acid substances.

[0078] Performance Testing

[0079] 1. Characterization of properties

[0080] Figure 1 This is the HNA drawing printed with capsaicin dot matrix prepared in Example 1. Figure 1 As shown, the pattern distance of the dot matrix is ​​less than 100 μm, and the arm span of the barnacle's byssus is about 100 μm, so the barnacle's byssus cannot adhere to the coating surface. It can be seen that the PE pipe prepared in Example 1 can effectively prevent marine shellfish such as barnacles from adhering to the PE pipe coating, which is beneficial to protecting the HDPE marine aquaculture cages.

[0081] Figure 2 This is the infrared spectrum of the antifouling coating on PE pipes prepared in Example 2. Figure 2 As shown, the stretching vibration peak of the NH bond on the NHCO group of trans-8-methyl-N-vanillyl-6-nonenamide is located at 3279 cm -1 , the -CH 2- , and the CH bond of -CH3 is located at 2926cm -1 、2855cm -1 The stretching peak of the COC bond of the methoxy group connected to the benzene ring is located at 1035 cm -1 and 1276cm -1 .1643cm -1 It is the stretching vibration peak of C=C on α-eleostearic acid triglyceride, 993cm -1 and 735cm -1 These are the bending vibration peaks of the cis- and trans-unsaturated CH in the α-eleostearic acid triglyceride molecule. -1 It is the stretching vibration peak of -OH of paper wood fiber.

[0082] From the above, it can be seen that trans-8-methyl-N-vanillyl-6-nonenamide is dissolved in the ink and printed on the surface of the drawing, adhering to the surface of the coating, and α-eleostearic acid triglyceride is also immersed in the drawing, which also provides a certain basis for the subsequent anti-fouling effect.

[0083] Figure 3 1 is the EDS spectrum of the PE pipe antifouling coating prepared in Example 3, and Table 1 is the element composition of the PE pipe antifouling coating prepared in Example 3. Figure 3 It can be concluded from Table 1 that the common element C in trans-8-methyl-N-vanillyl-6-nonenamide, α-tungoleic acid triglyceride and drawing materials accounts for 11.4% by mass, followed by element O, which accounts for 2.3% by mass. Element N is a unique element of trans-8-methyl-N-vanillyl-6-nonenamide in the three materials, and its mass fraction accounts for 0.5%, indicating that trans-8-methyl-N-vanillyl-6-nonenamide dissolves into the paper and forms an antifouling coating after curing with α-tungoleic acid triglyceride, which is beneficial to the antifouling effect of the coating on HDPE.

[0084] Table 1 Composition of various elements

[0085]

[0086] 2. Marine antifouling performance

[0087] The PE pipe prepared in Example 1 and the HDPE without antifouling coating were immersed in seawater with a depth of 1 to 2 meters for 90 days. Figure 4 As shown, after HDPE was immersed in the marine environment for 30 days, a small amount of barnacles attached to the surface; and after immersion for 90 days, the biological attachment area of ​​the HDPE surface was 10-15%, showing a more serious degree of pollution, which may be due to the strong adhesion of the biological adhesive secreted by the barnacles to the coating surface. However, after immersion in the marine environment for 30 days, the capsaicin-modified antifouling coating of the PE pipe prepared in Example 1 had almost no shellfish attached to the capsaicin-modified coating, but a small amount of aqueous solution entered the next coating from the gap between the coatings. After immersion for 90 days, the biological attachment area of ​​the capsaicin-modified antifouling coating of the PE pipe was 1-3%, indicating that capsaicin has the effect of irritation and the layer-by-layer shedding of the coating, which reduces the attachment of marine organisms to the surface. The effects of other embodiments are similar to those of Example 1.

[0088] It can be seen from Table 2 that the amount of biological attachment area in the hanging plate of the PE pipe with capsaicin modified antifouling coating obtained in Comparative Example 1 is higher than that in Example 1, and the effect is much lower than that in Example 1, indicating that the amount of capsaicin is small, resulting in a small amount of capsaicin in the coating that is insufficient to prevent the attachment of marine shellfish.

[0089] As can be seen from Table 2, the amount of biological attachment area in the hanging board of the PE pipe with capsaicin modified antifouling coating obtained in Comparative Example 2 is higher than that in Example 1, and the effect is much lower than that in Example 1, indicating that the amount of eleostearic acid substances is small. At the same curing temperature and curing time, eleostearic acid substances are not enough to completely cure the drawings, resulting in premature shedding of the drawings and marine organisms attaching to the surface of the pipe.

[0090] As can be seen from Table 2, the amount of biological attachment area in the hanging plate of the PE pipe with capsaicin modified antifouling coating obtained in Comparative Example 3 in seawater is higher than that in Example 1, and the effect is much lower than that in Example 1, indicating that the amount of eleostearic acid substances is large, resulting in excessive amount of residual eleostearic acid substances after curing, and the antifouling effect of the plastic pipe is not good.

[0091] Table 2 Biological attachment area of ​​each comparative example

[0092]

[0093] Obviously, the above embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. For those skilled in the art, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to list all the embodiments here. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the protection scope of the claims of the present invention.

Claims

1. A PE pipe coated with a capsaicin-modified antifouling coating, comprising a polyethylene substrate and an antifouling coating coated on the surface of the polyethylene substrate, characterized in that: The antifouling coating comprises waterproof paper printed with a capsaicin dot matrix and an eleostearic acid substance coated on the surface of the waterproof paper; Wherein, the spacing of the capsaicin lattice is 1 to 100 μm; The mass of the capsaicin is 2.5 to 4.1 g; The mass of the eleostearic acid substance is 4.1-8.3 g.

2. The PE pipe according to claim 1, characterized in that: The number of layers of the waterproof paper is greater than or equal to 2.

3. The PE pipe according to claim 1, characterized in that: Every 100cm 2 The surface of waterproof paper of area contains the following components by mass: Ink 0.8~8.3g Capsaicin 0.8~4.1g Eleuropein acid substances: 74.4-82.6g.

4. The PE pipe according to any one of claims 1 to 3, characterized in that: The capsaicin is selected from one or more of trans-8-methyl-N-vanillyl-6-nonenamide, dihydrocapsaicin, nordihydrocapsaicin, homodihydrocapsaicin or homocapsaicin.

5. The PE pipe according to any one of claims 1 to 3, characterized in that: The eleostearic acid substance is selected from one or more of α-eleostearic acid triglyceride, α-eleostearic acid or β-eleostearic acid.

6. A method for preparing a PE pipe coated with a capsaicin-modified antifouling coating, comprising the following steps: S1. Dissolve capsaicin in ink and print it on waterproof paper; S2. The surface of the PE pipe is coated with the waterproof paper, and the surface of each layer of waterproof paper is coated with a tung oil acid substance, and cured in air to obtain the PE pipe.

7. Use of the PE pipe coated with the capsaicin modified antifouling coating according to any one of claims 1 to 5 in the preparation of marine antifouling pipes.

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