Antibacterial antifouling composite material, multilayer structure and application thereof

Abstract

The invention discloses an antibacterial antifouling composite material, a multilayer structure and application thereof. The antibacterial antifouling composite material is prepared from the following raw materials: matrix resin, antifouling resin and additives which can be selectively used or not used, wherein the antifouling resin is mainly obtained by reacting zwitter-ion modified hydroxyl silicone oil with a furan dioxime antibacterial cross-linking agent. The antibacterial and antifouling composite material provided by the invention has excellent antibacterial and antifouling properties, is easy to prepare, and can be prepared only through melt extrusion; meanwhile, the antifouling resin has good compatibility with matrix resin, so that the influence on the mechanical property of the composite material under the condition of high addition amount is not obvious, the long-acting antifouling property of the composite material can be met, and the antifouling requirements of marine aquaculture facilities, cables, pipeline systems and the like can be well met.

Description

Technical Field

[0001] The invention relates to an antibacterial and antifouling composite material, and a multilayer structure based on the antibacterial and antifouling composite material and application thereof, belonging to the technical field of antifouling. Background Art

[0002] Marine fouling refers to the phenomenon of marine organisms attached to the surface of a substrate immersed in seawater. The losses caused by marine fouling exceed 1.4 trillion yuan each year, and many anti-fouling measures have been developed for this purpose. Among them, applying anti-fouling paint is the simplest and most economical and effective anti-fouling means, but at present, anti-fouling paint mainly achieves anti-fouling effect by adding high content of heavy metals such as cuprous oxide, which also leads to heavy metal pollution to marine ecology, especially in the field of aquaculture with high environmental protection requirements, which limits its large-scale application. At the same time, anti-fouling paint also has the problem of coating peeling, especially on non-metallic substrates, coating peeling is very prominent, which greatly reduces its anti-fouling effect and service life. In addition, some anti-fouling paints are continuously polished by surface resin to form a new interface to achieve the removal of fouling organisms, which also leads to the harm of microplastic pollution in the marine ecological environment. Therefore, in marine anti-fouling materials, intrinsic anti-fouling materials are urgently needed. At present, copper alloy materials are used in aquaculture systems to achieve intrinsic anti-fouling, but copper alloys are expensive, and there is an unstable corrosion rate in the marine environment, which leads to the fatal defect of a short service life. Summary of the invention

[0003] The main purpose of the present invention is to provide an antibacterial and antifouling composite material, a multilayer structure and applications thereof, so as to overcome the deficiencies in the prior art.

[0004] In order to achieve the above-mentioned invention object, the technical solution adopted by the present invention includes:

[0005] The present invention provides an antibacterial and antifouling composite material, the raw materials of which include a matrix resin, an antifouling resin and an auxiliary agent which can be used or not; wherein the antifouling resin is mainly obtained by reacting zwitterion-modified hydroxy silicone oil with a furandioxime antibacterial crosslinking agent.

[0006] The present invention also provides a method for preparing the aforementioned antibacterial and antifouling composite material, comprising:

[0007] The zwitterion-modified hydroxy silicone oil is reacted with a furan dioxime antibacterial crosslinking agent to obtain an antifouling resin;

[0008] The antifouling resin, the base resin, and the auxiliary agent which may be used or not are uniformly mixed to obtain a mixture;

[0009] And, the mixture is heated to a selected temperature for melt extrusion, and then injection molding or drawing is performed to obtain the antibacterial and antifouling composite material.

[0010] The present invention also provides a multi-layer structure, wherein at least one structural layer in the multi-layer structure is an antifouling material layer, and the antifouling material layer is formed by the aforementioned antibacterial and antifouling composite material.

[0011] The present invention also provides the use of the aforementioned antibacterial and antifouling composite material in preparing a marine aquaculture system, a cable or a pipe network system.

[0012] Compared with the prior art, the present invention has the following beneficial effects:

[0013] (1) The present invention combines an antifouling resin with a matrix resin. Since the antifouling resin has good compatibility with the matrix resin (such as PET resin), the antifouling resin can be well dispersed in the matrix resin. During long-term use, the antifouling resin will not separate from the matrix resin and precipitate. The composite material has excellent antibacterial and antifouling properties and a longer service life. Compared with traditional organic antifouling agents, the antifouling resin has better thermal stability and is therefore suitable for melt extrusion processing. Compared with traditional inorganic antifouling agents, which are prone to crystallization of PET materials and a decrease in their comprehensive mechanical properties, especially when added in high amounts, the antifouling resin in the antifouling resin has good compatibility with the PET matrix. When added in high amounts, the mechanical properties of the PET composite material are not significantly affected, and the long-term antifouling performance of the PET composite material can be met.

[0014] (2) The antibacterial and antifouling composite material of the present invention is easy to prepare and can be obtained only by melt extrusion. It has good long-term antifouling performance in seawater environment and is suitable for the antifouling needs of marine aquaculture facilities, cables and pipeline systems. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments recorded in the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0016] Figure 1 is the hydrogen nuclear magnetic resonance spectrum of the sulfobetaine-modified hydroxy silicone oil in Example 1 of the present invention;

[0017] Figure 2 A schematic diagram of a multilayer film structure in an application example of the present invention is shown;

[0018] Figure 3a-Figure 3b This is a picture of the composite material extruded when the amount of nano cuprous oxide added exceeds 3 parts in a typical embodiment of the present invention.

[0019] Explanation of the reference numerals: 1 - antifouling material layer. DETAILED DESCRIPTION

[0020] In view of the shortcomings of traditional antifouling methods, the inventor of this case has proposed the technical solution of the present invention after long-term research and extensive practice. PET is a general polymer material that can be modified to have excellent mechanical properties, thermal stability, solvent resistance and UV resistance and is widely used in mesh, packaging, pipelines and other fields. Based on the good stability of PET itself, it is feasible to prepare PET functional materials with excellent antifouling properties by adding environmentally friendly antifouling resins and / or other additives for compounding and modification.

[0021] The technical solution, its implementation process and principle are further explained as follows. It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the present invention. Unless otherwise specified, all technical and scientific terms used in this specification have the same meanings as those commonly understood by those of ordinary skill in the art to which the present invention belongs.

[0022] An aspect of an embodiment of the present invention provides an antibacterial and antifouling composite material, the raw materials of which include a base resin, an antifouling resin, and an auxiliary agent that can be used or not; wherein the antifouling resin is mainly obtained by reacting zwitterion-modified hydroxy silicone oil with furandioxime antibacterial crosslinking agent.

[0023] In some embodiments, the antifouling resin includes a compound having a structure as shown in formula (I):

[0024]

[0025] Wherein, X is 5 to 5000, R1 is derived from zwitterion-modified hydroxy silicone oil, and R2 is derived from furandioxime.

[0026] In some embodiments, the zwitterion-modified hydroxy silicone oil is selected from any one or a combination of two or more of the following structures:

[0027]

[0028] Among them, n∶m∶p∶q=75~95∶0.5~25∶0.5~24.5∶0.5~24.

[0029] Furthermore, the zwitterionic compound includes any one of sulfobetaine, carboxybetaine, and phosphorylcholine, or a combination of two or more thereof, but is not limited thereto.

[0030] Furthermore, the molecular weight of the hydroxy silicone oil is 2000-20000 g / mol.

[0031] Furthermore, the content of the zwitterionic compound segment in the zwitterionic modified hydroxy silicone oil is 2 wt % to 20 wt %.

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

[0033] In some embodiments, the furandioxime antibacterial cross-linking agent has a structure as shown in formula (II) and / or formula (III):

[0034]

[0035] In some embodiments, the method for preparing the antifouling resin of the present invention comprises: reacting zwitterion-modified hydroxy silicone oil with furandioxime antibacterial crosslinking agent at room temperature to obtain the antifouling resin.

[0036] Furthermore, the mass ratio of the zwitterion-modified hydroxy silicone oil to the furandioxime antibacterial crosslinking agent is 10:0.5 to 10:1.5.

[0037] In some embodiments, the base resin includes polyethylene terephthalate (PET base resin).

[0038] In some embodiments, the antibacterial and antifouling composite material is prepared by adding a small amount of high-efficiency antifouling resin into a matrix resin and performing melt blending.

[0039] In some embodiments, the auxiliary agent includes any one of an antioxidant and a lubricant or a combination of two or more thereof, but is not limited thereto.

[0040] Furthermore, the auxiliary agent includes any one or a combination of two or more of antioxidants, lubricants, anti-ultraviolet aging agents, etc., but is not limited thereto.

[0041] Furthermore, the antibacterial and antifouling composite material includes a PET matrix resin, an antioxidant, a lubricant, an antifouling resin, and the like.

[0042] Specifically, the antioxidant includes any one or more combinations of tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, triethylene glycol bis[triethylene glycol tert-butyl-4-hydroxy-5-methylphenyl)propionate], N,N′-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexanediamine and 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanuric acid, and is not limited thereto.

[0043] Specifically, the lubricant includes any one or more combinations of montanic acid esters / salts, stearates (such as calcium stearate), fatty amides or polyol esters, and is not limited thereto. In some embodiments, the content of the antifouling resin in the antibacterial and antifouling composite material is less than 20wt%, preferably less than 15wt%, and particularly preferably 5wt-10wt%.

[0044] In some embodiments, the antibacterial and antifouling composite material has a killing rate of Escherichia coli of more than 90%.

[0045] Accordingly, another aspect of the embodiments of the present invention provides a method for preparing an antibacterial and antifouling composite material, which comprises:

[0046] The zwitterion-modified hydroxy silicone oil is reacted with a furan dioxime antibacterial crosslinking agent to obtain an antifouling resin;

[0047] The antifouling resin, the base resin, and the auxiliary agent which may be used or not are uniformly mixed to obtain a mixture;

[0048] And, the mixture is heated to a selected temperature for melt extrusion, and then injection molding or drawing is performed to obtain the antibacterial and antifouling composite material.

[0049] In some embodiments, the selected temperature is 240°C to 280°C.

[0050] Furthermore, the selected temperature is 240°C to 260°C.

[0051] The antibacterial and antifouling composite material provided by the embodiment of the present invention has excellent antifouling performance, and this type of antifouling material is easy to process, without changing the traditional PET processing equipment and process, and the required antifouling products can be obtained only by melt extrusion or drawing. The antifouling effect of PET intrinsic material is obvious, and it is suitable for the antifouling needs of marine aquaculture systems, cables, and pipe network systems.

[0052] Another aspect of an embodiment of the present invention further provides a multi-layer structure, wherein at least one structural layer in the multi-layer structure is an antifouling material layer, and the antifouling material layer is formed by the aforementioned antibacterial and antifouling composite material.

[0053] Furthermore, another aspect of the embodiments of the present invention provides the use of the aforementioned antibacterial and antifouling composite material in manufacturing a marine aquaculture system, a cable or a pipe network system, etc.

[0054] The antibacterial and antifouling composite material provided by the present invention can be used to manufacture marine aquaculture systems, cables, pipe network systems, etc., but is not limited thereto.

[0055] In order to make the purpose, technical scheme and advantages of the present invention clearer, the technical scheme of the present invention is further described in detail below in conjunction with several preferred embodiments. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments in the present invention, all other embodiments obtained by ordinary technicians in the field without making creative work belong to the scope of protection of the present invention. Unless otherwise specified, the reagents and raw materials used in the following examples are commercially available, and the test methods for which specific conditions are not specified are usually carried out under conventional conditions or according to the conditions recommended by each manufacturer. In addition, unless otherwise specified, the experimental methods, detection methods, and preparation methods disclosed in the present invention all adopt conventional techniques in the art. These technologies have been fully described in the existing literature.

[0056] For example, in the following examples, the resins, additives, pigments, etc. involved can all be purchased from conventional biochemical reagent companies.

[0057] In the following embodiments, the antibacterial and antifouling composite materials involved can be prepared by the same equipment and process as the commonly known PET materials. For example, the aforementioned antifouling resin and PET base resin and other pigments, additives and other components added according to the material performance requirements of different service environments are added at once or in sequence, stirred and mixed, and then various PET antifouling materials required can be prepared by melt extrusion, injection molding or drawing.

[0058] For example, in the following embodiments, the components can be melt-blended and then the antibacterial and antifouling composite material can be prepared using methods including but not limited to injection molding and drawing.

[0059] In the following examples, the rating standards for the hanging sheet performance of the antibacterial and antifouling composite material samples with antifouling performance are shown in Table 1.

[0060] Table 1

[0061] Rating Area covered by the defacement 0 Less than 4% 1 4％-10％ 2 11％-15％ 3 16％-25％ 4 26％-45％ 5 Greater than 45%

[0062] Example 1

[0063] Sulfobetaine modified hydroxy silicone oil such as formula a:

[0064]

[0065] Furandioxime antibacterial crosslinking agent is as follows:

[0066]

[0067] 1. The preparation of antifouling resin specifically includes:

[0068] (1) 30 g of vinyl-modified hydroxy silicone oil and 3 g of 3-dimethylamino-1-propanethiol were uniformly mixed and reacted at 60° C. for 24 h. Then 5 g of 1,3-propyl sultone was added dropwise to the system and reacted at room temperature for 24 h to obtain sulfobetaine-modified hydroxy silicone oil. The product had a hydrogen nuclear magnetic resonance spectrum as shown in FIG. Figure 1 shown.

[0069] (2) The sulfobetaine-modified hydroxy silicone oil and the furandioxime antibacterial crosslinking agent are uniformly mixed in a mass ratio of 10:1 to prepare an antifouling resin.

[0070] 2. Preparation of antibacterial and antifouling composite materials:

[0071] (1) The prepared antifouling resin, PET base resin, and the auxiliary agent which may be used or not are uniformly mixed; the specific amounts are shown in Table 2;

[0072] The mixture is heated to a selected temperature and melt-extruded, and then injection-molded or drawn to obtain an antibacterial and antifouling composite material, wherein the selected temperature is 245° C. The characterization properties are shown in Table 2.

[0073] Example 2

[0074] Carboxybetaine modified hydroxy silicone oil as formula b:

[0075]

[0076] Furandioxime antibacterial crosslinking agent is as follows:

[0077]

[0078] 1. The preparation of antifouling resin specifically includes:

[0079] (1) 30 g of vinyl-modified hydroxy silicone oil and 3 g of 3-dimethylamino-1-propanethiol were uniformly mixed and reacted at 60° C. for 24 h. Then, 0.5 g of β-propiolactone was added dropwise into the system and reacted at room temperature for 24 h to obtain carboxybetaine-modified hydroxy silicone oil.

[0080] (2) The carboxybetaine-modified hydroxy silicone oil and the furandioxime antibacterial crosslinking agent are uniformly mixed in a mass ratio of 10:0.5 to prepare an antifouling resin.

[0081] 2. Preparation of antibacterial and antifouling composite materials:

[0082] (1) The prepared antifouling resin, PET base resin, and the auxiliary agent which may be used or not are uniformly mixed; the specific amounts are shown in Table 2;

[0083] The mixture is heated to a selected temperature and melt-extruded, and then injection-molded or drawn to obtain an antibacterial and antifouling composite material, wherein the selected temperature is 260° C. The characterization properties are shown in Table 2.

[0084] Example 3

[0085] Phosphorylcholine modified hydroxy silicone oil such as formula c:

[0086]

[0087] Furandioxime antibacterial crosslinking agent is as follows:

[0088]

[0089] 1. The preparation of antifouling resin specifically includes:

[0090] (1) 30 g of vinyl-modified hydroxy silicone oil and 3 g of thiolated methacryloyloxyethyl phosphorylcholine were uniformly mixed and reacted at 60° C. for 24 h to obtain phosphorylcholine-modified hydroxy silicone oil.

[0091] (2) Phosphorylcholine-modified hydroxy silicone oil and furan dioxime antibacterial crosslinking agent are uniformly mixed in a mass ratio of 10:0.7 to prepare an antifouling resin.

[0092] 2. Preparation of antibacterial and antifouling composite materials:

[0093] (1) The prepared antifouling resin, PET base resin, and the auxiliary agent which may be used or not are uniformly mixed; the specific amounts are shown in Table 2;

[0094] The mixture is heated to a selected temperature and melt-extruded, and then injection-molded or drawn to obtain an antibacterial and antifouling composite material, wherein the selected temperature is 245° C. The characterization properties are shown in Table 2.

[0095] Example 4

[0096] Carboxybetaine / sulfobetaine modified hydroxy silicone oil as formula d:

[0097]

[0098] Furandioxime antibacterial crosslinking agent is as follows:

[0099]

[0100] 1. The preparation of antifouling resin specifically includes:

[0101] (1) 30 g of vinyl-modified hydroxy silicone oil and 2 g of 3-dimethylamino-1-propanethiol were uniformly mixed and reacted at 60° C. for 24 h. Then, 3 g of 1,3-propyl sultone and 0.3 g of β-propiolactone were added dropwise to the system and reacted at room temperature for 24 h to obtain carboxybetaine / sulfobetaine-modified hydroxy silicone oil.

[0102] (2) Carboxybetaine / sulfobetaine modified hydroxy silicone oil and furandioxime antibacterial crosslinking agent are uniformly mixed in a mass ratio of 10:1 to prepare an antifouling resin.

[0103] 2. Preparation of antibacterial and antifouling composite materials:

[0104] (1) The prepared antifouling resin, PET base resin, and the auxiliary agent which may be used or not are uniformly mixed; the specific amounts are shown in Table 2;

[0105] The mixture is heated to a selected temperature and melt-extruded, and then injection-molded or drawn to obtain an antibacterial and antifouling composite material, wherein the selected temperature is 265° C. The characterization properties are shown in Table 2.

[0106] Example 5

[0107] Carboxybetaine / phosphorylcholine modified hydroxy silicone oil as formula f:

[0108]

[0109] Furandioxime antibacterial crosslinking agent is as follows:

[0110]

[0111] 1. The preparation of antifouling resin specifically includes:

[0112] (1) 30 g of vinyl-modified hydroxy silicone oil and 2 g of 3-dimethylamino-1-propanethiol were uniformly mixed and reacted at 60° C. for 24 h. Then, 3 g of thiolated methacryloyloxyethyl phosphorylcholine and 3 g of β-propiolactone were added dropwise into the system and reacted at room temperature for 24 h to obtain carboxybetaine / phosphorylcholine-modified hydroxy silicone oil.

[0113] (2) Carboxybetaine / phosphorylcholine modified hydroxy silicone oil and furandioxime antibacterial crosslinking agent are uniformly mixed in a mass ratio of 10:1.5 to prepare an antifouling resin.

[0114] 2. Preparation of antibacterial and antifouling composite materials:

[0115] (1) The prepared antifouling resin, PET base resin, and the auxiliary agent which may be used or not are uniformly mixed; the specific amounts are shown in Table 2;

[0116] The mixture is heated to a selected temperature and melt-extruded, and then injection-molded or drawn to obtain an antibacterial and antifouling composite material, wherein the selected temperature is 270° C. The characterization properties are shown in Table 2.

[0117] Example 6

[0118] Carboxybetaine / sulfobetaine / phosphorylcholine modified hydroxy silicone oil as formula g:

[0119]

[0120] Furandioxime antibacterial crosslinking agent is as follows:

[0121]

[0122] 1. The preparation of antifouling resin specifically includes:

[0123] (1) 30 g of vinyl-modified hydroxy silicone oil was uniformly mixed with 2 g of 3-dimethylamino-1-propanethiol and 1 g of thiolated methacryloyloxyethyl phosphorylcholine, and the mixture was reacted at 60° C. for 24 h. Then, 3 g of 1,3-propyl sultone and 3 g of β-propiolactone were added dropwise to the system, and the mixture was reacted at room temperature for 24 h to obtain carboxybetaine / sulfobetaine / phosphorylcholine-modified hydroxy silicone oil.

[0124] (2) Carboxybetaine / sulfobetaine / phosphorylcholine modified hydroxy silicone oil and furandioxime antibacterial crosslinking agent are uniformly mixed in a mass ratio of 10:1 to prepare an antifouling resin.

[0125] 2. Preparation of antibacterial and antifouling composite materials:

[0126] (1) The prepared antifouling resin, PET base resin, and the auxiliary agent which may be used or not are uniformly mixed; the specific amounts are shown in Table 2;

[0127] The mixture is heated to a selected temperature and melt-extruded, and then injection-molded or drawn to obtain an antibacterial and antifouling composite material, wherein the selected temperature is 260° C. The characterization properties are shown in Table 2.

[0128] Table 2 Raw material composition and performance test results of various antibacterial and antifouling PET products in Examples 1-6 of the present invention

[0129]

[0130]

[0131] Note: The data shown in columns D and G in Table 2 are the average values ​​after testing multiple samples;

[0132] Comparative Example 1

[0133] The method is the same as that of Example 1, except that the antibacterial and antifouling composite material does not contain antifouling resin; the characterization data are shown in Table 3.

[0134] Comparative Example 2

[0135] The method is the same as that of Example 1, except that the antifouling resin in Example 1 is replaced by a conventional inorganic antifouling agent; the characterization data are shown in Table 3.

[0136] Comparative Example 3

[0137] The method is the same as that of Example 1, except that the antifouling resin in Example 1 is replaced by a conventional organic antifouling agent; the characterization data are shown in Table 3.

[0138] Comparative Example 4

[0139] The method is the same as that of Example 1, except that the antifouling resin in the antibacterial and antifouling composite material is replaced by sulfobetaine-modified hydroxy silicone oil (Formula a); the characterization data are shown in Table 3.

[0140] Comparative Example 5

[0141] The method is the same as that of Example 1, except that the antifouling resin in the antibacterial and antifouling composite material is replaced by a furandioxime antibacterial crosslinking agent (Formula (I)); the characterization data are shown in Table 3.

[0142] Table 3 Raw material composition and performance test results of various antifouling PET products in Comparative Examples 1-5 of the present invention

[0143]

[0144]

[0145] Note: The data shown in columns D and G in Table 1 are the average values ​​after testing multiple samples;

[0146] It can be seen from Table 3 that although the antibacterial effect of the inorganic antifouling agent nano-cuprous oxide in Comparative Example 2 is good when the addition amount is 3 parts, if the antibacterial effect is to be further improved during the experiment, when the addition amount of nano-cuprous oxide is increased, the PET composite material cannot be formed. Figure 3a-Figure 3b As shown. The poor antibacterial effect of the organic antifouling agent copper pyrithione is mainly due to the decomposition of copper pyrithione at high temperature, which leads to the deterioration of its antibacterial and antifouling properties. Therefore, the antifouling PET composite material prepared in this application is more widely used than traditional organic and inorganic antifouling agents, and is not limited by the amount of antifouling resin added and the processing temperature.

[0147] For example, in a typical application case, a multilayer structure can be provided, as shown in FIG3 , wherein the multilayer structure includes a plurality of antifouling material layers 1 stacked and arranged, wherein the antifouling material layer is formed by the aforementioned polyethylene terephthalate antifouling composite material, and the preparation method can refer to the preparation method of the aforementioned polyethylene terephthalate antifouling composite material. The plurality of antifouling material layers can be compounded by bonding, pressing, etc. to obtain the multilayer structure.

[0148] The antifouling and anticorrosion performance of the multilayer structure was tested, and the results showed that the antifouling performance of the multilayer structure was significantly improved compared with the case where PET antifouling material was used alone, and the antifouling performance of the hanging piece was still level 0 after 2 months.

[0149] In addition, the inventors of this case also referred to the aforementioned embodiments and conducted experiments with other raw materials, process operations, and process conditions described in this specification, and obtained relatively ideal results.

[0150] Although the present invention has been described with reference to illustrative embodiments, it will be appreciated by those skilled in the art that various other changes, omissions and / or additions may be made and that elements of the described embodiments may be substituted with substantial equivalents without departing from the spirit and scope of the present invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the present invention without departing from the scope of the present invention. Therefore, it is not intended herein to limit the present invention to the specific disclosed embodiments for carrying out the present invention, but rather it is intended that the present invention will include all embodiments within the scope of the appended claims.

Claims

1. An antibacterial and antifouling composite material, characterized in that: The raw materials of the antibacterial and antifouling composite material include a matrix resin, an antifouling resin and an auxiliary agent that can be used or not; wherein the antifouling resin is mainly obtained by reacting zwitterion-modified hydroxy silicone oil with a furandioxime antibacterial crosslinking agent.

2. The antibacterial and antifouling composite material according to claim 1, characterized in that: The antifouling resin includes a compound having a structure as shown in formula (I): Wherein, X is 5 to 5000, R1 is derived from zwitterion-modified hydroxy silicone oil, and R2 is derived from furandioxime.

3. The antibacterial and antifouling composite material according to claim 1 or 2, characterized in that: The zwitterion-modified hydroxy silicone oil is selected from any one of the following structures or a combination of two or more thereof: Among them, n:m:p:q=75~95:0.5~25:0.5~24.5:0.5~24; And / or, the furan dioxime antibacterial cross-linking agent has a structure as shown in formula (II) and / or formula (III):

4. The antibacterial and antifouling composite material according to claim 1, characterized in that: The base resin includes polyethylene terephthalate.

5. The antibacterial and antifouling composite material according to claim 1, characterized in that: The auxiliary agent includes any one of an antioxidant and a lubricant or a combination of two or more thereof.

6. The antibacterial and antifouling composite material according to claim 1, characterized in that: The content of the antifouling resin in the antibacterial and antifouling composite material is below 20 wt %, preferably 5 to 10 wt %.

7. The antibacterial and antifouling composite material according to claim 1, characterized in that: The antibacterial and antifouling composite material has a killing rate of more than 90% on Escherichia coli.

8. The method for preparing the antibacterial and antifouling composite material according to any one of claims 1 to 7, characterized in that: include: The zwitterion-modified hydroxy silicone oil is reacted with a furandioxime antibacterial crosslinking agent to obtain an antifouling resin; The antifouling resin, the base resin, and the auxiliary agent which may be used or not are uniformly mixed to obtain a mixture; And, the mixture is heated to a selected temperature for melt extrusion, and then injection molding or drawing is performed to obtain the antibacterial and antifouling composite material.

9. A multi-layer structure, characterized in that: At least one structural layer in the multi-layer structure is an antifouling material layer, and the antifouling material layer is formed by the antibacterial and antifouling composite material according to any one of claims 1 to 7.

10. Use of the antibacterial and antifouling composite material according to any one of claims 1 to 7 in the preparation of a marine aquaculture system, a cable or a pipe network system.

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