Environment-friendly antifouling composite material, multi-layer structure and application of multi-layer structure

Abstract

The invention discloses an environment-friendly antifouling composite material, a multi-layer structure and application of the multi-layer structure. The environment-friendly antifouling composite material is prepared from the following raw materials: matrix resin, intrinsic antifouling resin and additives which can be selectively used or not used, the antifouling resin comprises a compound with a structure shown in the following formula: # imgabs0 #. The environment-friendly antifouling composite material provided by the invention has excellent sterilization and antifouling properties, is easy to prepare, and can be prepared only by blending the antifouling resin with the structure and PET matrix resin and then carrying out melt extrusion; meanwhile, the anti-fouling composite material does not contain a traditional anti-fouling agent and is prepared through melt blending with anti-fouling resin, the ecological environment problem caused by precipitation of the anti-fouling agent of a traditional anti-fouling material is avoided, and the anti-fouling requirements of marine aquaculture facilities, cables, pipeline systems and the like can be well met.

Description

Technical Field

[0001] The invention relates to an environment-friendly antifouling composite material, a multilayer structure and application thereof, and belongs 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 polished by surface resin to form a new interface to achieve the prevention and 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 environmentally friendly 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 embodiment of the present invention provides an environmentally friendly antifouling composite material, wherein the raw materials of the antifouling composite material include a base resin, an antifouling resin, and an auxiliary agent that can be used or not;

[0006] The antifouling resin includes a compound having a structure as shown in formula (I):

[0007]

[0008]

[0009] Wherein, X is 5 to 5000, R1 is a polymer soft segment, the polymer soft segment is derived from a soft segment polymer, and the soft segment polymer includes any one or more polymers selected from tetrakis dimethyl ether glycol, polycaprolactone alcohol, poly(ethylene adipate), polyhydroxyalkanoate, and bisphenol A polyoxypropylene ether as shown in the following formula;

[0010] R2 is derived from any of the following structural residues:

[0011]

[0012] Wherein, the values ​​of x and y are x=y and are integers between 1 and 3, and M is selected from Cu, Zn or Ag;

[0013] R3 is a polyisocyanate segment, and the polyisocyanate segment is derived from a polyisocyanate residue, and the polyisocyanate includes any one or more combinations of diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, naphthalene 1,5-diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, meta-xylylene diisocyanate, tetramethyl meta-xylylene diisocyanate, 1,4-cyclohexane diisocyanate, methylcyclohexane diisocyanate, 1,4-phenylene diisocyanate, norbornane dimethylene isocyanate, and L-lysine diisocyanate.

[0014] The embodiment of the present invention further provides a method for preparing the aforementioned environmentally friendly antifouling composite material, which comprises:

[0015] The antifouling resin, the base resin, and the auxiliary agent which may be used or not used are uniformly mixed to obtain a mixture;

[0016] The mixture is heated to a selected temperature and melted and extruded, and then injection molded or drawn to obtain the environmentally friendly antifouling composite material.

[0017] 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 environmentally friendly antifouling composite material.

[0018] The embodiment of the present invention further provides the use of the aforementioned environmentally friendly antifouling composite material in preparing a marine aquaculture system, a cable or a pipe network system.

[0019] Compared with the prior art, the present invention has the following beneficial effects:

[0020] (1) The present invention combines the antifouling resin with the matrix resin. Since the antifouling resin has good compatibility with the matrix resin (such as PET), the antifouling resin can be evenly dispersed in the matrix resin. During long-term use, the antifouling resin will not separate from the matrix resin and precipitate. The intrinsic composite material is endowed with excellent sterilization and antifouling properties and a longer service life. Surprisingly, the antifouling composite material can also exhibit good environmental performance.

[0021] (2) The environmentally friendly 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 and environmental protection performance in seawater environment and is suitable for the antifouling needs of marine aquaculture facilities, cables and pipeline systems, etc. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] 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.

[0023] Figure 1 is the hydrogen nuclear magnetic resonance spectrum of the antifouling resin prepared in Example 1 of the present invention;

[0024] Figure 2 A schematic diagram of a multilayer film structure in an application example of the present invention is shown;

[0025] Explanation of reference numerals: 1 - antifouling material layer. DETAILED DESCRIPTION

[0026] 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. The technical solution, its implementation process and principle, etc. will be further explained as follows. It should be noted that the following detailed descriptions are exemplary and are intended to provide further explanation of the present invention. Unless otherwise specified, all technical and scientific terms used in this specification have the same meaning as those commonly understood by ordinary technicians in the technical field to which the present invention belongs.

[0027] An aspect of an embodiment of the present invention provides an environmentally friendly 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;

[0028] The antifouling resin includes a compound having a structure as shown in formula (I):

[0029]

[0030] Wherein, X is 5 to 5000, R1 is a polymer soft segment, the polymer soft segment is derived from a soft segment polymer, and the soft segment polymer includes any one or more polymers selected from tetrakis dimethyl ether glycol, polycaprolactone alcohol, poly(ethylene adipate), polyhydroxyalkanoate, and bisphenol A polyoxypropylene ether as shown in the following formula;

[0031]

[0032] R2 is derived from any of the following structural residues:

[0033]

[0034] Wherein, the values ​​of x and y are x=y and are integers between 1 and 3, and M is selected from Cu, Zn or Ag;

[0035] R3 is a polyisocyanate segment, and the polyisocyanate segment is derived from a polyisocyanate residue, and the polyisocyanate includes any one or more combinations of diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, naphthalene 1,5-diisocyanate, dicyclohexylmethane-4,4-diisocyanate, meta-xylylene diisocyanate, tetramethyl meta-xylylene diisocyanate, 1,4-cyclohexane diisocyanate, methylcyclohexane diisocyanate, 1,4-phenylene diisocyanate, norbornane dimethylene isocyanate, and L-lysine diisocyanate.

[0036] In some embodiments, R1 is selected from any one of the following structures:

[0037]

[0038] Among them, n is 1 to 100000.

[0039] In some embodiments, the antifouling resin includes a compound having a structure as shown in any one of Formula (II) to Formula (VII):

[0040]

[0041]

[0042] Among them, n is 1 to 100000.

[0043] In some embodiments, the method for preparing the antifouling resin of the present invention comprises:

[0044] Conducting a prepolymerization reaction of a prepolymerization system comprising polyisocyanate, a soft segment polymer, a catalyst and a solvent to obtain a prepolymer;

[0045] And, furan dioxime is dissolved in a solvent and mixed with the prepolymer to carry out polymerization reaction to prepare an antifouling resin.

[0046] Further, the polyisocyanate includes any one or more combinations of diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, naphthalene 1,5-diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, meta-xylylene diisocyanate, tetramethyl meta-xylylene diisocyanate, 1,4-cyclohexane diisocyanate, methylcyclohexane diisocyanate, 1,4-phenylene diisocyanate, norbornane dimethylene isocyanate, and L-lysine diisocyanate, and is not limited thereto.

[0047] Further, the soft segment polymer includes any one or more polymers selected from tetrakis dimethyl ether glycol, polycaprolactone alcohol, poly(ethylene adipate), polyhydroxyalkanoate, and bisphenol A polyoxypropylene ether, but is not limited thereto.

[0048] Further, the catalyst includes any one of dibutyltin dilaurate, stannous octoate, dibutyltin didodecylsulfide, and dibutyltin diacetate, or a combination of two or more thereof, but is not limited thereto.

[0049] Further, the solvent includes any one or more combinations of ethanol, methanol, isopropanol, toluene, xylene, n-hexane, cyclohexane, ether, petroleum ether, dichloromethane, chloroform, carbon tetrachloride, ethyl acetate, tetrahydrofuran, acetonitrile, N,N-dimethylformamide, and N,N-dimethylacetamide, and is not limited thereto.

[0050] Furthermore, the furan dioxime is selected from any one or a combination of two or more of the following compounds:

[0051]

[0052] The values ​​of x and y are x=y and are integers between 1 and 3, and M is selected from Cu, Zn or Ag.

[0053] Furthermore, the molar ratio of the polyisocyanate, the soft segment polymer and the catalyst is 1 to 4:1:0.2.

[0054] Furthermore, the molar ratio of furan dioxime to prepolymer is 0.5-2:2-5.

[0055] Furthermore, the temperature of the prepolymerization reaction is 50°C to 90°C.

[0056] Furthermore, the temperature of the prepolymerization reaction is 60°C to 80°C.

[0057] Furthermore, the prepolymerization reaction time is 3h to 12h.

[0058] Furthermore, the prepolymerization reaction time is 5 to 8 hours.

[0059] Furthermore, the polymerization reaction temperature is 50°C to 90°C.

[0060] Furthermore, the polymerization reaction temperature is 60°C to 80°C.

[0061] Furthermore, the polymerization reaction time is 3h to 12h.

[0062] Furthermore, the polymerization reaction time is 5 to 8 hours.

[0063] Furthermore, the preparation method further comprises: after the polymerization reaction is completed, vacuum drying the obtained product.

[0064] Furthermore, the vacuum drying treatment is performed at a temperature of 90° C. to 150° C. and for a time of 24 h to 96 h.

[0065] Furthermore, the preparation method further comprises: after the polymerization reaction is completed, vacuum drying the obtained product; wherein the temperature of the vacuum drying treatment is 90 to 120° C., and the time is 24 to 48 hours.

[0066] In some more specific implementations, the method for preparing the antifouling resin includes:

[0067] (1) dissolving polyisocyanate and dibutyltin dilaurate (DBTDL) in a solvent, adding the mixture to the soft segment polymer, and stirring at 70° C. for 5 h to synthesize a prepolymer;

[0068] (2) dissolving furan dioxime in a solvent and adding the mixture to the prepolymer, stirring at 70° C. for 5 h to obtain the target product;

[0069] (3) The target product is vacuum dried at 90° C. for more than 24 hours to obtain an antifouling resin.

[0070] In some embodiments, the environmentally friendly antifouling composite material is prepared by adding an antifouling resin to a matrix resin and performing melt blending.

[0071] In some embodiments, the auxiliary agent includes any one or a combination of two or more of an antioxidant and a toughening agent, but is not limited thereto.

[0072] In some embodiments, the base resin includes polyethylene terephthalate (PET base resin), but is not limited thereto.

[0073] Furthermore, the environmentally friendly antifouling composite material includes a PET matrix resin, an antioxidant, a toughening agent, an antifouling resin, and the like.

[0074] 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.

[0075] Specifically, the toughening agent 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 antifouling composite material is less than 20wt%, preferably less than 15wt%, and particularly preferably 5wt% to 10wt%.

[0076] In some embodiments, the antifouling composite material has a killing rate of Escherichia coli of more than 90%.

[0077] Accordingly, another aspect of the embodiments of the present invention provides a method for preparing an environmentally friendly antifouling composite material, which comprises:

[0078] The antifouling resin, the PET base resin, and the auxiliary agent which may be used or not used are uniformly mixed to obtain a mixture;

[0079] The mixture is heated to a selected temperature and melted and extruded, and then injection molded or drawn to obtain the environmentally friendly antifouling composite material.

[0080] In some embodiments, the selected temperature is 240°C to 280°C.

[0081] Furthermore, the selected temperature is 240°C to 260°C.

[0082] Specifically, the environmentally friendly antifouling composite material provided by the embodiment of the present invention has excellent antifouling performance. At the same time, because it is prepared by melt blending with the antifouling resin, it avoids the harm of traditional antifouling materials causing environmental ecological risks by releasing antifouling agents into the environment; and this type of antifouling material is easy to process, and there is no need to change the equipment and process of traditional PET processing and modification. The required antifouling products can be obtained only by melt extrusion or drawing, thus realizing the antifouling effect of PET intrinsic materials, and is suitable for the antifouling needs of marine aquaculture systems, cables, and pipe network systems.

[0083] Another aspect of the embodiments 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 environmentally friendly antifouling composite material.

[0084] Furthermore, another aspect of the embodiments of the present invention provides the use of the aforementioned environmentally friendly antifouling composite material in manufacturing a marine aquaculture system, a cable or a pipe network system, etc.

[0085] The environmentally friendly 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.

[0086] 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.

[0087] For example, in the following examples, the resins, additives, etc. involved can all be purchased from conventional biochemical reagent companies.

[0088] In the following embodiments, the environmentally friendly 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 fillers, 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 environmentally friendly antifouling composite materials required can be prepared by melt extrusion, injection molding or drawing.

[0089] For example, in the following embodiments, the components can be melt-blended and then prepared using methods including but not limited to injection molding, drawing, and the like.

[0090] In the following examples, the rating standards for the hanging sheet performance of the antifouling composite material samples with antifouling performance are shown in Table 1.

[0091] Table 1

[0092] 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%

[0093] Example 1

[0094] 1. The preparation of intrinsic antifouling resin specifically includes:

[0095] (1) Prepare the following reactants: polytetramethyl ether diol, isophorone diisocyanate, dibutyltin dilaurate (DBTDL), 2,5-furandioxime, wherein the molecular structure of 2,5-furandioxime is shown in the following formula;

[0096]

[0097] (2) 5 g of isophorone diisocyanate and 0.05 g of dibutyltin dilaurate (DBTDL) were dissolved in a solvent and added to 60 g of polytetrakis dimethyl ether glycol. The mixture was stirred at 70° C. for 5 hours to synthesize a prepolymer.

[0098] (3) 2 g of furan dioxime was dissolved in a solvent and added to the prepolymer. The mixture was stirred at 70° C. for 5 hours to obtain the target product.

[0099] (4) The target product was vacuum dried at 90° C. for 36 hours to obtain an intrinsic antifouling resin, the structural formula of which is shown in FIG. (1):

[0100]

[0101] Figure 1 This is the hydrogen nuclear magnetic resonance spectrum of the intrinsic antifouling resin prepared in this example.

[0102] 2. Preparation of antifouling composite materials:

[0103] (1) The prepared intrinsic antifouling resin, PET base resin, and an auxiliary agent which may be used or not are uniformly mixed to obtain a mixture; the specific amounts are shown in Table 2;

[0104] The mixture is heated to a selected temperature and melt-extruded, and then injection-molded or drawn to obtain an intrinsic antifouling composite material, wherein the selected temperature is 260° C. The characteristic properties are shown in Table 2.

[0105] Example 2

[0106] The preparation of the intrinsic antifouling resin specifically includes:

[0107] (1) preparing the following reactants: polytetramethyl ether glycol, diphenylmethane diisocyanate, dibutyltin dilaurate (DBTDL), and 2,5-furandioxime, wherein the molecular structure of 2,5-furandioxime is shown in the following formula;

[0108]

[0109] (2) 5 g of diphenylmethane diisocyanate and 0.05 g of dibutyltin dilaurate (DBTDL) were dissolved in a solvent, added to 45 g of polytetrakis dimethyl ether glycol, and stirred at 90° C. for 3 hours to synthesize a prepolymer.

[0110] (3) 2 g of furan dioxime was dissolved in a solvent and added to the prepolymer. The mixture was stirred at 90° C. for 10 hours to obtain the target product.

[0111] (4) The target product is vacuum dried at 100° C. for 40 hours to obtain an intrinsic antifouling resin, the structural formula of which is shown in FIG. (2):

[0112]

[0113] 2. Preparation of antifouling composite materials:

[0114] (1) The prepared intrinsic antifouling resin, PET base resin, and an auxiliary agent which may be used or not are uniformly mixed to obtain a mixture; the specific amounts are shown in Table 2;

[0115] The mixture is heated to a selected temperature and melt-extruded, and then injection-molded or drawn to obtain an intrinsic antifouling composite material, wherein the selected temperature is 255° C. The characteristic properties are shown in Table 2.

[0116] Example 3

[0117] The preparation of the intrinsic antifouling resin specifically includes:

[0118] (1) Prepare the following reactants: polycaprolactone alcohol, isophorone diisocyanate, dibutyltin dilaurate (DBTDL), and 2,5-furandioxime, wherein the molecular structure of 2,5-furandioxime is shown in the following formula;

[0119]

[0120] (2) 5 g of isophorone diisocyanate and 0.5 g of dibutyltin dilaurate (DBTDL) were dissolved in a solvent, added to 80 g of polycaprolactone alcohol, and stirred at 60° C. for 10 hours to synthesize a prepolymer.

[0121] (3) 2 g of furan dioxime was dissolved in a solvent and added to the prepolymer. The mixture was stirred at 80° C. for 4 hours to obtain the target product.

[0122] (4) The target product is vacuum dried at 120° C. for 24 hours to obtain an intrinsic antifouling resin, the structural formula of which is shown in FIG. (3):

[0123]

[0124] 2. Preparation of antifouling composite materials:

[0125] (1) The prepared intrinsic antifouling resin, PET base resin, and an auxiliary agent which may be used or not are uniformly mixed to obtain a mixture; the specific amounts are shown in Table 2;

[0126] The mixture is heated to a selected temperature and melt-extruded, and then injection-molded or drawn to obtain an intrinsic antifouling composite material, wherein the selected temperature is 265° C. The characteristic properties are shown in Table 2.

[0127] Example 4

[0128] The preparation of the intrinsic antifouling resin specifically includes:

[0129] (1) preparing the following reactants: bisphenol A polyoxypropylene ether, diphenylmethane diisocyanate, dibutyltin dilaurate (DBTDL), 2,5-furandioxime, wherein the molecular structure of 2,5-furandioxime is shown in the following formula;

[0130]

[0131] (2) 5 g of diphenylmethane diisocyanate and 0.05 g of dibutyltin dilaurate (DBTDL) were dissolved in a solvent, added to 85 g of bisphenol A polyoxypropylene ether, and stirred at 90° C. for 4 hours to synthesize a prepolymer.

[0132] (3) 2 g of furan dioxime was dissolved in a solvent and added to the prepolymer. The mixture was stirred at 80° C. for 4 hours to obtain the target product.

[0133] (4) The target product is vacuum dried at 100° C. for 30 hours to obtain an intrinsic antifouling resin, the structural formula of which is shown in FIG. (4):

[0134]

[0135] 2. Preparation of antifouling composite materials:

[0136] (1) The prepared intrinsic antifouling resin, PET base resin, and an auxiliary agent which may be used or not are uniformly mixed to obtain a mixture; the specific amounts are shown in Table 2;

[0137] The mixture is heated to a selected temperature and melt-extruded, and then injection-molded or drawn to obtain an intrinsic antifouling composite material, wherein the selected temperature is 270° C. The characteristic properties are shown in Table 2.

[0138] Example 5

[0139] The preparation of the intrinsic antifouling resin specifically includes:

[0140] (1) preparing the following reactants: polytetrakis dimethyl ether glycol, dicyclohexylmethane-4,4′-diisocyanate, dibutyltin dilaurate (DBTDL), and 2,5-furandioxime, wherein the molecular structure of 2,5-furandioxime is shown in the following formula;

[0141]

[0142] (2) 5 g of dicyclohexylmethane-4,4′-diisocyanate and 0.5 g of dibutyltin dilaurate (DBTDL) were dissolved in a solvent and added to 55 g of polytetrakis dimethyl ether glycol. The mixture was stirred at 70° C. for 5 hours to synthesize a prepolymer.

[0143] (3) 2 g of furan dioxime was dissolved in a solvent and added to the prepolymer. The mixture was stirred at 80° C. for 5 hours to obtain the target product.

[0144] (4) The target product is vacuum dried at 90° C. for 24 hours to obtain an intrinsic antifouling resin, the structural formula of which is shown in FIG. (5):

[0145]

[0146] 2. Preparation of antifouling composite materials:

[0147] (1) The prepared intrinsic antifouling resin, PET base resin, and an auxiliary agent which may be used or not are uniformly mixed to obtain a mixture; the specific amounts are shown in Table 2;

[0148] The mixture is heated to a selected temperature and melt-extruded, and then injection-molded or drawn to obtain an intrinsic antifouling composite material, wherein the selected temperature is 260° C. The characteristic properties are shown in Table 2.

[0149] Example 6

[0150] The preparation of the intrinsic antifouling resin specifically includes:

[0151] (1) preparing the following reactants: poly(ethylene adipate), isophorone diisocyanate, dibutyltin dilaurate (DBTDL), and 2,5-furandioxime, wherein the molecular structure of 2,5-furandioxime is shown in the following formula;

[0152]

[0153] (2) 5 g of isophorone diisocyanate and 0.5 g of dibutyltin dilaurate (DBTDL) were dissolved in a solvent, added to 65 g of poly(ethylene adipate), and stirred at 70° C. for 5 hours to synthesize a prepolymer.

[0154] (3) 2 g of furan dioxime was dissolved in a solvent and added to the prepolymer. The mixture was stirred at 70° C. for 5 hours to obtain the target product.

[0155] (4) The target product is vacuum dried at 90° C. for 48 hours to obtain an intrinsic antifouling resin, the structural formula of which is shown in FIG. (6):

[0156]

[0157] 2. Preparation of antifouling composite materials:

[0158] (1) The prepared intrinsic antifouling resin, PET base resin, and an auxiliary agent which may be used or not are uniformly mixed to obtain a mixture; the specific amounts are shown in Table 2;

[0159] The mixture is heated to a selected temperature and melt-extruded, and then injection-molded or drawn to obtain an intrinsic antifouling composite material, wherein the selected temperature is 260° C. The characteristic properties are shown in Table 2.

[0160] Example 7

[0161] The preparation of the intrinsic antifouling resin specifically includes:

[0162] (1) preparing the following reactants: polytetrakis dimethyl ether glycol, dicyclohexylmethane-4,4′-diisocyanate, dibutyltin dilaurate (DBTDL), 2,5-furandioxime, wherein the molecular structure of 2,5-furandioxime is as shown below, wherein the metal is Cu;

[0163]

[0164] (2) 5 g of dicyclohexylmethane-4,4′-diisocyanate and 0.5 g of dibutyltin dilaurate (DBTDL) were dissolved in a solvent and added to 55 g of polytetrakis dimethyl ether glycol. The mixture was stirred at 70° C. for 5 hours to synthesize a prepolymer.

[0165] (3) 4 g of furan dioxime was dissolved in a solvent and added to the prepolymer. The mixture was stirred at 80° C. for 5 hours to obtain the target product.

[0166] (4) The target product is vacuum dried at 90° C. for 48 hours to obtain an intrinsic antifouling resin, the structural formula of which is shown in FIG. (7):

[0167]

[0168] 2. Preparation of antifouling composite materials:

[0169] (1) The prepared intrinsic antifouling resin, PET base resin, and an auxiliary agent which may be used or not are uniformly mixed to obtain a mixture; the specific amounts are shown in Table 2;

[0170] The mixture is heated to a selected temperature and melt-extruded, and then injection-molded or drawn to obtain an intrinsic antifouling composite material, wherein the selected temperature is 270° C. The characteristic properties are shown in Table 2.

[0171] Table 2 Raw material composition and performance test results of various antibacterial and antifouling PET products in the embodiments of the present invention

[0172]

[0173]

[0174] Note: The data shown in columns D and G in Table 1 are the average values ​​after testing multiple samples;

[0175] Comparative Example 1

[0176] The method is the same as that of Example 1, except that the antifouling composite material does not contain antifouling resin; the specific amount used and the characterization properties are shown in Table 2.

[0177] Comparative Example 2

[0178] 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 specific dosage and characterization properties are shown in Table 2.

[0179] Comparative Example 3

[0180] 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 specific amount used and the characterization properties are shown in Table 2.

[0181] Comparative Example 4

[0182] The method is the same as that in Example 1, except that the antifouling resin in Example 1 is replaced by a conventional inorganic antifouling agent cuprous oxide and an organic antifouling agent copper pyrithione (the mass ratio of the two is 1:1); the specific dosage and characterization properties are shown in Table 3.

[0183] Table 3 Raw material composition and performance test results of various antifouling PET products in comparative examples of the present invention

[0184]

[0185]

[0186] Note: The data shown in columns D and G in Table 1 are the average values ​​after testing multiple samples;

[0187] It can be seen from Table 3 that when the amount of inorganic antifouling agent nano cuprous oxide added exceeds 3%, the PET composite material tends to become brittle and even cannot be drawn into strips, so the maximum addition amount is selected to be 3%. The poor 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 by this method has many restrictions on traditional organic and inorganic antifouling agents.

[0188] For example, in a typical application case, a multi-layer structure can be provided, see Figure 2As shown, the multilayer structure includes a plurality of antifouling material layers 1 stacked and arranged, wherein the antifouling material layers are 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.

[0189] The antifouling and anticorrosion properties of the multilayer structure were tested, and the results showed that the antifouling performance of the multilayer structure was significantly improved compared with that when PET antifouling material was used alone.

[0190] 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.

[0191] 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 environmentally friendly antifouling composite material, characterized in that: The raw materials of the antifouling composite material include base resin, antifouling resin and auxiliary agents which can be used or not; The antifouling resin includes a compound having a structure as shown in formula (I): Wherein, X is 5 to 5000, R1 is a polymer soft segment, the polymer soft segment is derived from a soft segment polymer, and the soft segment polymer includes any one or more polymers selected from tetrakis dimethyl ether glycol, polycaprolactone alcohol, poly(ethylene adipate), polyhydroxyalkanoate, and bisphenol A polyoxypropylene ether as shown in the following formula; R2 is derived from any of the following structural residues: Wherein, the values ​​of x and y are x=y and are integers between 1 and 3, and M is selected from Cu, Zn or Ag; R3 is a polyisocyanate segment, and the polyisocyanate segment is derived from a polyisocyanate residue, and the polyisocyanate includes any one or more combinations of diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, naphthalene 1,5-diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, meta-xylylene diisocyanate, tetramethyl meta-xylylene diisocyanate, 1,4-cyclohexane diisocyanate, methylcyclohexane diisocyanate, 1,4-phenylene diisocyanate, norbornane dimethylene isocyanate, and L-lysine diisocyanate.

2. The environmentally friendly antifouling composite material according to claim 1, characterized in that: The antifouling resin includes a compound having a structure as shown in any one of formula (II) to formula (VII): Among them, n is 1 to 100000.

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

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

5. The environmentally friendly antifouling composite material according to claim 1, characterized in that: The content of the antifouling resin in the antifouling composite material is below 20 wt %, preferably 10 to 15 wt %.

6. The environmentally friendly antifouling composite material according to claim 1, characterized in that: The anti-fouling composite material has a killing rate of more than 90% on Escherichia coli.

7. The method for preparing the environmentally friendly antifouling composite material according to any one of claims 1 to 6, characterized in that: include: The antifouling resin, the base resin, and the auxiliary agent which may be used or not used are uniformly mixed to obtain a mixture; The mixture is heated to a selected temperature and melted and extruded, and then injection molded or drawn to obtain the environmentally friendly antifouling composite material.

8. The preparation method according to claim 7, characterized in that: The selected temperature is 240°C to 280°C, preferably 240°C to 260°C.

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 environmentally friendly antifouling composite material according to any one of claims 1 to 6.

10. Use of the environmentally friendly antifouling composite material according to any one of claims 1 to 6 in the preparation of a marine aquaculture system, a cable or a pipe network system.

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