Antifouling composite structure and manufacturing method thereof

Abstract

This disclosure provides an antifouling composite structure comprising an elastic membrane and an antifouling membrane. One material of the elastic membrane is polydimethylsiloxane, and the antifouling membrane is disposed on a surface of the elastic membrane. The cross-sectional shape of the surfaces of both the antifouling membrane and the elastic membrane is wrinkled. The antifouling membrane comprises a copolymer polymer composed of a plurality of polydimethylsiloxane units and a plurality of polystyrene units, wherein the polydimethylsiloxane units constitute 10% to 80% of the copolymer polymer. The copolymer polymer has a structure as shown in Formula (I), where each symbol is as defined in the specification. This achieves antifouling and anti-bioadhesion effects and helps extend the lifespan of the antifouling composite structure.

Description

Technical Field

[0001] This disclosure relates to an antifouling composite structure and its preparation method, particularly to a long-lasting and durable antifouling composite structure and its preparation method. Prior Technology

[0002] There are currently two solutions to problems such as anti-fouling or anti-biofouling. One is to use anti-biofouling coatings, which use hydrophilic polymers (such as polyethylene glycol) with surface energy similar to water to inhibit the adhesion of organisms or dirt. The other is slippery liquid-infused porous surface (SLIPS), which uses low surface energy materials in combination with a smooth liquid, so that the smooth liquid exists in the porous surface of the low surface energy material, thus forming a surface that is difficult for organisms or dirt to adhere to.

[0003] However, anti-bioadhesion coatings have poor long-term stability and are easily oxidized and degraded by microorganisms. Once bioadhesion occurs on the coating, it is difficult to remove and can lead to coating failure. In addition, the smoothing liquid injected into porous surfaces is consumed during use and is easily lost in liquid environments, which limits the application of smoothing liquid injection into porous surfaces.

[0004] In view of this, developing a material that can be applied in different environments and has long-term stable anti-fouling and anti-biofouling effects has become the goal of relevant industries. Summary of the Invention

[0005] The purpose of this disclosure is to provide an anti-fouling composite structure that, by selecting specific structures and materials, extends the anti-fouling and anti-bioadhesion effects of the anti-fouling composite structure.

[0006] One embodiment of this disclosure provides an antifouling composite structure comprising an elastic membrane and an antifouling membrane. The elastic membrane is made of polydimethylsiloxane, and the antifouling membrane is disposed on a surface of the elastic membrane. The cross-sectional shape of the surfaces of both the antifouling membrane and the elastic membrane is wrinkled. The antifouling membrane comprises a copolymer polymer, which is copolymerized from a plurality of polydimethylsiloxane units and a plurality of polystyrene units, wherein the polydimethylsiloxane units constitute 10% to 80% of the copolymer polymer. The copolymer polymer has a structure as shown in formula (I): Formula (I); Where m is a value between 0 and 11, n is a value between 0 and 8, and R is a hydrogen atom or a trimethylsilyl group.

[0007] Accordingly, the antifouling composite structure disclosed herein, by configuring an elastic membrane and an antifouling membrane, and using a specific material for the antifouling membrane, can produce a wrinkled surface structure with a smooth surface. Therefore, it can achieve antifouling and anti-bioadhesion effects without applying a smooth liquid. Its effect is stable and not easily decayed, which helps to extend the life of the antifouling composite structure.

[0008] Based on the aforementioned antifouling composite structure, the antifouling membrane may include a wetting layer, and the wetting layer may be located on the side of the antifouling membrane away from the elastic membrane.

[0009] Based on the aforementioned antifouling composite structure, the antifouling membrane may include a wetting layer, and the wetting layer may be located on the side of the antifouling membrane adjacent to the elastic membrane.

[0010] Based on the aforementioned anti-fouling composite structure, when the volume fraction of polydimethylsiloxane units in the copolymer is 17%, m is 0.153 and n is 1; when the volume fraction of polydimethylsiloxane units in the copolymer is 58%, m is 1.0097 and n is 1; when the volume fraction of polydimethylsiloxane units in the copolymer is 76%, m is 2.369 and n is 1.

[0011] Another embodiment of this disclosure provides a method for preparing an antifouling composite structure, comprising the following steps: A substrate is provided, one surface of which has a sacrificial layer. A copolymer polymer is coated onto the sacrificial layer to form an antifouling film. An elastic polymer is coated onto the antifouling film to form an elastic film, wherein one material of the elastic film comprises polydimethylsiloxane. The sacrificial layer is removed, causing the antifouling film and the elastic film to separate from the substrate and spontaneously deform to form an antifouling composite structure. The antifouling film and the elastic film are connected. A cross-sectional shape of one surface of the antifouling film is wrinkled. The polymer is copolymerized from a plurality of polydimethylsiloxane units and a plurality of polystyrene units, wherein the polydimethylsiloxane units account for 10% to 80% of the integral fraction of the copolymer polymer, and the copolymer polymer has a structure as shown in formula (I): Formula (I); Where m is a value between 0 and 11, n is a value between 0 and 8, and R is a hydrogen atom or a trimethylsilyl group.

[0012] According to the aforementioned method for preparing the anti-fouling composite structure, one material of the sacrificial layer may include polyvinyl alcohol.

[0013] According to the aforementioned method for preparing the antifouling composite structure, before coating the copolymer polymer onto the sacrificial layer, a brush-like polymer can be coated onto the sacrificial layer to form a selective layer. One material of the selective layer may include polydimethylsiloxane.

[0014] According to the aforementioned method for preparing the antifouling composite structure, before removing the sacrificial layer, the substrate, the antifouling membrane, and the elastic membrane can be heated to solidify the antifouling membrane and the elastic membrane.

[0015] The aforementioned method for preparing the antifouling composite structure may further include heating the antifouling composite structure to promote the formation and stabilize the cross-sectional shape of the surfaces of the antifouling film and the elastic film.

[0016] According to the aforementioned method for preparing the antifouling composite structure, when the volume fraction of polydimethylsiloxane units in the copolymer is 17%, m is 0.153 and n is 1; when the volume fraction of polydimethylsiloxane units in the copolymer is 58%, m is 1.0097 and n is 1; when the volume fraction of polydimethylsiloxane units in the copolymer is 76%, m is 2.369 and n is 1. Simple Explanation of the Diagram

[0017] To make the above and other objects, features, advantages and embodiments of this disclosure more apparent and understandable, the accompanying drawings are described below: Figure 1 is a three-dimensional schematic diagram of the anti-fouling composite structure according to one embodiment of the present disclosure; Figure 2 is a flowchart of the preparation method of the antifouling composite structure according to another embodiment of the present disclosure; Figure 3 is a three-dimensional schematic diagram of each step in the preparation method of the anti-fouling composite structure; Figure 4 is a schematic diagram of the formation of the wetting layer in the anti-fouling composite structure; Figure 5A is a transmission electron microscope image of the anti-fouling composite structure of the first embodiment; Figure 5B is a transmission electron microscope image of the anti-fouling composite structure of the second embodiment; Figure 5C is a transmission electron microscope image of the anti-fouling composite structure of the third embodiment; Figure 6A shows atomic force microscopy images of the antifouling composite structures of Embodiments 1 to 3 without heat treatment; Figure 6B is a scanning electron microscope image of the antifouling composite structure of Embodiments 1 to 3 without heat treatment; Figure 7A shows an atomic force microscope image of the antifouling composite structure of Embodiments 1 to 3 after heat treatment; Figure 7B is a scanning electron microscope image of the antifouling composite structure of Embodiments 1 to 3 after heat treatment; Figure 8A is a comparison of the amount of green algae cells attached to the composite structures of Comparative Examples 1 to 5; Figure 8B is a comparison of the amount of green algae cells attached to the antifouling composite structures of Examples 1 to 3 and the composite structures of Comparative Example 6 and Comparative Example 7; Figure 9 is a comparison of cell adhesion amounts in the antifouling composite structures of Embodiments 1 to 3; Figure 10 is a comparison diagram of the water contact angle changes of the antifouling composite structures of Embodiments 1 to 3 and the composite structure of Comparative Example 8; and Figure 11 is a comparison diagram of the transmittance of the anti-fouling composite structure of the first to third embodiments and the composite structure of the seventh comparative example. Implementation

[0018] The various embodiments of this disclosure will be discussed in more detail below. However, these embodiments can be applications of various inventive concepts and can be implemented in various different specific scopes. The specific embodiments are for illustrative purposes only and are not limited to the scope of the disclosure.

[0019] Please refer to Figure 1, which is a perspective view of the antifouling composite structure 100 according to one embodiment of this disclosure. The antifouling composite structure 100 includes an elastic membrane 110 and an antifouling membrane 120, with the antifouling membrane 120 disposed on a surface of the elastic membrane 110. A cross-sectional shape of the surfaces of the antifouling membrane 120 and the elastic membrane 110 is wrinkled. When the wrinkles are regularly wavy, the average wavelength can be from 5 μm to 30 μm, and the average amplitude can be from 200 nm to 600 nm.

[0020] In addition to the regular wavy shape shown in Figure 1, the shape of the surface does not need to be completely smooth, and its ridges or depressions may have different heights or depths, and may be on the micrometer scale. Furthermore, wrinkles may extend and be arranged in the same direction, or may be distributed in multiple directions simultaneously, so the content of this disclosure is not limited to the shape shown in Figure 1.

[0021] The elastic membrane 110 is made of polydimethylsiloxane, and its thickness can be from 1 mm to 5 mm. The antifouling membrane 120 has a thickness from 100 nm to 500 nm. The antifouling membrane 120 comprises a copolymer polymer having a structure as shown in formula (I): Formula (I); Wherein, m has a value ranging from 0 to 11, n has a value ranging from 0 to 8, and R is a hydrogen atom or a trimethylsilyl group, while the waveform on the left side of formula (I) may represent phenylethyl or other chemical structures, but this disclosure is not limited thereto.

[0022] In detail, the copolymer can be formed by copolymerizing a plurality of polydimethylsiloxane units and a plurality of polystyrene units, and the polydimethylsiloxane units and polystyrene units can form a biodegradable diblock copolymer (diBCP). The volume fraction of polydimethylsiloxane units in the copolymer can be 10% to 80%, and the volume fraction of polystyrene units in the copolymer can be 20% to 90%. The above volume fractions are calculated based on a density of 0.97 g / cm3 for polydimethylsiloxane units and a density of 1.02 g / cm3 for polystyrene units. For example, when the volume fraction of dimethylsiloxane units in the copolymer is 17% and the volume fraction of polystyrene units in the copolymer is 83%, m is 0.153 and n is 1; when the volume fraction of dimethylsiloxane units in the copolymer is 58% and the volume fraction of polystyrene units in the copolymer is 42%, m is 1.0097 and n is 1; when the volume fraction of dimethylsiloxane units in the copolymer is 76% and the volume fraction of polystyrene units in the copolymer is 24%, m is 2.369 and n is 1. Furthermore, the number average molecular weight (Mn) of the polydimethylsiloxane units can be from 5 kg / mol to 90 kg / mol, and the number average molecular weight of the polystyrene units can be from 25 kg / mol to 50 kg / mol. Furthermore, the polydispersity index (PDI) of the copolymer can be between 1.00 and 1.50.

[0023] This disclosure, by configuring an elastic membrane 110 and an antifouling membrane 120, enables the antifouling composite structure 100 to self-assemble and produce a wrinkled surface structure. This wrinkled surface structure reduces the adhesion points of dirt or organisms, thereby achieving antifouling and anti-biofouling effects. Furthermore, by selecting specific materials, the antifouling composite structure 100 of this disclosure can have a smooth, liquid-like surface, further enhancing its antifouling and anti-biofouling capabilities and facilitating the removal of deposits from the antifouling composite structure 100, thus extending its lifespan.

[0024] The antifouling membrane 120 may include a wetting layer (not shown), which may be located on the side of the antifouling membrane 120 away from the elastic membrane 110 or on the side adjacent to the elastic membrane 110. Alternatively, the antifouling membrane 120 may include two wetting layers, located on opposite sides of the antifouling membrane 120. The wetting layer may be made of polydimethylsiloxane, and its thickness may be 50 nm to 80 nm. By forming a wetting layer, the antifouling and antibiofabrication capabilities can be further enhanced.

[0025] Please refer to Figures 2 and 3. Figure 2 is a flowchart of the steps of the method 200 for preparing an antifouling composite structure according to another embodiment of this disclosure, and Figure 3 is a three-dimensional schematic diagram of each step of the method 200 for preparing an antifouling composite structure. The method 200 for preparing an antifouling composite structure includes steps 210, 220, 230, and 240.

[0026] Step 210 involves providing a substrate S, one surface of which has a sacrificial layer L. The substrate S may be made of glass and may be first cleaned by ultrasonic vibration and then irradiated with ultraviolet light-ozone to make the surface of the substrate S hydrophilic, so as to facilitate the setting of the sacrificial layer L. The material of the sacrificial layer L may include polyvinyl alcohol (PVA).

[0027] Step 220 involves coating a copolymer polymer onto the sacrificial layer L to form an antifouling film 120. The copolymer polymer may have the same details as the copolymer polymer in the previous embodiment, and will not be repeated here. The copolymer polymer can be coated onto the sacrificial layer L by spin coating and cured to form the antifouling film 120.

[0028] Please refer to Figure 4, which is a schematic diagram of the formation of the wetting layer 121 of the antifouling composite structure 100. Before coating the copolymer polymer onto the sacrificial layer L, a brush-like polymer can be coated onto the sacrificial layer L to form a selective layer B. The selective layer B may contain polydimethylsiloxane, and the average molecular weight of the polydimethylsiloxane may be 3000 g / mol, with chlorine atoms at its ends. Since the copolymer polymer may contain multiple polydimethylsiloxane units, when the copolymer polymer is heated and cured, the polydimethylsiloxane units will move to a lower energy interface, such as near the selective layer B or the surface in contact with the external environment, forming a structure of two wetting layers 121 sandwiching an intermediate layer 122. Therefore, the selective layer B helps to form the wetting layer 121 when the antifouling film 120 is cured.

[0029] Step 230 involves coating an elastic polymer P onto the antifouling membrane 120 to form an elastic membrane 110, wherein one material of the elastic membrane 110 comprises polydimethylsiloxane. The elastic polymer P may comprise polydimethylsiloxane and is formed into the elastic membrane 110 by curing, and the elastic membrane 110 may have the same details as the elastic membrane 110 of the previous embodiment, which will not be repeated here.

[0030] Step 240 involves removing the sacrificial layer L, causing the antifouling membrane 120 and the elastic membrane 110 to separate from the substrate S and spontaneously deform, thereby forming an antifouling composite structure 100. Specifically, before removing the sacrificial layer L, the substrate S, the antifouling membrane 120, and the elastic membrane 110 can be heated to solidify them. After the sacrificial layer L is removed, the volume shrinkage of the antifouling membrane 120 and the elastic membrane 110 due to solidification will cause deformation due to dynamic release driven by hydrolysis, resulting in a wrinkled cross-sectional shape on one surface of the antifouling membrane 120 where it connects to the elastic membrane 110.

[0031] Furthermore, the method 200 for preparing the antifouling composite structure disclosed herein may further include heating the antifouling composite structure 100 to promote the formation and stabilize the cross-sectional shape of the surfaces of the antifouling membrane 120 and the elastic membrane 110, thereby making the structure of the antifouling composite structure 100 more stable.

[0032] The following specific embodiments further illustrate the contents of this disclosure, so that those skilled in the art to which this disclosure pertains can fully utilize and practice this disclosure without excessive interpretation. These embodiments should not be regarded as limitations on the scope of this disclosure, but rather as materials and methods for illustrating how to implement this disclosure.

[0033] <Examples and Comparative Examples>

[0034] <Embodiments 1 to 3>

[0035] The antifouling composite structures of Embodiments 1 to 3 are prepared using the method for preparing antifouling composite structures disclosed herein. The copolymer polymers used in Embodiments 1 to 3 contain a plurality of polydimethylsiloxane units and a plurality of polystyrene units, and their material parameters are shown in Table 1 below. Table 1. Parameters of the copolymer polymer materials in Examples 1 to 3 Polydimethylsiloxane unit polystyrene unit polydispersity index Volume fraction (%) Average number molecular weight (kg / mol) Volume fraction (%) Average number molecular weight (kg / mol) Example 1 17 9.0 83 47.1 1.10 Example 2 58 39.0 42 30.0 1.02 3rd Embodiment 76 85.0 twenty four 28.0 1.25

[0036] <Comparative Examples 1 to 8>

[0037] The composite structures of Comparative Examples 1 to 8 include an antifouling membrane, and the material and cross-sectional shape of the antifouling membrane are shown in Table 2 below: Table 2. Antifouling membrane parameters for Comparative Examples 1 to 8 Anti-fouling membrane material Antifouling membrane cross-sectional shape Comparative Example 1 polystyrene planar Second Comparative Example Compared with the first embodiment Copolymers are the same planar Third Comparative Example Compared with the second embodiment Copolymers are the same planar 4th Comparative Example Compared with the third embodiment Copolymers are the same planar Fifth Comparative Example Polydimethylsiloxane planar Comparative Example 6 polystyrene wrinkled Comparative Example 7 Polydimethylsiloxane wrinkled Comparative Example 8 Styrene-lactic acid block Copolymer (PS-b-PLA) wrinkled

[0038] Morphological Analysis of Anti-fouling Composite Structures

[0039] Please refer to Figures 5A to 5C. Figure 5A is a transmission electron microscope image of the antifouling composite structure of the first embodiment, Figure 5B is a transmission electron microscope image of the antifouling composite structure of the second embodiment, and Figure 5C is a transmission electron microscope image of the antifouling composite structure of the third embodiment. In this experiment, morphological analysis was performed on the antifouling composite structures of the first to third embodiments to determine their microphase separation status.

[0040] In Figures 5A to 5C, the dark areas represent polydimethylsiloxane units, and the light areas represent polystyrene units. This indicates that the polydimethylsiloxane units in the first embodiment are primarily distributed in a cylindrical phase, while those in the second and third embodiments are distributed in both cylindrical and lamellar phases. Particularly in Figure 5B, the area indicated by the white arrow is somewhat blurred, showing a coexistence of cylindrical and lamellar phases. Because the antifouling composite structures of the first to third embodiments have an appropriate distribution of polydimethylsiloxane units, and these units have a low glass transition temperature and maintain fluidity at room temperature, it can be deduced that the antifouling composite structures of the first to third embodiments possess good deformability and can form wrinkles.

[0041] <The Influence of Heat Treatment on the Formation of the Wetting Layer>

[0042] In this experiment, the anti-fouling composite structures of the first to third embodiments were heat-treated and observed using an atomic force microscope (AFM) and a scanning electron microscope. Before observation with a scanning electron microscope, the anti-fouling composite structures were first treated with oxygen reactive ion etching (O2-RIE).

[0043] Please refer to Figures 6A, 6B, 7A, and 7B. Figure 6A is an atomic force microscope (AFM) image of the antifouling composite structure of Embodiments 1 to 3 before heat treatment. Figure 6B is a scanning electron microscope (SEM) image of the antifouling composite structure of Embodiments 1 to 3 before heat treatment. Figure 7A is an AFM image of the antifouling composite structure of Embodiments 1 to 3 after heat treatment. Figure 7B is a SEM image of the antifouling composite structure of Embodiments 1 to 3 after heat treatment. Figures 6A and 6B show that the polydimethylsiloxane units (dark areas) are distributed between the polystyrene units (bright areas), and may form an elliptical distribution as indicated by the white arrow.

[0044] Furthermore, a comparison with Figures 7A and 7B reveals that after heat treatment, the distribution area of ​​polydimethylsiloxane units on the antifouling membrane surface increases, and the distribution of polydimethylsiloxane units on the antifouling membrane surface in the second and third embodiments is quite uniform. This indicates that heat treatment facilitates the migration of polydimethylsiloxane units to the antifouling membrane surface and the formation of a wetting layer.

[0045] <Bioadhesion Test>

[0046] In this experiment, the antifouling composite structures of Examples 1 to 3 and the composite structures of Comparative Examples 1 to 7 were cultured in contact with green algae culture medium or lake water concentrate. After the culture was completed, the structures were washed to remove unattached green algae cells or biological cells, and the number of attached cells was counted.

[0047] Please refer to Figures 8A and 8B. Figure 8A is a comparison of the amount of algal cell adhesion in the composite structures of Comparative Examples 1 to 5, and Figure 8B is a comparison of the amount of algal cell adhesion in the antifouling composite structures of Examples 1 to 3, and Comparative Examples 6 and 7. It can be seen that the antifouling membrane cross-section of Comparative Examples 1 to 5 is planar, making it easy for algal cells to adhere. In contrast, the antifouling membrane cross-section of Examples 1, 2, 6, and 7 is wrinkled, reducing algal cell adhesion. This demonstrates that the wrinkled surface structure enhances the antifouling composite structure's resistance to biofouling. Furthermore, although the degree of algal cell adhesion in Example 3 did not decrease significantly, compared to other comparative examples, the antifouling composite structure of Example 3 already possesses a considerably good antifouling effect.

[0048] Please refer to Figure 9, which compares the cell adhesion amounts of the antifouling composite structures in Examples 1 to 3. Figure 9 shows that although the antifouling composite structures in Examples 1 to 3 exhibited more biological cell adhesion after contact culture with concentrated lake water compared to those cultured with green algae culture medium, they still maintained sufficient antifouling effects.

[0049] <Surface property stability>

[0050] In this experiment, the antifouling composite structures of Embodiments 1 to 3 and the composite structure of Comparative Example 8 were placed in an ultrasonic water bath and vibrated for 30 minutes. Then, they were removed and their water contact angle changes were tested. Please refer to Figure 10, which is a comparison of the water contact angle changes of the antifouling composite structures of Embodiments 1 to 3 and the composite structure of Comparative Example 8. As shown in Figure 10, the water contact angle of the antifouling composite structures of Embodiments 1 to 3 did not change significantly after ultrasonic vibration. Conversely, the water contact angle of the composite structure of Comparative Example 8 decreased significantly after ultrasonic vibration due to the loss of the smooth liquid on its surface, thus affecting its anti-adhesion ability. Therefore, the antifouling composite structure disclosed herein can maintain long-term stable antifouling and anti-bioadhesion effects because it does not require the application of a smooth liquid.

[0051] <Optical Transmission>

[0052] In this experiment, the anti-fouling composite structures of Embodiments 1 to 3 and the composite structure of Comparative Example 7 were irradiated with light of different wavelengths, and the light transmittance was measured. Please refer to Figure 11, which is a comparison chart of the transmittance of the anti-fouling composite structures of Embodiments 1 to 3 and the composite structure of Comparative Example 7. As can be seen from Figure 11, the anti-fouling composite structures of Embodiments 2 and 3 possess excellent transmittance comparable to glass, which is beneficial for applications in precision optical instruments. Although the transmittance of the anti-fouling composite structure of Embodiment 1 is slightly lower, it still possesses good transmittance of over 70%.

[0053] In addition to the aforementioned material properties, the anti-fouling composite structure disclosed herein also possesses excellent self-cleaning ability, anti-icing effect, and easy processing properties, making it applicable to different products and scenarios.

[0054] In summary, the antifouling composite structure disclosed herein, by configuring an elastic membrane and an antifouling membrane, and using a specific material for the antifouling membrane, can produce a wrinkled surface structure with a smooth surface. Therefore, it can achieve antifouling and anti-bioadhesion effects without the application of a smoothing liquid. Its effects are stable and do not easily diminish, helping to extend the lifespan of the antifouling composite structure. Furthermore, the preparation method of the antifouling composite structure disclosed herein does not require the use of a smoothing liquid, which simplifies the preparation process and reduces manufacturing costs.

[0055] Although the present disclosure has been presented above with reference to embodiments, it is not intended to limit the present disclosure. Anyone skilled in the art may make various modifications and alterations without departing from the spirit and scope of the present disclosure. Therefore, the scope of protection of the present disclosure shall be determined by the appended claims.

[0056] 100: Anti-fouling composite structure 110: Elastic membrane 120: Anti-fouling membrane 121: Wetting layer 122: Intermediate Layer 200: Preparation method of anti-fouling composite structure 210, 220, 230, 240: Steps S: Substrate L: Sacrificial Layer B: Select Layer P: Elastic polymer

Claims

1. An antifouling composite structure, comprising: an elastic membrane, one material of which comprises polydimethylsiloxane; and an antifouling membrane disposed on a surface of the elastic membrane; wherein, The antifouling membrane and the surface of the elastic membrane have a wrinkled cross-sectional shape; wherein the antifouling membrane comprises a copolymer polymer, which is copolymerized from a plurality of polydimethylsiloxane units and a plurality of polystyrene units, and the polydimethylsiloxane units account for 10% to 80% of the integral fraction of the copolymer polymer, and the copolymer polymer has a structure as shown in formula (I): Formula (I); wherein a value of m is greater than 0 and less than or equal to 11, a value of n is greater than 0 and less than or equal to 8, and R is a hydrogen atom or a trimethylsilyl group.

2. The antifouling composite structure as claimed in claim 1, wherein the antifouling membrane includes a wetting layer and the wetting layer is located on the side of the antifouling membrane away from the elastic membrane.

3. The antifouling composite structure as claimed in claim 1, wherein the antifouling membrane includes a wetting layer and the wetting layer is located on the side of the antifouling membrane adjacent to the elastic membrane.

4. The antifouling composite structure as claimed in claim 1, wherein when the volume fraction of the polydimethylsiloxane units in the copolymer is 17%, m is 0.153 and n is 1; when the volume fraction of the polydimethylsiloxane units in the copolymer is 58%, m is 1.0097 and n is 1; and when the volume fraction of the polydimethylsiloxane units in the copolymer is 76%, m is 2.369 and n is 1.

5. A method for preparing an antifouling composite structure, comprising: providing a substrate having a sacrificial layer on a surface of the substrate; coating a copolymer polymer onto the sacrificial layer to form an antifouling film; coating an elastic polymer onto the antifouling film to form an elastic film, wherein a material of the elastic film comprises polydimethylsiloxane; and removing the sacrificial layer, causing the antifouling film and the elastic film to separate from the substrate and spontaneously deform to form an antifouling composite structure; wherein... The antifouling membrane is connected to the elastic membrane. A cross-sectional shape of one surface of the antifouling membrane is wrinkled. The copolymer is composed of a plurality of polydimethylsiloxane units and a plurality of polystyrene units, and the polydimethylsiloxane units account for 10% to 80% of the integral fraction of the copolymer. The copolymer has a structure as shown in Formula (I): Formula (I); where m is greater than 0 and less than or equal to 11, n is greater than 0 and less than or equal to 8, and R is a hydrogen atom or a trimethylsilyl group.

6. The method for preparing the antifouling composite structure as described in claim 5, wherein one material of the sacrificial layer comprises polyvinyl alcohol.

7. The method for preparing the antifouling composite structure as described in claim 5, wherein before coating the copolymer polymer onto the sacrificial layer, a brush-like polymer is first coated onto the sacrificial layer to form a selective layer; wherein, One material of the selective layer contains polydimethylsiloxane.

8. The method for preparing the antifouling composite structure as claimed in claim 5, wherein before removing the sacrificial layer, the substrate, the antifouling membrane, and the elastic membrane are heated to cure the antifouling membrane and the elastic membrane.

9. The method for preparing the antifouling composite structure as claimed in claim 5 further comprises: heating the antifouling composite structure to promote the formation and stabilize the cross-sectional shape of the surfaces of the antifouling membrane and the elastic membrane.

10. The method for preparing the antifouling composite structure as claimed in claim 5, wherein when the volume fraction of the polydimethylsiloxane units in the copolymer is 17%, m is 0.153 and n is 1; when the volume fraction of the polydimethylsiloxane units in the copolymer is 58%, m is 1.0097 and n is 1; and when the volume fraction of the polydimethylsiloxane units in the copolymer is 76%, m is 2.369 and n is 1.

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