Antifouling composite material and preparation method and application thereof

Abstract

The application provides an antifouling composite material and a preparation method and application thereof. The antifouling composite material is prepared from 100 parts by weight of a polymer matrix and 1-100 parts by weight of a slow-release filler, wherein the polymer matrix is a polyurethane with a main chain capable of being degraded into non-toxic small molecules, and the slow-release filler is halloysite nanotubes loaded with an antifouling agent. The polyurethane of the application can be continuously degraded into non-toxic small molecules, and the slow-release filler can release the antifouling agent for a long time, and the combination of the two guarantees the continuous dynamic updating of the surface of the composite material and excellent dynamic / static long-term antifouling performance. The antifouling composite material provided by the application can be coated on the surface of marine engineering equipment to form a long-term protection circle around the marine engineering equipment and prevent marine organisms from adhering or growing on the surface of the equipment.

Description

Technical Field

[0001] This invention relates to the field of functional composite materials, and more specifically, to an antifouling composite material, its preparation method, and its application. Background Technology

[0002] Marine biofouling refers to the biological scale formed by the adsorption, growth, and reproduction of marine microorganisms, plants, and animals on the surface of objects submerged in seawater. It can cause significant damage to marine engineering equipment such as ships, nuclear power plants, and oil platforms. Without protective measures, a large amount of fouling can accumulate on the bottom of a ship in a short period of time, reducing the ship's speed, increasing fuel consumption, shortening the hull's lifespan, and resulting in substantial economic losses in subsequent maintenance.

[0003] Marine antifouling utilizes physical or chemical methods to prevent marine organisms from attaching and growing on object surfaces, or to detach them. Traditional antifouling coatings kill marine life by releasing toxic materials such as tin, mercury, and lead. Studies have found that heavy metals accumulate over time in various fish, shellfish, and marine plants, leading to genetic mutations and entering the food chain, causing incalculable ecological problems. Therefore, developing green and efficient antifouling materials that do not contain heavy metals is of significant practical importance.

[0004] Existing self-polishing antifouling materials rely on shearing and tearing forces for degradation, requiring seawater scouring to achieve surface self-polishing and remove fouling substances, thus providing an antifouling effect. This is unfavorable for facilities fixed in seawater. Furthermore, the degradation primarily involves the hydrolysis of side groups, producing small molecules, while the main chain, being non-degradable, persists in the ocean long-term, causing microplastic pollution. To achieve better antifouling performance, antifouling agents are typically compounded, but these agents are usually directly physical blended with the matrix, migrating to the coating surface and being released within a short time, significantly reducing the antifouling effect. Therefore, there is a need to develop an environmentally friendly and long-lasting marine antifouling material. Summary of the Invention

[0005] To address the aforementioned problems, this invention provides an antifouling composite material, its preparation method, and its applications. This invention utilizes biodegradable polyurethane material and slow-release fillers to prepare the antifouling composite material. The polyurethane continuously degrades into non-toxic small molecules, while the slow-release filler provides a long-lasting release of the antifouling agent. The combination of these two elements ensures both continuous dynamic renewal of the composite material's surface and excellent dynamic / static long-term antifouling performance. The antifouling composite material provided by this invention can be coated onto the surface of marine engineering equipment, forming a long-lasting protective ring around the equipment to prevent marine organisms from attaching to or growing on the equipment's surface.

[0006] Firstly, one of the objectives of this invention is to provide a stain-resistant composite material.

[0007] The antifouling composite material is prepared from raw materials comprising the following components, which are in parts by weight:

[0008] 100 parts by weight of polymer matrix, wherein the polymer matrix is ​​a polyurethane polymer whose main chain can be degraded into non-toxic small molecules, preferably one of polycaprolactone type polyurethane, polylactic acid type polyurethane, and polycarbonate type polyurethane.

[0009] The slow-release filler is 1 to 100 parts by weight, preferably 1 to 60 parts by weight. The slow-release filler is halloysite nanotubes loaded with an antifouling agent. Preferably, the antifouling agent is selected from maleimide, isothiazolinone, and capsaicin antifouling agents.

[0010] Furthermore, the polymer matrix is ​​prepared by the following method:

[0011] Polyester polyol, diisocyanate and catalyst are mixed and reacted to obtain a prepolymer, and then a chain extender is added to react to obtain a biodegradable polymer matrix.

[0012] Specifically, the following steps can be taken:

[0013] Polyester polyol was dehydrated under vacuum at 115°C, then cooled to 80°C. Diisocyanate and catalyst were added under normal pressure and nitrogen atmosphere. After reacting for a period of time, a prepolymer was obtained. A chain extender was added to continue the reaction. After the reaction was completed, the product was placed in a vacuum oven for curing. The curing temperature was controlled at 80-110°C to obtain a biodegradable polyurethane matrix.

[0014] Preferably, the polyester polyol is one of polycaprolactone diol, polypropylene carbonate diol, and poly-L-lactide diol; the diisocyanate is one of isophorone diisocyanate, hexamethylene diisocyanate, and 4,4'-dicyclohexylmethane diisocyanate; the catalyst is one of dimethylcyclohexylamine and dibutyltin dilaurate; and the chain extender is one of 1,4-butanediol, 1,6-hexanediol, and ethylene glycol.

[0015] Furthermore, halloysite nanotubes loaded with antifouling agents were prepared by the following method:

[0016] Step 1: Place halloysite nanotubes in a muffle furnace and treat them at a high temperature of 120–1000℃ for 1–3 hours;

[0017] Step 2: Dissolve the antifouling agent in a solvent to prepare an antifouling agent solution with a concentration of 10-150 g / L, wherein the solvent is selected from ethanol or xylene;

[0018] Step 3: Add the halloysite nanotubes treated in Step 1 to the antifouling agent solution prepared in Step 2 to form a suspension. Disperse the suspension by ultrasonication to make the concentration of halloysite in the suspension 5-300 g / L.

[0019] Step 4: Using the vacuum loading method, the suspension prepared in Step 3 is circulated and stirred 3-5 times under vacuum / normal pressure, followed by centrifugation, washing, drying, and grinding to obtain halloysite nanotubes loaded with antifouling agent. The vacuum pressure is -0.095 to -0.01 MPa, the centrifugation speed is 5000-8000 r / min, and the drying temperature is 60-80℃.

[0020] Halloysite exists in nature as hollow nanotubes, and its lumens can be loaded with functional agents. However, the proportion of functional agents loaded with hollow tubular fillers in composite materials is lower than that of granular fillers. Currently, the main methods for preparing halloysite loaded with functional agents are vacuum adsorption (without stirring during preparation) or simple stirring adsorption. These methods result in uneven loading and poor loading effects. To achieve good functional agent loading effects with halloysite, this invention first disperses the halloysite nanotubes using ultrasound before loading, and then uses a method of circulating under vacuum / normal pressure while mechanically stirring to achieve better dispersion during loading. Thermogravimetric analysis results show that the halloysite nanotubes loaded with antifouling agents in this invention have good loading effects, and the theoretical loading rate can be achieved by adjusting the raw material ratio.

[0021] Secondly, one of the objectives of this invention is to provide a method for preparing the antifouling composite material, which is one of the objectives of this invention.

[0022] Includes the following steps:

[0023] Antifouling composite material is prepared by blending polymer matrix and slow-release filler in the required amounts.

[0024] Specifically, the following steps can be taken:

[0025] The polymer matrix and slow-release filler are mixed at 150°C using a Hacker mixer and then hot-pressed to obtain an antifouling composite material.

[0026] Furthermore, a third objective of this invention is to provide the application of the antifouling composite material, which is one of the objectives of this invention, in marine engineering equipment.

[0027] The antifouling composite material provided by this invention can be coated on the surface of marine engineering equipment to form a long-lasting protective ring around the equipment, preventing marine organisms from attaching to or growing on the surface of the equipment.

[0028] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0029] 1. The antifouling composite material provided by this invention is a green, environmentally friendly, and slow-release composite material. It does not contain heavy metals, and the matrix can be degraded into non-toxic small molecules, which does not pollute the marine environment. Moreover, the degradation of the matrix does not depend on the scouring of strong water flow, and can achieve antifouling in static waters.

[0030] 2. The antifouling composite material provided by this invention solves the problem of early release of antifouling agent, prolongs the action time of antifouling agent, requires less antifouling agent, and has a longer antifouling time.

[0031] 3. The antifouling composite material provided by this invention has a polymer matrix backbone that can be degraded into non-toxic small molecules, enabling dynamic / static surface self-renewal. The slow-release filler can extend the release time of the antifouling agent, thus constructing an eco-friendly antifouling system with excellent dynamic / static long-term antifouling capabilities. Furthermore, this invention combines the slow-release filler with the degradable matrix to achieve a combination of dynamic surface removal and slow-release antifouling agent antifouling strategies, enabling the antifouling composite material to achieve better antifouling effects.

[0032] 4. The antifouling composite material provided by the present invention uses halloysite nanotubes treated at high temperature as the matrix. The antifouling agent is loaded into the halloysite tube cavity by vacuum loading and stirring. Finally, the halloysite nanotubes loaded with antifouling agent are combined with a biodegradable polymer matrix to give the antifouling composite material good mechanical properties.

[0033] 5. The antifouling composite material preparation method provided by the present invention uses readily available raw materials and has a simple and easy-to-implement process, and has broad application potential. Attached Figure Description

[0034] Figure 1 The static hydrolysis curves are those of the biodegradable polycaprolactone polyurethane matrix prepared in Examples 1-4 of this invention.

[0035] Figure 2 Thermogravimetric analysis curves for antifouling agent (TCPM) and halloysite (HNTs);

[0036] Figure 3 Thermogravimetric analysis curves of halloysite nanotubes loaded with antifouling agents prepared in Examples 7-9 of this invention;

[0037] Figure 4 Antifouling agent release curves of halloysite nanotubes (HNTs-TCPM) loaded with antifouling agent prepared in Example 8 of the present invention in different solvents;

[0038] Figure 5 SEM(a) and TEM(b) images of the antifouling composite material prepared in Example 12 of the present invention;

[0039] Figure 6The antifouling agent release curves of the antifouling composite material (PCLU / HNTs-TCPM) prepared in Example 12 of the present invention and the composite material (PCLU / TCPM) prepared in Comparative Example 1 are shown.

[0040] Figure 7 The images are SEM images of the composite materials prepared in Examples 12, 13, Comparative Example 1 and Comparative Example 2 after being suspended in a culture medium of Vibrio natans for three days. Among them, (a) corresponds to the SEM image of Example 13, (b) corresponds to the SEM image of Comparative Example 2, (c) corresponds to the SEM image of Comparative Example 1, and (d) corresponds to the SEM image of Example 12.

[0041] Figure 8 The images are SEM images of the surfaces of the composite materials prepared in Example 12 and Comparative Example 1 after being placed in artificial seawater for 60 days. (a) corresponds to the SEM image of Comparative Example 1 and (b) corresponds to the SEM image of Example 12. Detailed Implementation

[0042] The present invention will now be described in detail with reference to the accompanying drawings and embodiments. It should be noted that the following embodiments are only used to further illustrate the present invention and should not be construed as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made by those skilled in the art based on the content of the present invention are still within the scope of protection of the present invention.

[0043] Sources and types of raw materials used in the examples:

[0044]

[0045]

[0046] Example 1

[0047] This example illustrates the preparation of a polycaprolactone polyurethane polymer matrix.

[0048] 30g of polycaprolactone diol was dehydrated under vacuum at 115℃, then cooled to 80℃. 19.7g of hexamethylene diisocyanate and 0.0149g of dibutyltin dilaurate were added under normal pressure and a nitrogen atmosphere. After reacting for a period of time, a prepolymer was obtained. 5.41g of 1,4-butanediol was added to continue the reaction. After the reaction was completed, the product was placed in a vacuum oven at 90℃ to cure, resulting in a biodegradable polycaprolactone polyurethane polymer matrix, abbreviated as PCLU-54.

[0049] Example 2

[0050] This example illustrates the preparation of a polycaprolactone polyurethane polymer matrix.

[0051] 30g of polycaprolactone diol was dehydrated under vacuum at 115℃, then cooled to 80℃. 11.2g of hexamethylene diisocyanate and 0.0124g of dibutyltin dilaurate were added under normal pressure and a nitrogen atmosphere. After reacting for a period of time, a prepolymer was obtained. 2.51g of 1,4-butanediol was added to continue the reaction. After the reaction was completed, the product was placed in a vacuum oven at 90℃ to cure, resulting in a biodegradable polycaprolactone polyurethane polymer matrix, abbreviated as PCLU-68.

[0052] Example 3

[0053] This example illustrates the preparation of a polycaprolactone polyurethane polymer matrix.

[0054] 30g of polycaprolactone diol was dehydrated under vacuum at 115℃, then cooled to 80℃. 7.87g of hexamethylene diisocyanate and 0.0114g of dibutyltin dilaurate were added under normal pressure and a nitrogen atmosphere. After reacting for a period of time, a prepolymer was obtained. 1.35g of 1,4-butanediol was added to continue the reaction. After the reaction was completed, the product was placed in a vacuum oven at 90℃ to cure, resulting in a biodegradable polycaprolactone polyurethane polymer matrix, abbreviated as PCLU-74.

[0055] Example 4

[0056] This example illustrates the preparation of a polycaprolactone polyurethane polymer matrix.

[0057] 30g of polycaprolactone diol was dehydrated under vacuum at 115℃, then cooled to 80℃. 4.92g of hexamethylene diisocyanate and 0.0105g of dibutyltin dilaurate were added under normal pressure and a nitrogen atmosphere. After reacting for a period of time, a prepolymer was obtained. 0.338g of 1,4-butanediol was added to continue the reaction. After the reaction was completed, the product was placed in a vacuum oven at 90℃ to cure, resulting in a biodegradable polycaprolactone polyurethane polymer matrix, abbreviated as PCLU-85.

[0058] Figure 1 The static hydrolysis curves are for the biodegradable polycaprolactone polyurethane matrix prepared in Examples 1-4 above.

[0059] As shown in the figure, the polycaprolactone-type polyurethane (PCLU) prepared in Examples 1-4 all exhibit degradability. When used as a matrix for composite materials, they can achieve dynamic surface self-renewal to remove surface contaminants. Furthermore, the figure shows that the degradation rate varies depending on the soft segment content in the polymer matrix. The polycaprolactone-type polyurethane (PCLU-74) prepared in Example 3 has the fastest hydrolysis rate, while the polycaprolactone polyurethane (PCLU-68) prepared in Example 2 has a slightly lower hydrolysis rate. The polycaprolactone polyurethanes prepared in Examples 1 and 4 have the slowest hydrolysis rates. This is because, on the one hand, increasing the polycaprolactone (PCL) content increases the crystallinity of the polymer (PCLU), weakening its hydrolytic ability; on the other hand, increasing the polycaprolactone (PCL) content increases the number of hydrolyzable ester groups, enhancing its hydrolytic ability. These two factors result in the polymer (PCLU-74) prepared in Example 3 having the fastest hydrolysis rate. Based on the figure, it is speculated that the polymer (PCLU-74) prepared in Example 3 requires at least three years to completely degrade.

[0060] Example 5

[0061] This example illustrates the preparation of a polylactic acid polyurethane polymer matrix (PLLAU).

[0062] The preparation method of this embodiment is basically the same as that of Example 3. The difference is that the soft segment used in this embodiment is poly-L-lactide diol, the isocyanate is hexamethylene diisocyanate, the chain extender is ethylene glycol, and the catalyst is dimethylcyclohexylamine.

[0063] Example 6

[0064] This example illustrates the preparation of a polypropylene carbonate (PPCU) polymer matrix.

[0065] The preparation method of this embodiment is basically the same as that of Example 3. The difference is that the soft segment used in this embodiment is polypropylene carbonate diol, the isocyanate is isophorone diisocyanate, and the chain extender is 1,6-hexanediol.

[0066] Example 7

[0067] This embodiment illustrates the preparation of halloysite nanotubes loaded with N-(2,4,6-trichlorophenyl)maleimide antifouling agent.

[0068] Halloysite nanotubes were placed in a muffle furnace and treated at 550℃ for 3 hours. The antifouling agent N-(2,4,6-trichlorophenyl)maleimide (TCPM) was dissolved in ethanol to prepare an antifouling agent solution with a concentration of 25 g / L. The treated halloysite nanotubes were added to the antifouling agent solution to form a suspension. The suspension was dispersed in an ultrasonic bath, with a halloysite concentration of 50 g / L. A vacuum loading method was used, with a vacuum loading pressure of -0.01 MPa. The suspension was circulated and stirred three times under vacuum / atmospheric pressure. After completion, the suspension was centrifuged at 8000 r / min, washed, dried at 70℃, and ground to obtain halloysite nanotubes loaded with N-(2,4,6-trichlorophenyl)maleimide antifouling agent, abbreviated as HNTs-TCPM.

[0069] Example 8

[0070] This embodiment illustrates the preparation of halloysite nanotubes loaded with N-(2,4,6-trichlorophenyl)maleimide antifouling agent.

[0071] The preparation method of this embodiment is basically the same as that of Example 7, except that the concentration of halloysite in the suspension in this embodiment is 25 g / L.

[0072] Furthermore, the antifouling agent release process of halloysite nanotubes (HNTs / TCPM) loaded with antifouling agent prepared in Example 8 was tested.

[0073] The specific steps are as follows:

[0074] 100 mg of halloysite nanotubes loaded with the antifouling agent prepared in Example 8 were placed in 2 ml of deionized water or cyclohexane and stirred. The solution was centrifuged at regular intervals, and fresh solvent was added afterward. The supernatant was analyzed using UV-Vis absorption spectroscopy to obtain the antifouling agent release curve, as shown below. Figure 4 As shown.

[0075] Example 9

[0076] This embodiment illustrates the preparation of halloysite nanotubes loaded with N-(2,4,6-trichlorophenyl)maleimide antifouling agent.

[0077] The preparation method of this embodiment is basically the same as that of Example 7, except that the concentration of halloysite in the suspension in this embodiment is 12.5 g / L.

[0078] Figure 2 Thermogravimetric analysis curves for antifouling agent (TCPM) and halloysite (HNTs).

[0079] Figure 3 Thermogravimetric analysis curves of halloysite nanotubes (HNTs-TCPM) loaded with antifouling agents prepared in Examples 7-9 above.

[0080] Figure 4 Antifouling agent release curves of halloysite nanotubes (HNTs-TCPM) loaded with antifouling agent prepared in Example 8 above in water or cyclohexane.

[0081] Depend on Figure 2 , 3 It can be seen from the thermogravimetric curves that the antifouling agent loading of the halloysite nanotubes prepared in Examples 7-9 was calculated to be 1.6 wt.%, 11.6 wt.%, and 17.0 wt.%, respectively. Furthermore, from... Figure 3 It can be seen that as the concentration of the antifouling agent increases, the loading rate of halloysite also increases.

[0082] Depend on Figure 4 It can be seen that the release curve of the antifouling agent (TCPM) in the halloysite (HNTs / TCPM) loaded with antifouling agent prepared in Example 8 tends to be flat, proving that halloysite has a slow-release effect on the release of the antifouling agent, prolonging the release time of the antifouling agent. Furthermore, the release rate in deionized water is slower than the release rate in cyclohexane.

[0083] Example 10

[0084] This embodiment illustrates the preparation of halloysite nanotubes loaded with 4,5-dichloro-N-octyl-4-isothiazolin-3-one antifouling agent.

[0085] The preparation method in this embodiment is basically the same as that in Example 7, except that the antifouling agent used in this embodiment is 4,5-dichloro-N-octyl-4-isothiazolin-3-one, the solvent is xylene, and the resulting product is abbreviated as HNTs-DCOIT. The antifouling agent loading of halloysite nanotubes is 9.8 wt.%.

[0086] Example 11

[0087] This embodiment illustrates the preparation of halloysite nanotubes loaded with capsaicin antifouling agent.

[0088] The preparation method in this embodiment is basically the same as that in Example 7, except that the antifouling agent used in this embodiment is capsaicin, and the resulting product is abbreviated as HNTs-Capsaicin. The antifouling agent loading of halloysite nanotubes is 3.2 wt.%.

[0089] Example 12

[0090] This embodiment illustrates the preparation of the antifouling composite material PCLU / HNTs-TCPM.

[0091] 100 parts by weight of the polycaprolactone polyurethane matrix (PCLU) prepared in Example 3 and 40 parts by weight of the halloysite nanotubes (HNTs-TCPM) loaded with antifouling agent prepared in Example 8 were weighed, added to a Hacker mixer at 150°C for mixing, and then taken out and hot-pressed into a flat plate to obtain an antifouling composite material, abbreviated as PCLU / HNTs-TCPM.

[0092] Figure 5 SEM and TEM images of the antifouling composite material (PCLU / HNTs-TCPM) prepared in Example 12.

[0093] As shown in the figure, halloysite is well dispersed in polycaprolactone polyurethane matrix without agglomeration, and can maintain its original tubular structure after being mixed in a Hacker internal mixer.

[0094] Example 13

[0095] This embodiment illustrates the preparation of the antifouling composite material PCLU / HNTs-TCPM.

[0096] The preparation method of this embodiment is basically the same as that of Example 12. The difference is that in this embodiment, the halloysite nanotubes (HNTs-TCPM) raw material loaded with antifouling agent prepared in Example 8 is weighed in 1 part by weight, and the antifouling composite material is abbreviated as PCLU / HNTs-TCPM.

[0097] Example 14

[0098] This example illustrates the preparation of the antifouling composite material PLLAU / HNTs-DCOIT.

[0099] 100 parts by weight of the poly-L-lactide polyurethane matrix (PLLAU) prepared in Example 5 and 60 parts by weight of halloysite nanotubes loaded with antifouling agent (HNTs-DCOIT) prepared in Example 10 were weighed, added to a Hacker mixer at 150°C for mixing, and then taken out and hot-pressed into a flat plate to obtain an antifouling composite material, abbreviated as PLLAU / HNTs-DCOIT.

[0100] Example 15

[0101] This embodiment illustrates the preparation of the antifouling composite material PPCU / HNTs-Capsaicin.

[0102] 100 parts by weight of the polypropylene carbonate polyurethane matrix (PPCU) prepared in Example 6 and 40 parts by weight of the halloysite nanotubes (HNTs-Capsaicin) loaded with antifouling agent prepared in Example 11 were weighed, added to a Hacker mixer at 150°C for blending, and then taken out and hot-pressed into a flat plate to obtain an antifouling composite material, abbreviated as PPCU / HNTs-Capsaicin.

[0103] Comparative Example 1

[0104] This comparative example is used to illustrate the preparation of the composite material PCLU / TCPM.

[0105] The preparation method of this comparative example is basically the same as that of Example 12. The difference is that the raw materials of this comparative example are 100 parts by weight of polycaprolactone polyurethane matrix (PCLU) prepared in Example 3 and 4.6 parts by weight of antifouling agent (TCPM). The resulting composite material is abbreviated as PCLU / TCPM.

[0106] Comparative Example 2

[0107] This comparative example is used to illustrate the preparation of the composite material PCLU / HNTs.

[0108] The preparation method of this comparative example is basically the same as that of Example 12. The difference is that the raw materials of this comparative example are 100 parts by weight of polycaprolactone polyurethane matrix (PCLU) prepared in Example 3 and 40 parts by weight of halloysite nanotubes, and the resulting composite material is abbreviated as PCLU / HNTs.

[0109] The following describes the performance of antifouling agent release in antifouling composite materials:

[0110] The antifouling agent release process was tested on the antifouling composite material (PCLU / / HNTs-TCPM) prepared in Example 12 and the composite material (PCLU / TCPM) prepared in Comparative Example 1.

[0111] The specific steps are as follows:

[0112] Weigh 2g of the composite material into 5ml of deionized water. After centrifuging at regular intervals, replenish the solution with fresh solvent. Analyze the supernatant using UV-Vis absorption spectroscopy to obtain the antifouling agent release curve, as shown below. Figure 6 As shown.

[0113] Depend on Figure 6 It can be seen that the antifouling agent release of the composite material of Example 12 is slower than that of the composite material of Comparative Example 1. In other words, loading the antifouling agent into halloysite can effectively prolong the release time of the antifouling agent compared to adding the antifouling agent directly to the matrix.

[0114] The following is used to illustrate the antibacterial properties of antifouling composite materials:

[0115] Test 1:

[0116] Samples prepared in Examples 12, 13, Comparative Example 1, and Comparative Example 2 were cut into 1cm × 1cm slices and suspended in prepared sodium-dependent Vibrio culture medium. They were cultured at 30°C with shaking at 200 rpm for three days. The sample surface was washed with PBS buffer, and then the samples were solidified in 2% glutaraldehyde PBS buffer for 4 hours. Finally, they were dehydrated stepwise with 60%, 70%, 80%, 90%, and 99.2% ethanol solutions and dried at low temperature. The growth of sodium-dependent Vibrio on the surface was observed using SEM. Figure 7 As shown.

[0117] Test 2:

[0118] The samples prepared in Example 12 and Comparative Example 1 were cut into 1cm × 1cm slices and placed in 100ml of pre-prepared artificial seawater. The mixture was mechanically stirred at 200 rpm at room temperature, with the artificial seawater replaced periodically every 7 days. The samples were removed after 60 days. Following the same procedure as in Test 1, the samples were cultured in sodium-dependent Vibrio culture medium for three days. The adhesion and growth of sodium-dependent Vibrio on the sample surface were observed using SEM. Figure 8 As shown.

[0119] Figure 7 SEM images of the surface of the composite materials prepared in Examples 12, 13, Comparative Example 1 and Comparative Example 2 after being suspended in sodium-dependent Vibrio culture medium for three days.

[0120] Figure 8 The image shows the SEM images of the surface of the composite materials prepared in Example 12 and Comparative Example 1 after being placed in artificial seawater for 60 days.

[0121] Depend on Figure 7 It can be seen that in the composite material (PCLU / HNTs-TCPM) prepared in Example 13, due to the small amount of HNTs-TCPM added, bacterial adhesion appeared on the surface (see details). Figure 7 a) The composite material (PCLU / HNTs) prepared in Comparative Example 2 showed a higher number of bacteria adhering to its surface, forming a biofilm. This is because the added HNTs increased surface roughness, making it easier for bacteria to settle and proliferate (see details). Figure 7 b); The surface of the composite material (PCLU / TCPM) sample prepared in Comparative Example 1 showed almost no bacterial adhesion (see details). Figure 7 c) A small number of bacteria adhered to the surface of the composite material (PCLU / HNTs-TCPM) sample prepared in Example 12 (see details). Figure 7 d) This shows that the samples prepared in Comparative Example 1 and Example 8 can inhibit bacterial adhesion and prevent the formation of biofilm. Furthermore, the composite material in Comparative Example 1 releases the antifouling agent at a faster rate, thus exhibiting better antibacterial effect in the early stages.

[0122] Depend on Figure 8 It can be seen that after the composite material (PCLU / TCPM) sample prepared in Comparative Example 1 was placed in seawater for 60 days, sodium-dependent Vibrio bacteria began to attach and proliferate on the sample surface after being cultured in sodium-dependent Vibrio culture medium for 3 days (see details). Figure 8 a) No bacteria were found on the surface of the composite material (PCLU / HNTs-TCPM) sample prepared in Example 12 (see details). Figure 8 (b) This is because during seawater immersion, TCPM molecules in the composite material (PCLU / TCPM) of Comparative Example 1 migrate to the surface at a relatively fast rate, resulting in most TCPM being released into the seawater, thus weakening its inhibitory effect on bacteria. The composite material (PCLU / HNTs-TCPM) prepared in Example 12, with the aid of HNTs carriers, allows the sample with added HNTs-TCPM filler to release antifouling molecules into the environment at a low level and continuously, preventing the attachment of marine bacteria for a long time and improving the utilization rate of the antifouling agent.

Claims

1. An antifouling composite material, characterized by, The antifouling composite material is prepared from raw materials comprising The antifouling composite material is prepared from raw materials comprising The components are as follows in terms of weight parts: 100 parts by weight of the polymer matrix; 1-100 parts by weight of the slow-release filler; The polymer matrix is a polyurethane with a main chain degradable into non-toxic small molecules; the slow-release filler is halloysite nanotubes loaded with an antifouling agent. The polymer matrix is one of a polycaprolactone type polyurethane, a polylactic acid type polyurethane, and a polycarbonate type polyurethane. The halloysite nanotubes loaded with the antifouling agent are prepared by the following method: Step one: place the halloysite nanotubes in a muffle furnace and treat them at a high temperature of 120-1000℃ for 1-3h; Step two: dissolve the antifouling agent in a solvent to prepare an antifouling agent solution with a concentration of 10-150 g / L; Step three: add the halloysite nanotubes treated in step one to the antifouling agent solution prepared in step two to prepare a suspension, and perform ultrasonic dispersion treatment on the suspension to make the concentration of halloysite in the suspension 5-300 g / L; Step four: use a vacuum loading method to cyclically stir the suspension prepared in step three under vacuum / normal pressure for 3-5 times, and then perform centrifugal separation, washing, drying, and grinding to obtain the halloysite nanotubes loaded with the antifouling agent.

2. The antifouling composite material according to claim 1, wherein The components are as follows in terms of weight parts: 100 parts by weight of the polymer matrix; 1-60 parts by weight of the slow-release filler.

3. The antifouling composite material according to claim 1, wherein The polymer matrix is prepared by the following method: mix polyester polyol, diisocyanate, and catalyst to obtain a prepolymer, and then add a chain extender to obtain a degradable polymer matrix.

4. The antifouling composite material according to claim 3, wherein The polyester polyol is one of polycaprolactone diol, polypropylene carbonate diol, and poly-L-lactide diol; The diisocyanate is one of isophorone diisocyanate, hexamethylene diisocyanate, and 4,4'-dicyclohexylmethane diisocyanate; The catalyst is one of dimethylcyclohexylamine and dibutyltin dilaurate; The chain extender is one of 1,4-butanediol, 1,6-hexanediol, and ethylene glycol.

5. The antifouling composite material according to claim 1, wherein The antifouling agent is one of a maleimide type, an isothiazolinone type, and a capsaicin type antifouling agent.

6. The antifouling composite material according to claim 1, wherein In step two, the solvent used is one of ethanol and dimethylbenzene; In step four, the vacuum pressure is -0.095 - -0.01 MPa, the centrifugal separation speed is 5000-8000 r / min, and the drying temperature is 60-80℃.

7. A method for preparing the composite material according to any one of claims 1-6, wherein The antifouling composite material is prepared by blending the polymer matrix and the slow-release filler in the required amounts.

8. Use of the composite material according to any one of claims 1-6 in marine engineering equipment.

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