Marine organism prevention high-density polyethylene composite material and preparation method thereof

Abstract

The invention belongs to the technical field of marine organism prevention materials, and particularly discloses a marine organism prevention high-density polyethylene composite material and a preparation method thereof. The preparation method comprises the following steps: firstly, preparing a Ti < 3 > C < 2 > T < x > MXene (at) Cu2O composite material based on an in-situ growth method; the material is composed of two-dimensional Ti < 3 > C < 2 > T < x > MXene and Cu2O nanoparticles which grow on the surface of the two-dimensional Ti < 3 > C < 2 > T < x > MXene in situ and have bactericidal performance, the nanocomposite has the enhancement effect of the nanoparticles and the two-dimensional material on macromolecules at the same time, and good enhancement and marine organism prevention effects are guaranteed. Besides, PE-g-MAH is added in the formula to serve as a compatibilizer, in an HDPE amorphous region, a large number of hydroxyl groups on the surface of Ti3C2Tx MXene coated Cu2O are connected with acid anhydride groups in the compatibilizer PE-g-MAH through chemical ester bonds, a polyethylene chain of PE-g-MAH is mixed and dissolved with an HDPE matrix, and therefore the mechanical strength of the material can be improved in the amorphous region at the same time. Cu2O growing on the surface of MXene in situ can release cuprous ions after seawater permeates, and marine organisms such as algae spores, bacteria and barnacles and mussels are killed.

Description

Technical Field

[0001] The invention belongs to the technical field of marine biodegradable materials, and in particular relates to a marine biodegradable high-density polyethylene composite material and a preparation method thereof. Background Art

[0002] In marine engineering, especially on structures such as offshore platform jackets and offshore wind power steel pipe piles, the attachment and growth of marine organisms is a long-standing problem. These marine organisms may not only threaten the stability of the structure, but also affect the normal operation and maintenance of the equipment. In response to this problem, a variety of methods and measures have been adopted at home and abroad to prevent and control it.

[0003] At present, the main methods of preventing marine organisms include the use of anti-marine organism coatings, encapsulated anti-marine organism methods, electrochemical antifouling and mechanical prevention methods. Anti-marine organism coatings prevent marine organisms from attaching by forming a protective film on the surface of the structure. However, this method is not effective in a static environment, and the durability and environmental protection of the coating still need to be further improved. The encapsulated anti-marine organism method prevents marine organisms from attaching by wrapping a layer of anti-marine organism material, but this method is expensive and has certain operational difficulties in practical applications. The electrochemical antifouling method uses the principle of electrolysis to produce toxic substances to kill or drive away marine organisms. However, this method is mainly suitable for semi-closed pipeline systems and is not effective for open marine environments. Mechanical prevention methods mainly use physical means to remove marine organisms attached to structures. At present, commonly used cleaning technologies include high-pressure water washing technology, cavitation jet washing technology and hydraulic grinding technology. Although these technologies can remove marine organisms to a certain extent, they have problems such as high prices and high construction risks. In particular, mechanical control methods that mainly rely on manual cleaning or ROV (remotely operated underwater vehicle) are not only costly, but also pose greater risks when operating in deep sea or severe weather conditions.

[0004] In view of the various defects of the existing methods, a new method of preventing marine organisms has gradually attracted attention in recent years. This method uses natural marine phenomena such as tides and waves as driving forces. By designing a special anti-fouling device, the device continuously hits the jacket frame, pile legs and other components under the action of waves, thereby mechanically preventing marine organisms from attaching, such as patents ZL 202222132298.4, ZL 202222130500X, ZL 2023222234256, ZL 20232222211589 and other patents. This new anti-fouling device has the advantages of low cost, environmental protection, easy maintenance, and can adapt to various marine environments.

[0005] However, since this device is used in seawater for a long time, the mechanical properties of the roller material are required to be high, and the device itself must not grow marine organisms. Therefore, it is necessary to develop a special material with high strength and anti-marine organism function to meet the use requirements of this new anti-fouling device. Summary of the invention

[0006] In order to solve the above technical problems, the present invention proposes a marine life-proof high-density polyethylene composite material and a preparation method thereof, so as to improve the mechanical strength and marine life-proof performance of the polyethylene material, so that it can become a special marine life-proof material.

[0007] In order to achieve the above object, the present invention is achieved through the following technical solutions:

[0008] A marine biorepellent high-density polyethylene composite material, comprising a Ti3C2Tx MXene@Cu2O composite material, a polyethylene matrix, a compatibilizer, and an antioxidant; the compatibilizer is polyethylene grafted maleic anhydride HDPE-g-MAH.

[0009] The density of the polyethylene matrix is ​​0.94-0.96 g / cm 3 .

[0010] The present invention also provides a method for preparing the above-mentioned marine biorepellent high-density polyethylene composite material, comprising the following steps:

[0011] S1. Preparation of Ti3C2Tx MXene@Cu2O composite material: CuCl2 and amine hydrochloride (NH2OH·HCl) are in situ hydrolyzed, precipitated and dried on the surface of Ti3C2Tx MXene nanosheets, and then treated with a plasma generator to generate a large number of hydroxyl groups on the surface to prepare Ti3C2Tx MXene@Cu2O composite material;

[0012] S2. Preparation of high-density polyethylene composite materials: mixing the Ti3C2Tx MXene@Cu2O composite material, polyethylene matrix, polyethylene grafted maleic anhydride, antioxidant and processing aid, and injection molding the composite material using an injection molding machine to obtain a high-density polyethylene composite material.

[0013] Preferably, the specific steps of preparing the Ti3C2Tx MXene@Cu2O composite material in S1 are: under constant temperature conditions, adding CuCl2 solution and sodium dodecyl sulfate (SDS) powder to deionized water, adding Ti3C2Tx MXene nanosheets to the solution after the powder is dissolved, adding NaOH after ultrasonic water bath treatment, the solution immediately turns blue, and then quickly injecting NH2OH·HCl, ultrasonically treating the solution and then centrifuging it, finally washing the precipitate with an ethanol / water mixture, and drying it under vacuum to obtain the Ti3C2Tx MXene@Cu2O composite material.

[0014] Preferably, the constant temperature condition is 35°C; after injecting NH2OH·HCl, the solution is ultrasonically treated for 1 hour to ensure crystal growth, and then centrifuged at 10000 rpm for 5 minutes; finally, the precipitate is washed with an ethanol / water mixture with a volume ratio of 1:1, and vacuum dried at 60°C for 12 hours to obtain a Ti3C2Tx MXene@Cu2O composite material.

[0015] Preferably, the maleic anhydride in the polyethylene grafted maleic anhydride in S2 not only reacts with Ti3C2Tx MXene@Cu2O to form ester bonds, but its polyethylene main chain is miscible with the polyethylene matrix to form chemical bonding sites between organic and inorganic in the mixed system.

[0016] Finally, the present invention provides the use of the above-mentioned marine organism-proof high-density polyethylene composite material in the preparation of a marine organism-proof device.

[0017] The beneficial effects of the present invention are:

[0018] First, a Ti3C2Tx MXene@Cu2O composite material was prepared based on the in-situ growth method. The material consists of two-dimensional Ti3C2Tx MXene and Cu2O nanoparticles with bactericidal properties grown in situ on its surface. The nanocomposite has both the reinforcing effect of nanoparticles and two-dimensional materials on polymers, and is tightly combined without phase separation, thereby ensuring good reinforcing and anti-marine biological effects. In addition, polyethylene grafted maleic anhydride (PE-g-MAH) is added to the formula as a compatibilizer. Through this design, in the HDPE amorphous region, a large number of hydroxyl groups on the surface of Ti3C2Tx MXene@Cu2O are connected to the anhydride groups in the compatibilizer PE-g-MAH through chemical ester bonds, while the polyethylene chains of PE-g-MAH are miscible with the HDPE matrix, thereby improving the mechanical strength of the material in the amorphous region at the same time. The Cu2O grown in situ on the MXene surface can release cuprous ions after seawater penetrates in, killing algae spores, bacteria, and marine organisms such as barnacles and mussels. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings required for describing the embodiments will be briefly introduced below. Obviously, the accompanying drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other accompanying drawings can be obtained based on these accompanying drawings without paying creative work.

[0020] Figure 1 Scanning electron microscope image of the prepared Ti3C2Tx MXene@Cu2O.

[0021] Figure 2 XRD pattern of prepared Ti3C2Tx MXene@Cu2O.

[0022] Figure 3 Infrared spectrum of the prepared Ti3C2Tx MXene@Cu2O.

[0023] Figure 4 Antibacterial test results of Examples 1-6 (af) and Comparative Examples 1-3 (gi). DETAILED DESCRIPTION

[0024] The technical solutions in the embodiments of the present invention will be described clearly and completely below in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all the embodiments.

[0025] 1. Raw materials and reagents

[0026] Cupric chloride (CuCl2, 98%), sodium dodecyl sulfate (SDS, 95%), sodium hydroxide (NaOH, 99%), hydroxylammonium chloride (NH2OH·HCl, 98.5%), Ti3C2Tx Mxene, MacLean. High-density polyethylene, 5000S; polyethylene grafted maleic anhydride (PE-g-MAH), CMG5804; antioxidant 1010, analytical grade.

[0027] 2. The reinforced marine biorepellent high-density polyethylene composite materials of the embodiments and comparative examples of the present invention are prepared by the following preparation method:

[0028] S1. At a constant temperature of 35 °C, 100 mL of deionized water was added to a 250 mL round-bottom flask. Subsequently, 50 mL of 0.1 M CuCl2 solution and 5.0 g of sodium dodecyl sulfate (SDS) powder were introduced under continuous stirring. After the SDS powder was completely dissolved, 5 g of Ti3C2Tx MXene nanosheets were added to the solution, and the solution was transferred to an ultrasonic water bath for 5 minutes. After that, 2 mL of 1 M NaOH was added, and the solution immediately turned blue. Finally, 8 mL of 0.1 M NH2OH·HCl was quickly injected. The solution was ultrasonicated for 1 hour to ensure crystal growth and then centrifuged at 10,000 rpm for 5 minutes. The precipitate was washed twice with 40 mL of ethanol / water mixture with a volume ratio of 1:1. Finally, the precipitate was washed with 40 mL of ethanol and dried in vacuum at 60 °C for 12 hours to obtain the Ti3C2TxMXene@Cu2O composite material. The electron microscope scanning image of the Ti3C2Tx MXene@Cu2O composite material is shown in Figure 1 As shown, the XRD pattern is Figure 2 As shown, the infrared spectrum is Figure 3 shown.

[0029] S2. High-density polyethylene, Ti3C2Tx MXene@Cu2O, PE-g-MAH, antioxidant and processing aid are mixed, and then the composite material is injection molded at 175°C using an injection molding machine to obtain Ti3C2Tx MXene@Cu2O / HDPE special material.

[0030] Performance test: Tensile strength is tested according to GB / T1040.1-2006 standard. Elongation at break is tested according to GB / T1040.1-2006 standard. Bending strength is tested according to GB / T9341-2008 standard.

[0031] In order to illustrate the present invention, Examples 1-6 and Comparative Examples 1-3 are designed.

[0032] The weight proportions of the components of the reinforced marine biorepellent polyethylene composite materials in Examples 1-6 and Comparative Examples 1-3 are shown in Table 1.

[0033] Table 1 Mass fractions of each component in the reinforced marine biorepellent polyethylene composite material in Examples 1-6 and Comparative Examples 1-3

[0034]

[0035] The 5 / 5 in Ti3C2Tx MXene@Cu2O means that the mass fraction of Ti3C2Tx MXene is 5 parts and the mass fraction of Cu2O is 5 parts.

[0036] The performance test results of the reinforced anti-marine biomass polyethylene composite materials in each embodiment and comparative example according to the above-mentioned method are shown in Table 2.

[0037] Table 2 Test results of various embodiments and comparative examples

[0038] serial number Tensile strength(MPa) Elongation at break (%) Bending strength(MPa) Example 1 31.08 563.1 23.2 Example 2 31.95 682.0 24.3 Example 3 32.83 803.9 25.9 Example 4 33.95 955.3 26.4 Example 5 33.88 910.7 26.2 Example 6 33.64 889.7 26.1 Comparative Example 1 30.99 565.6 23.0 Comparative Example 2 28.29 338.5 21.3 Comparative Example 3 31.58 854.6 25.3

[0039] It can be seen from Examples 1-6 that under the condition of fixed addition of 5 parts of PE-g-MAH compatibilizer and 5 parts of Ti3C2Tx MXene, the elongation at break of HDPE with 5-30 parts of Cu2O attached to Ti3C2Tx MXene is greatly improved. When 5 / 20 parts of Ti3C2Tx MXene@Cu2O are added, the elongation at break is increased from 565.6 of pure HDPE to 955.3%. This is because the in-situ preparation method makes the Cu2O nanoparticles and the two-dimensional Ti3C2Tx MXene nanosheets closely combined, and the presence of PE-g-MAH compatibilizer enhances the interfacial compatibility between the nanocomposite material and the HDPE matrix. Correspondingly, with the increase of Ti3C2Tx MXene@Cu2O content, the tensile strength and flexural strength are significantly improved, but the increase is not as large as the elongation. The tensile strength increased from 30.99Mpa to 33.95Mpa of HDPE+5 / 20Ti3C2Tx MXene@Cu2O, and the flexural strength increased from 23Mpa of pure HDPE to 26.4MPa of HDPE+5 / 20Ti3C2Tx MXene@Cu2O, indicating that the system has significantly improved the strength performance of HDPE. At the same time, we also found that HDPE+5 / 20Ti3C2Tx MXene@Cu2O has the best performance indicators. As the Cu2O content continues to increase, the mechanical properties of the system gradually decrease. This may be because the agglomeration caused by the excessive Cu2O content affects the mechanical properties of the material.

[0040] It can be seen from the comparative example that the mechanical properties of the 5 / 20Ti3C2Tx MXene@Cu2O are significantly lower when 20 parts of Cu2O particles are simply added, indicating that the two-dimensional MXene has a more obvious modification of the mechanical properties of the system. Similarly, although the mechanical properties of the material are also improved by simply adding Ti3C2TxMXene, the mechanical properties are quite different from those of the Ti3C2Tx MXene@Cu2O composite material. The above comparative example shows that the prepared Ti3C2Tx MXene@Cu2O can better improve the mechanical properties of the material than using a single modifier.

[0041] The antibacterial results of the materials were verified by taking Shewanella (S. oneidensis MR-1) which is widely present in the ocean as a representative. The antibacterial performance test results of the reinforced marine biofilm-proof polyethylene composite materials in each embodiment and comparative example were as follows: Figure 1 shown.

[0042] from Figure 4 It can be seen that under the conditions of fixed addition of 5 parts of PE-g-MAH compatibilizer and 5 parts of Ti3C2Tx MXene, the anti-marine biological performance of HDPE with the addition of 5-30 parts of Cu2O attached to Ti3C2Tx MXene gradually increases, among which there is no bacterial growth on the surface of the sample with 30 parts of Cu2O added.

[0043] From the comparative example, it can be seen that the anti-marine biological performance of HDPE alone is poor, and a large number of bacteria grow on the surface of the sample. The anti-marine biological performance of simply adding 20 parts of Cu2O is better, but the antibacterial performance is slightly weaker than the corresponding addition of 5 / 20 parts of Ti3C2Tx MXene@Cu2O, which proves that the introduction of MXene makes the dispersion of Cu2O more uniform, thus having a better antibacterial effect. Similarly, the antibacterial effect of simply adding 5 parts of Ti3C2Tx MXene is also poor. This shows that this combination scheme has a high efficiency antibacterial effect.

[0044] In summary, the composite material of the present invention comprises Ti3C2Tx MXene@Cu2O 、 PE-g-MAH, and HDPE matrix, the modified HDPE has good bending strength, tensile strength and anti-marine biological performance. The raw materials included in the formula are low in cost, and the prepared materials have the advantages of high mechanical strength, good anti-marine biological performance, etc., which is economical and convenient, and has no pollution emissions.

[0045] The preferred embodiments of the present invention disclosed above are only used to help illustrate the present invention. The preferred embodiments do not describe all details in detail, nor do they limit the invention to only the specific embodiments described. Obviously, many modifications and changes can be made according to the content of this specification.

Claims

1. A high-density polyethylene composite material for preventing marine organisms, characterized in that: The composite material comprises a Ti3C2TxMXene@Cu2O composite material, a polyethylene matrix, a compatibilizer, and an antioxidant; the compatibilizer is polyethylene grafted maleic anhydride HDPE-g-MAH.

2. The marine biorepellent high-density polyethylene composite material according to claim 1, characterized in that: The density of the polyethylene matrix is ​​0.94-0.96 g / cm 3 .

3. The method for preparing the marine biorepellent high-density polyethylene composite material according to claim 1, characterized in that: The following steps are involved: S1. Preparation of Ti3C2Tx MXene@Cu2O composite material: CuCl2 and amine hydrochloride (NH2OH·HCl) were in situ hydrolyzed, precipitated and dried on the surface of Ti3C2TxMXene nanosheets, and then treated with a plasma generator to generate a large number of hydroxyl groups on the surface to prepare Ti3C2Tx MXene@Cu2O composite material; S2. Preparation of high-density polyethylene composite materials: mixing the Ti3C2Tx MXene@Cu2O composite material, polyethylene matrix, polyethylene grafted maleic anhydride, antioxidant and processing aid, and injection molding the composite material using an injection molding machine to obtain a high-density polyethylene composite material.

4. The method for preparing the marine biorepellent high-density polyethylene composite material according to claim 3, characterized in that: The specific steps of preparing the Ti3C2Tx MXene@Cu2O composite material in S1 are as follows: under constant temperature conditions, adding CuCl2 solution and sodium dodecyl sulfate (SDS) powder to deionized water, adding Ti3C2Tx MXene nanosheets to the solution after the powder is dissolved, adding NaOH after ultrasonic water bath treatment, the solution immediately turns blue, and then quickly injecting NH2OH·HCl, ultrasonically treating the solution and then centrifuging it, finally washing the precipitate with an ethanol / water mixture, and drying it under vacuum to obtain the Ti3C2Tx MXene@Cu2O composite material.

5. The method for preparing the marine biorepellent high-density polyethylene composite material according to claim 4, characterized in that: The constant temperature condition is 35°C; after injecting NH2OH·HCl, the solution is ultrasonically treated for 1 hour to ensure crystal growth, and then centrifuged at 10000 rpm for 5 minutes; finally, the precipitate is washed with an ethanol / water mixture with a volume ratio of 1:1, and vacuum dried at 60°C for 12 hours to obtain a Ti3C2Tx MXene@Cu2O composite material.

6. The method for preparing the marine biorepellent high-density polyethylene composite material according to claim 3, characterized in that: In the polyethylene-grafted maleic anhydride in S2, in addition to reacting with Ti3C2Tx MXene@Cu2O to form ester bonds, its polyethylene main chain is miscible with the polyethylene matrix, forming chemical bonding sites between organic and inorganic in the mixed system.

7. Use of the anti-marine organism high-density polyethylene composite material prepared according to claim 3 in the preparation of anti-marine organism devices.

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