Environment-friendly anti-fouling polyethylene glycol terephthalate composite material, multi-layer structure and application of multi-layer structure

Abstract

The invention discloses a polyethylene glycol terephthalate environment-friendly antifouling composite material and application thereof. The raw materials of the environment-friendly anti-fouling composite material of the polyethylene glycol terephthalate comprise PET matrix resin, anti-fouling resin and an auxiliary agent which can be selectively used or not used, and the anti-fouling resin has a structure as shown in the following formula: # imgabs0 #. The environment-friendly intrinsic anti-fouling composite material provided by the invention has excellent anti-fouling and antibacterial properties and is easy to prepare; the anti-fouling material can be prepared only by blending the anti-fouling resin and the 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 by melting and blending the anti-fouling composite material and intrinsic anti-fouling resin, so that the ecological environment problem caused by precipitation of the anti-fouling agent of the traditional anti-fouling material is avoided; the antifouling composite material disclosed by the invention can well meet the antifouling requirements of mariculture facilities, cables, pipeline systems and the like.

Description

Technical Field

[0001] The invention relates to an environmentally friendly antifouling composite material of polyethylene terephthalate (PET), and in particular to a material capable of improving the antifouling performance of polyethylene terephthalate, as well as a multilayer structure based on the antifouling material and its use, 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 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 they have unstable corrosion rates 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 of polyethylene terephthalate and its application, 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 environmentally friendly antifouling composite material of polyethylene terephthalate, wherein the raw materials of the composite material include a PET base resin, an antifouling resin, and an auxiliary agent that can be used or not, and the antifouling resin has a structure as shown in formula (I):

[0006]

[0007] Among them, X is 5 to 5000, R 1 Select any one of the following structures:

[0008]

[0009] Wherein, n∶m∶p∶q=75~95∶0.5~25∶0.5~24.5∶0.5~24, and the wavy lines represent the bond connections;

[0010] R 2 Select any one of the following structures:

[0011]

[0012] Wherein, the values ​​of x and y are x=y, and x and y are integers between 0 and 3, M is selected from Cu, Zn or Ag, and the wavy line represents the bond connection;

[0013] R 3 A residue derived from a polyisocyanate, wherein the polyisocyanate includes any one or a combination of two or more of diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, 1,5-naphthalene 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] R 4 Residues derived from 4,4'-diaminodiphenyl disulfide and / or 4,4'-dihydroxydiphenyl disulfide.

[0015] The present invention also provides a method for preparing the aforementioned polyethylene terephthalate environment-friendly antifouling composite material, which comprises:

[0016] 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;

[0017] The mixture is heated to a selected temperature for melt extrusion, and then injection molding or drawing is performed to obtain the polyethylene terephthalate environmentally friendly antifouling composite material, wherein the selected temperature is 240° C. to 280° C.

[0018] 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 polyethylene terephthalate environment-friendly antifouling composite material.

[0019] The present invention also provides the use of the aforementioned polyethylene terephthalate environmentally friendly antifouling composite material in the preparation of a marine aquaculture system, a cable or a pipe network system.

[0020] Compared with the prior art, the present invention has the following beneficial effects:

[0021] (1) The present invention composites the antifouling resin with PET resin. Since the antifouling resin has good compatibility with PET resin, the antifouling resin can be well dispersed in the PET matrix resin, and will not separate from the matrix resin and precipitate during long-term service. The environmentally friendly antifouling composite material of polyethylene terephthalate has excellent antibacterial and antifouling properties and a longer service life.

[0022] (2) The polyethylene terephthalate environmentally friendly antifouling composite material of the present invention is easy to prepare. The PET antifouling material with intrinsic antifouling performance 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

[0023] 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.

[0024] Figure 1 is the hydrogen nuclear magnetic resonance spectrum of the sulfobetaine-modified polydimethylsiloxane prepared in Example 1 of the present invention;

[0025] Figure 2 is a hydrogen nuclear magnetic resonance spectrum of the antifouling resin prepared in Example 1 of the present invention;

[0026] Figure 3 A schematic diagram of a multilayer film structure in an application example of the present invention is shown;

[0027] Explanation of reference numerals: 1 - antifouling material layer. DETAILED DESCRIPTION

[0028] 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 other characteristics and is widely used in the fields of mesh, packaging, pipelines, etc. Based on the good stability of PET itself, it is feasible to prepare PET functional materials with excellent antifouling properties by adding antifouling resins and / or other additives for compounding and modification.

[0029] 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.

[0030] An aspect of an embodiment of the present invention provides a polyethylene terephthalate environment-friendly antifouling composite material, the raw materials of which include a PET base resin, an antifouling resin, and an auxiliary agent that can be used or not, wherein the antifouling resin includes a compound having a structure as shown in formula (I):

[0031]

[0032] Among them, X is 5 to 5000, R 1 Select any one of the following structures:

[0033]

[0034] Wherein, n∶m∶p∶q=75~95∶0.5~25∶0.5~24.5∶0.5~24, and the wavy lines represent the bond connections;

[0035] R 2 Select any one of the following structures:

[0036]

[0037] Wherein, the values ​​of x and y are x=y, and x and y are integers between 0 and 3, M is selected from Cu, Zn or Ag, and the wavy line represents the bond connection;

[0038] R 3 A residue derived from a polyisocyanate, wherein the polyisocyanate includes any one or a combination of two or more of diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, 1,5-naphthalene 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;

[0039] R 4 Residues derived from 4,4'-diaminodiphenyl disulfide and / or 4,4'-dihydroxydiphenyl disulfide.

[0040] In some embodiments, the antifouling resin includes a compound having a structure as shown in any one of Formula (II) to Formula (V):

[0041]

[0042]

[0043] Among them, n∶m∶p∶q=75~95∶0.5~25∶0.5~24.5∶0.5~24.

[0044] In some embodiments, the method for preparing the antifouling resin of the present invention comprises:

[0045] A prepolymerization system comprising polyisocyanate, zwitterion-modified polydimethylsiloxane, a catalyst and a solvent is subjected to a prepolymerization reaction to prepare a prepolymer;

[0046] And, 4,4'-diaminodiphenyl disulfide and / or 4,4'-dihydroxydiphenyl disulfide, furan dioxime and the prepolymer are mixed and reacted to prepare the antifouling resin.

[0047] Further, the polyisocyanate includes any one or a combination of two or more of diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, 1,5-naphthalene 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.

[0048] Furthermore, the zwitterion-modified polydimethylsiloxane is selected from any one of the following structures:

[0049]

[0050]

[0051] Among them, n∶m∶p∶q=75~95∶0.5~25∶0.5~24.5∶0.5~24.

[0052] Furthermore, the furan dioxime is selected from any one or a combination of two or more of the following structures:

[0053]

[0054] The values ​​of x and y are x=y, and x and y are integers between 0 and 3, and M is selected from Cu, Zn or Ag.

[0055] 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.

[0056] Furthermore, the solvent includes any one or a combination of two or more 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.

[0057] Furthermore, the molar ratio of the polyisocyanate, the zwitterion-modified polydimethylsiloxane and the catalyst is 1-4:1:0.02.

[0058] Furthermore, the molar ratio of the 4,4'-diaminodiphenyl disulfide and / or 4,4'-dihydroxydiphenyl disulfide, furan dioxime and the prepolymer is 0.5-2:0.5-2:2-5.

[0059] Furthermore, the prepolymerization reaction temperature is 50°C to 90°C, preferably 70°C.

[0060] Furthermore, the prepolymerization reaction time is 3 h to 12 h, preferably 5 h.

[0061] Furthermore, the preparation method comprises: mixing 4,4′-diaminodiphenyl disulfide and / or 4,4′-dihydroxydiphenyl disulfide, furan dioxime and a solvent, adding the prepolymer, and reacting at 50°C to 90°C for 3h to 12h, and then drying to obtain the antifouling resin.

[0062] Furthermore, the preparation method comprises: mixing 4,4′-diaminodiphenyl disulfide and / or 4,4′-dihydroxydiphenyl disulfide, furan dioxime and a solvent, adding the prepolymer, and reacting at 70° C. for 5 hours, and then vacuum drying the obtained product at 90° C. for 24 hours to obtain the antifouling resin.

[0063] In some embodiments, the polyethylene terephthalate environmentally friendly antifouling composite material is prepared by adding a certain amount of antifouling resin to the PET matrix resin and melt blending. This method can effectively reduce the ecological risks caused by the dissolution of traditional metal compound antifouling resins.

[0064] In some embodiments, the auxiliary agent includes any one or a combination of two or more of an antioxidant, a lubricant, an anti-ultraviolet aging agent, a pigment, etc., but is not limited thereto.

[0065] Furthermore, the polyethylene terephthalate environmentally friendly antifouling composite material includes a PET matrix resin, an antioxidant, a lubricant, an antifouling resin, and the like.

[0066] 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.

[0067] Specifically, the lubricant includes any one or more combinations of montanic acid esters / salts, stearates (such as calcium stearate), fatty amides or polyol esters, but is not limited thereto.

[0068] In some embodiments, the content of the antifouling resin in the polyethylene terephthalate environment-friendly antifouling composite material is below 20 wt %, preferably below 15 wt %, and particularly preferably 5 wt % to 10 wt %.

[0069] The antifouling resin provided in the above embodiments of the present invention has excellent antifouling performance and can be evenly dispersed in PET resin, and has good compatibility with PET resin, and has good stability in the prepared PET antifouling material, and is suitable for preparing PET antifouling materials with intrinsic antifouling function.

[0070] In some embodiments, the antifouling composite material has a killing rate of Escherichia coli of more than 90%.

[0071] Accordingly, another aspect of the embodiments of the present invention provides a method for preparing an environmentally friendly antifouling composite material of polyethylene terephthalate, comprising:

[0072] 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;

[0073] The mixture is heated to a selected temperature for melt extrusion, and then injection molding or drawing is performed to obtain the polyethylene terephthalate environmentally friendly antifouling composite material, wherein the selected temperature is 240° C. to 280° C.

[0074] In some embodiments, the selected temperature is 240°C to 260°C.

[0075] The environmentally friendly antifouling composite material of polyethylene terephthalate in the present invention is simple 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. 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.

[0076] 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 polyethylene terephthalate environment-friendly antifouling composite material.

[0077] Furthermore, another aspect of the embodiments of the present invention provides the use of the aforementioned polyethylene terephthalate environmentally friendly antifouling composite material in manufacturing marine aquaculture systems, cables or pipe network systems, etc.

[0078] The polyethylene terephthalate environment-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.

[0079] 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.

[0080] For example, in the following examples, the resins, additives, pigments, etc. involved can all be purchased from conventional biochemical reagent companies.

[0081] In the following embodiments, the PET antifouling 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 additives 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.

[0082] For example, in the following examples, the components can be melt-blended and then the PET antifouling material can be prepared using methods including but not limited to injection molding, drawing, and the like.

[0083] In the following examples, the rating standards for the hanging sheet performance of the PET samples with antifouling properties are shown in Table 1.

[0084] Table 1

[0085]

[0086]

[0087] Example 1

[0088] 1. The preparation of antifouling resin specifically includes:

[0089] (1) preparing the following reactants: isophorone diisocyanate, dibutyltin dilaurate (DBTDL), furan dioxime, 4,4′-diaminodiphenyl disulfide, tetrahydrofuran, wherein furan dioxime is selected from formula A, and x=y=1;

[0090]

[0091] (2) 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 polydimethylsiloxane. The product had a hydrogen nuclear magnetic resonance spectrum as shown in the attached figure. Figure 1 Its structural formula is shown below:

[0092]

[0093] (3) 5 g of isophorone diisocyanate and 0.1 g of dibutyltin dilaurate (DBTDL) were dissolved in tetrahydrofuran and added to 60 g of sulfobetaine-modified polydimethylsiloxane. The mixture was stirred at 70° C. for 5 h to synthesize a prepolymer.

[0094] (4) Dissolve 2 g of furan dioxime and 2 g of 4,4′-diaminodiphenyl disulfide in tetrahydrofuran and add the mixture to the prepolymer. Stir at 70° C. for 5 h to obtain the target product.

[0095] (5) The target product was vacuum dried at 90° C. for 24 h to obtain an antifouling resin, the structural formula of which is shown below:

[0096]

[0097] The nuclear magnetic resonance hydrogen spectrum of the prepared antifouling resin is as follows Figure 2 As shown, the successful synthesis of the product was demonstrated.

[0098] 2. Preparation of environmentally friendly antifouling composite materials of polyethylene terephthalate:

[0099] (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;

[0100] The mixture is heated to a selected temperature and melt-extruded, and then injection-molded or drawn to obtain a polyethylene terephthalate environmentally friendly antifouling composite material, wherein the selected temperature is 260° C. The characterization properties are shown in Table 2.

[0101] Example 2

[0102] 1. The preparation of antifouling resin specifically includes:

[0103] (1) preparing the following reactants: isophorone diisocyanate, dibutyltin dilaurate (DBTDL), furan dioxime, 4,4′-dihydroxydiphenyl disulfide, tetrahydrofuran, wherein furan dioxime is selected from formula A, and x=y=1;

[0104]

[0105] (2) 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 β-propiolactone was added dropwise to the system and reacted at room temperature for 24 h to obtain carboxybetaine-modified polydimethylsiloxane, the structural formula of which is shown below:

[0106]

[0107] (3) 4.5 g of isophorone diisocyanate and 0.1 g of dibutyltin dilaurate (DBTDL) were dissolved in a solvent and added to 55 g of carboxybetaine-modified polydimethylsiloxane, and stirred at 70° C. for 5 h to synthesize a prepolymer.

[0108] (4) 3 g of furan dioxime and 3 g of 4,4′-dihydroxydiphenyl disulfide were dissolved in a solvent and added to the prepolymer. The mixture was stirred at 70° C. for 5 h to obtain the target product.

[0109] (5) The target product was vacuum dried at 90° C. for 24 h to obtain an antifouling resin, the structural formula of which is shown below:

[0110]

[0111] 2. Preparation of environmentally friendly antifouling composite materials of polyethylene terephthalate:

[0112] (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;

[0113] The mixture is heated to a selected temperature for melt extrusion, and then injection molding or drawing is performed to obtain a polyethylene terephthalate environmentally friendly antifouling composite material, wherein the selected temperature is 250° C. The characterization properties are shown in Table 2.

[0114] Example 3

[0115] 1. The preparation of antifouling resin specifically includes:

[0116] (1) preparing the following reactants: isophorone diisocyanate, dibutyltin dilaurate (DBTDL), furan dioxime, 4,4′-dihydroxydiphenyl disulfide, tetrahydrofuran, wherein furan dioxime is selected from formula A, and x=y=1;

[0117]

[0118] (2) 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 polydimethylsiloxane, the structural formula of which is shown below:

[0119]

[0120] (3) 7 g of isophorone diisocyanate and 0.1 g of dibutyltin dilaurate (DBTDL) were dissolved in a solvent and added to 66 g of phosphorylcholine betaine-modified polydimethylsiloxane, and stirred at 70° C. for 5 h to synthesize a prepolymer.

[0121] (4) 3.5 g of furan dioxime and 3.3 g of 4,4′-dihydroxydiphenyl disulfide were dissolved in tetrahydrofuran and added to the prepolymer. The mixture was stirred at 70° C. for 5 h to obtain the target product.

[0122] (5) The target product was vacuum dried at 90° C. for 24 h to obtain an antifouling resin, the structural formula of which is shown below:

[0123]

[0124] 2. Preparation of environmentally friendly antifouling composite materials of polyethylene terephthalate:

[0125] (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;

[0126] The mixture is heated to a selected temperature and melt-extruded, and then injection-molded or drawn to obtain a polyethylene terephthalate environmentally friendly antifouling composite material, wherein the selected temperature is 240° C. The characterization properties are shown in Table 2.

[0127] Example 4

[0128] 1. The preparation of antifouling resin specifically includes:

[0129] (1) preparing the following reactants: isophorone diisocyanate, dibutyltin dilaurate (DBTDL), furan dioxime, 4,4′-dihydroxydiphenyl disulfide, tetrahydrofuran, wherein furan dioxime is selected from formula A, and x=y=0;

[0130]

[0131] (2) 30 g of vinyl-modified hydroxy silicone oil, 2 g of 3-dimethylamino-1-propanethiol and 1 g of thiolated methacryloyloxyethyl phosphorylcholine were uniformly mixed and 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 reacted at room temperature for 24 h to obtain carboxybetaine / sulfobetaine / phosphorylcholine-modified polydimethylsiloxane, the structural formula of which is shown below:

[0132]

[0133] (3) 7.5 g of isophorone diisocyanate and 0.2 g of dibutyltin dilaurate (DBTDL) were dissolved in a solvent and added to 78 g of carboxybetaine / sulfobetaine / phosphorylcholine-modified polydimethylsiloxane, and stirred at 70° C. for 5 h to synthesize a prepolymer.

[0134] (4) 3.3 g of furan dioxime and 2.2 g of 4,4′-dihydroxydiphenyl disulfide were dissolved in a solvent and added to the prepolymer. The mixture was stirred at 70° C. for 5 h to obtain the target product.

[0135] (5) The target product was vacuum dried at 90° C. for 24 h to obtain an antifouling resin, the structural formula of which is shown below:

[0136]

[0137] 2. Preparation of environmentally friendly antifouling composite materials of polyethylene terephthalate:

[0138] (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;

[0139] The mixture is heated to a selected temperature and melt-extruded, and then injection-molded or drawn to obtain a polyethylene terephthalate environmentally friendly antifouling composite material, wherein the selected temperature is 260° C. The characterization properties are shown in Table 2.

[0140] Comparative Example 1

[0141] The method is the same as that of Example 1, except that the composite material does not contain antifouling resin. The characterization properties are shown in Table 2.

[0142] Comparative Example 2

[0143] The method is the same as that of Example 1, except that the antifouling resin in Example 1 is replaced by conventional inorganic antifouling agent cuprous oxide. The characterization properties are shown in Table 2.

[0144] Comparative Example 3

[0145] The method is the same as that of Example 1, except that the conventional organic antifouling agent copper pyrithione is used to replace the antifouling resin in Example 1. The characterization properties are shown in Table 2.

[0146] Comparative Example 4

[0147] 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 cuprous oxide and an organic antifouling agent copper pyrithione composition (and the mass ratio of nano cuprous oxide to copper pyrithione in the composition is 3:5). The characterization properties are shown in Table 2.

[0148] Table 2 Raw material composition and performance test results of various antibacterial and antifouling PET products in Examples 1-4 of the present invention and Comparative Examples 1-4

[0149]

[0150]

[0151] Note: The data shown in columns D and G in Table 2 are the average values ​​after testing multiple samples;

[0152] It can be seen from Table 2 that although the inorganic antifouling agent nano cuprous oxide in Comparative Example 2 is 3% and has a good antibacterial effect, during the test, when its addition amount exceeds 3%, the PET composite material tends to become brittle and even cannot be drawn into strips, so the maximum addition amount of nano cuprous oxide is 3%; the poor effect of the organic antifouling agent copper pyrithione is mainly due to the decomposition of copper pyrithione under the high temperature 260°C product preparation conditions, resulting in poor antibacterial and antifouling properties. Therefore, the antifouling PET composite material prepared by this method has many restrictions on the addition of traditional organic and inorganic antifouling agents.

[0153] For example, in a typical application case, a multi-layer structure can be provided, see Figure 3 As 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 environment-friendly antifouling composite material, and the preparation method can refer to the preparation method of the aforementioned polyethylene terephthalate environment-friendly antifouling composite material. The plurality of antifouling material layers can be compounded by bonding, pressing, etc. to obtain the multilayer structure.

[0154] 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 considered to be level 0 after 2 months.

[0155] In addition, the inventors of this case also referred to the aforementioned embodiments and conducted repeated verifications with other raw materials, process operations, and process conditions described in this specification, and obtained relatively ideal results.

[0156] 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. A polyethylene terephthalate environmentally friendly antifouling composite material, characterized in that: The raw materials of the composite material include PET matrix resin, antifouling resin and auxiliary agents that can be used or not, and the antifouling resin has a structure as shown in formula (I): Wherein, X is 5 to 5000, and R1 is selected from any one of the following structures: Wherein, n∶m∶p∶q=75~95∶0.5~25∶0.5~24.5∶0.5~24, and the wavy lines represent the bond connections; R2 is selected from any one of the following structures: Wherein, the values ​​of x and y are x=y, and x and y are integers between 0 and 3, M is selected from Cu, Zn or Ag, and the wavy line represents the bond connection; R3 is derived from the residue of a polyisocyanate, wherein the polyisocyanate includes any one or a combination of two or more of diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, 1,5-naphthalene 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; R4 is derived from the residue of 4,4'-diaminodiphenyl disulfide and / or 4,4'-dihydroxydiphenyl disulfide.

2. The environmentally friendly antifouling composite material of polyethylene terephthalate 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 (V): Among them, n∶m∶p∶q=75~95∶0.5~25∶0.5~24.5∶0.5~24.

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

4. The environmentally friendly antifouling composite material of polyethylene terephthalate according to claim 1, characterized in that: The content of the antifouling resin in the polyethylene terephthalate environment-friendly antifouling composite material is below 20wt%.

5. The environmentally friendly antifouling composite material of polyethylene terephthalate according to claim 4, characterized in that: The content of the antifouling resin in the polyethylene terephthalate environment-friendly antifouling composite material is less than 15wt%.

6. The environmentally friendly antifouling composite material of polyethylene terephthalate according to claim 1, characterized in that: The killing rate of the polyethylene terephthalate environment-friendly antifouling composite material on Escherichia coli is above 90%.

7. The method for preparing the environmentally friendly antifouling composite material of polyethylene terephthalate according to any one of claims 1 to 6, characterized in that: include: 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; The mixture is heated to a selected temperature for melt extrusion, and then injection molding or drawing is performed to obtain the polyethylene terephthalate environmentally friendly antifouling composite material, wherein the selected temperature is 240° C. to 280° C.

8. The preparation method according to claim 7, characterized in that: The selected temperature is 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 polyethylene terephthalate environment-friendly antifouling composite material according to any one of claims 1 to 6.

10. Use of the polyethylene terephthalate 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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