CN116285063A - A kind of anti-biological adhesion material and its preparation method and anti-biological adhesion floating body - Google Patents

Abstract

The invention belongs to the field of polymer materials, and in particular relates to an anti-biological adhesion material, a preparation method thereof and an anti-biological adhesion floating body. In parts by weight, the raw materials for the preparation of the anti-fouling material provided by the invention include: 70-100 parts of polymer base material, 0.5-5.0 parts of nano-zinc oxide, 0.5 parts of 2-(methoxycarbamoyl) benzimidazole ～3.0 parts, 0.5～3.0 parts of zinc pyrithione, 0.5～3.0 parts of hydrophobic white carbon black, 5～15 parts of copper ion fiber, 0.6～4.0 parts of additives. The invention obtains a material with good anti-biological adhesion ability by optimizing the raw material formula of the polymer material, which can effectively prevent bio-adhesion for a long time; when the material is used as a floating body material, it can effectively reduce the damage to the surface of the floating body Manual cleaning, so as to avoid the negative impact of frequent manual cleaning on the floating body, has a good application prospect in the field of floating body materials for offshore photovoltaic power generation.

Description

A kind of anti-biological adhesion material and its preparation method and anti-biological adhesion floating body

technical field

The invention belongs to the field of polymer materials, and in particular relates to an anti-biological adhesion material, a preparation method thereof and an anti-biological adhesion floating body.

Background technique

Offshore photovoltaic power generation is a new energy utilization method and resource development model, which has the characteristics of high power generation, less land occupation, and easy integration with other industries. Due to the vast ocean area, offshore photovoltaic power generation has sufficient potential. However, the marine water environment is complex, and fouling organisms will attach and grow on the surface of offshore photovoltaic floating bodies, resulting in a decrease in the carrying capacity of the floating body. The maintenance method of manual cleaning is inefficient and expensive, and is not suitable for large-scale photovoltaic power generation systems. Damage to the surface will accelerate the aging of the floating body, increase the tendency of cracking, and affect the service life of the floating body.

Therefore, it is an urgent problem to be solved in this field to develop a floating body material for offshore photovoltaic power generation that can effectively prevent biofouling for a long time.

Contents of the invention

In view of this, the object of the present invention is to provide an anti-fouling material and its preparation method and an anti-fouling floating body. The material provided by the invention has good anti-fouling properties and can effectively prevent long-term fouling. The field of floating body materials has a good application prospect.

The invention provides an anti-fouling material, in parts by weight, its preparation raw materials include:

Preferably, the polymer base material includes high-density polyethylene and polyolefin thermoplastic elastomer.

Preferably, the melt flow rate of the high-density polyethylene under the condition of 190°C and 2.16kg load is 10-20g/10min; the environmental stress cracking resistance of the high-density polyethylene under the condition of 50°C and 10% Igepal The time _F50 is ≥2000h; the Mooney viscosity ML(1+4)121°C of the polyolefin thermoplastic elastomer is ≤20MU; the tear strength of the polyolefin thermoplastic elastomer is ≥25kN/m; the polyolefin thermoplastic elastomer The glass transition temperature of olefinic thermoplastic elastomer is ≤-55°C.

Preferably, the particle size of the nano zinc oxide is 5-20 nm.

Preferably, the specific surface area of the hydrophobic white carbon black is 300-500 m ² /g; the water contact angle of the hydrophobic white carbon black is ≥150°.

Preferably, the matrix material of the copper ion fiber is one or more of polyethylene terephthalate, polyamide and polyether ether ketone; the copper element content in the copper ion fiber is 5000- 50000ppm; the diameter of the copper ion fiber is 0.5-10 μm; the aspect ratio of the copper ion fiber is ≥100.

Preferably, the auxiliary agent includes one or more of coupling agent, dispersant, antioxidant and weather resistance agent.

Preferably, in parts by weight, the preparation raw materials include:

The present invention provides a method for preparing the anti-fouling material described in the above technical solution, comprising the following steps:

The preparation raw materials are melted, blended and extruded to obtain the anti-biological adhesion material.

The present invention provides an anti-bio-adhesion floating body, the surface material of the anti-bio-adhesion floating body is the anti-bio-adhesion material described in the above technical solution.

Compared with the prior art, the invention provides an anti-biological adhesion material, a preparation method thereof and an anti-biological adhesion floating body. In parts by weight, the raw materials for the preparation of the anti-fouling material provided by the invention include: 70-100 parts of polymer base material, 0.5-5.0 parts of nano-zinc oxide, 0.5 parts of 2-(methoxycarbamoyl) benzimidazole ～3.0 parts, 0.5～3.0 parts of zinc pyrithione, 0.5～3.0 parts of hydrophobic white carbon black, 5～15 parts of copper ion fiber, 0.6～4.0 parts of additives. The invention obtains a material with good anti-biological adhesion ability by optimizing the raw material formula of the polymer material, which can effectively prevent bio-adhesion for a long time; when the material is used as a floating body material, it can effectively reduce the damage to the surface of the floating body Manual cleaning, so as to avoid the negative impact of frequent manual cleaning on the floating body, has a good application prospect in the field of floating body materials for offshore photovoltaic power generation.

Detailed ways

The following clearly and completely describes the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only some of the embodiments of the present invention, but not all of them. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without making creative efforts belong to the protection scope of the present invention.

The invention provides an anti-fouling material, in parts by weight, its preparation raw materials include:

In the anti-fouling material provided by the present invention, the polymer base material preferably includes high-density polyethylene and polyolefin thermoplastic elastomer. Wherein, the melt flow rate (190°C, load 2.16kg) of the high-density polyethylene is preferably 10-20g/10min, specifically 10g/10min, 11g/10min, 12g/10min, 13g/10min, 14g/10min, 10min, 15g/10min, 16g/10min, 17g/10min, 18g/10min, 19g/10min or 20g/10min; the environmental stress cracking time F of the high density polyethylene ( ₅₀ ℃, 10% Igepal) is preferably ≥2000h, more preferably 2000-8000h, specifically 2000h, 2500h, 3000h, 3500h, 4000h, 4500h, 5000h, 5500h, 6000h, 6500h, 7000h, 7500h or 8000h.

In the anti-fouling material provided by the present invention, in the polymer base material, the polyolefin thermoplastic elastomer has the advantages of high elasticity of rubber and easy processing of plastics, and has good compatibility with polyolefin, and is suitable for inorganic fillers. It has good tolerance and has good toughening and modifying effects on polyethylene and other materials. In the present invention, the Mooney viscosity ML(1+4)121°C of the polyolefin thermoplastic elastomer is preferably ≤20MU, specifically 10MU, 11MU, 12MU, 13MU, 14MU, 15MU, 16MU, 17MU, 18MU, 19MU or 20MU; the tear strength of the polyolefin thermoplastic elastomer is preferably ≥ 25kN/m, more preferably 25-40kN/m, specifically 25kN/m, 26kN/m, 27kN/m, 28kN/m, 29kN/m, 30kN/m, 31kN/m, 32kN/m, 33kN/m, 34kN/m, 35kN/m, 36kN/m, 37kN/m, 38kN/m, 39kN/m or 40kN/m; The glass transition temperature of the polyolefin thermoplastic elastomer is preferably ≤-55°C, more preferably -55 to -65°C, specifically -55°C, -56°C, -57°C, -58°C, -59°C, -60°C, -61°C, -62°C, -63°C, -64°C or -65°C.

In the anti-fouling material provided by the present invention, the content of the polymer base material in the raw materials can be 70 parts by weight, 71 parts by weight, 72 parts by weight, 73 parts by weight, 74 parts by weight, 75 parts by weight, 76 parts by weight, 77 parts by weight, 78 parts by weight, 79 parts by weight, 80 parts by weight, 81 parts by weight, 82 parts by weight, 83 parts by weight, 84 parts by weight, 85 parts by weight, 86 parts by weight, 87 parts by weight, 88 parts by weight Parts, 89 parts by weight, 90 parts by weight, 91 parts by weight, 92 parts by weight, 93 parts by weight, 94 parts by weight, 95 parts by weight, 96 parts by weight, 97 parts by weight, 98 parts by weight, 99 parts by weight or 100 parts by weight.

In the anti-fouling material provided by the present invention, for the embodiment in which the polymer base material includes high-density polyethylene and polyolefin thermoplastic elastomer, the content of the high-density polyethylene in the raw materials is preferably 60% ~75 parts by weight, specifically 60 parts by weight, 60.9 parts by weight, 61 parts by weight, 62 parts by weight, 63 parts by weight, 64 parts by weight, 65 parts by weight, 66 parts by weight, 67 parts by weight, 68 parts by weight, 69 parts by weight parts, 70 parts by weight, 71 parts by weight, 72 parts by weight, 73 parts by weight, 74 parts by weight or 75 parts by weight; the content of the polyolefin thermoplastic elastomer in the raw material is preferably 10 to 25 parts by weight, specifically 10 parts by weight, 11 parts by weight, 12 parts by weight, 13 parts by weight, 14 parts by weight, 15 parts by weight, 16 parts by weight, 17 parts by weight, 18 parts by weight, 19 parts by weight, 20 parts by weight, 21 parts by weight, 22 parts by weight parts, 23 parts by weight, 24 parts by weight or 25 parts by weight.

In the anti-fouling material provided by the present invention, the nano-zinc oxide is used as an inorganic antibacterial component, which can decompose negatively charged electrons in water and air by itself under the irradiation of sunlight, especially ultraviolet light, while leaving positively charged holes, which can stimulate the oxygen in the air to become active oxygen, and oxidize with a variety of microorganisms to play a bactericidal effect; in addition, zinc ions will gradually dissociate, when it and bacteria When in contact with each other, it will combine with the active protease in the bacteria to make it inactive, thereby killing the bacteria and improving the long-term anti-bioadhesion effect of the material. In the present invention, the particle size of the nano zinc oxide is preferably 5-20nm, specifically 5nm, 6nm, 7nm, 8nm, 9nm, 10nm, 11nm, 12nm, 13nm, 14nm, 15nm, 16nm, 17nm, 18nm, 19nm or 20nm.

In the anti-fouling material provided by the present invention, the content of the nano-zinc oxide in the raw materials can be 0.5 parts by weight, 0.7 parts by weight, 1 part by weight, 1.2 parts by weight, 1.5 parts by weight, 1.7 parts by weight, 2 Parts by weight, 2.3 parts by weight, 2.5 parts by weight, 2.7 parts by weight, 3 parts by weight, 3.2 parts by weight, 3.5 parts by weight, 3.7 parts by weight, 4 parts by weight, 4.2 parts by weight, 4.5 parts by weight, 4.7 parts by weight or 5 parts by weight .

In the anti-fouling material provided by the present invention, the 2-(methoxycarbamoyl)benzimidazole (CASNo.10605-21-7), also known as carbendazim, is a broad-spectrum bactericidal It is a high-efficiency and low-toxic systemic fungicide, which can prevent and control diseases caused by fungi (such as fungi and polyascomycetes), interfere with the formation of spindles in mitosis of pathogenic bacteria, affect cell division, and play a bactericidal role. Its structural formula is as follows:

In the anti-fouling material provided by the present invention, the content of the 2-(methoxycarbamoyl) benzimidazole in the raw materials can be 0.5 parts by weight, 0.6 parts by weight, 0.7 parts by weight, 0.8 parts by weight , 0.9 parts by weight, 1 part by weight, 1.1 parts by weight, 1.2 parts by weight, 1.3 parts by weight, 1.4 parts by weight, 1.5 parts by weight, 1.6 parts by weight, 1.7 parts by weight, 1.8 parts by weight, 1.9 parts by weight, 2 parts by weight, 2.1 parts by weight Parts by weight, 2.2 parts by weight, 2.3 parts by weight, 2.4 parts by weight, 2.5 parts by weight, 2.6 parts by weight, 2.7 parts by weight, 2.8 parts by weight, 2.9 parts by weight or 3 parts by weight.

In the anti-fouling material provided by the present invention, the zinc pyrithione (CASNo.13463-41-7) is a coordination complex of zinc and pyrithione, which can inhibit Gram-positive and negative bacteria and Mold growth, has a powerful anti-fungal effect. Its structural formula is as follows:

In the anti-fouling material provided by the present invention, the content of the zinc pyrithione in the raw materials for preparation can specifically be 0.5 parts by weight, 0.6 parts by weight, 0.7 parts by weight, 0.8 parts by weight, 0.9 parts by weight, 1 part by weight, 1.1 parts by weight, 1.2 parts by weight, 1.3 parts by weight, 1.4 parts by weight, 1.5 parts by weight, 1.6 parts by weight, 1.7 parts by weight, 1.8 parts by weight, 1.9 parts by weight, 2 parts by weight, 2.1 parts by weight, 2.2 parts by weight, 2.3 parts by weight 2.4 parts by weight, 2.5 parts by weight, 2.6 parts by weight, 2.7 parts by weight, 2.8 parts by weight, 2.9 parts by weight or 3 parts by weight.

In the anti-fouling material provided by the present invention, the hydrophobic white carbon black is a porous substance whose composition can be represented by SiO ₂ ·nH ₂ O. It has a large specific surface area, strong adsorption capacity, and extremely strong hydrophobicity. It is mixed with the organic antibacterial component, which can make the functional auxiliary agent fully adsorbed in the surface folds and internal pores of the superhydrophobic silica, and can improve the dispersibility of the functional auxiliary agent, so that the functional auxiliary agent can be fully absorbed in the matrix. Play its functionality, and at the same time, the three-dimensional network structure has an adjustable slow-release function for functional additives, which can effectively improve the anti-bioadhesion ability. In the present invention, the specific surface area of the hydrophobic silica is preferably 300-500m ² /g, specifically 300m ² /g, 310m ² /g, 320m ² /g, 330m ² /g, 340m ² /g g, 350m ² /g, 360m ² /g, 370m ² /g, 380m ² /g, 390m ² /g, ^{400m 2} /g, 410m 2 /g, 420m ² /g, 430m ² /g, 440m ² /g g, 450m ² /g, 460m ² /g, 470m ² /g, 480m ² /g, 490m ² /g or 500m ² /g; the water contact angle of the hydrophobic silica is preferably ≥150°, more Preferably 150°～170°, specifically 150°, 151°, 152°, 153°, 154°, 155°, 156°, 157°, 158°, 159°, 160°, 161°, 162°, 163°, 164°, 165°, 166°, 167°, 168°, 169° or 170°.

In the anti-fouling material provided by the present invention, the content of the hydrophobic white carbon black in the raw materials can be 0.5 parts by weight, 0.6 parts by weight, 0.7 parts by weight, 0.8 parts by weight, 0.9 parts by weight, or 1 part by weight. , 1.1 parts by weight, 1.2 parts by weight, 1.3 parts by weight, 1.4 parts by weight, 1.5 parts by weight, 1.6 parts by weight, 1.7 parts by weight, 1.8 parts by weight, 1.9 parts by weight, 2 parts by weight, 2.1 parts by weight, 2.2 parts by weight, 2.3 parts by weight Parts by weight, 2.4 parts by weight, 2.5 parts by weight, 2.6 parts by weight, 2.7 parts by weight, 2.8 parts by weight, 2.9 parts by weight or 3 parts by weight.

In the anti-fouling material provided by the present invention, the copper ion fiber is a synthetic fiber containing copper, which has good antibacterial effect, high safety, no drug resistance, and mechanical properties, heat resistance and Excellent chemical stability. In the present invention, the base material of the copper ion fiber is preferably one or more of polyethylene terephthalate, polyamide and polyether ether ketone; the copper element content in the copper ion fiber Preferably 5000-50000ppm, specifically 5000ppm, 10000ppm, 15000ppm, 20000ppm, 25000ppm, 30000ppm, 35000ppm, 40000ppm, 45000ppm or 50000ppm; the diameter of the copper ion fiber is preferably 0.5-10μm, specifically 0.5μm, 1μm, 1.5 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm or 10 μm; the aspect ratio of the copper ion fiber is preferably ≥100, more preferably 100-200, specifically 100, 110, 120 . , 760MPa, 780MPa, 800MPa, 820MPa, 840MPa, 860MPa, 880MPa or 900MPa.

In the anti-fouling material provided by the present invention, the content of the copper ion fiber in the raw material can be 5 parts by weight, 5.5 parts by weight, 6 parts by weight, 6.5 parts by weight, 7 parts by weight, 7.5 parts by weight, 8 parts by weight, Parts by weight, 8.5 parts by weight, 9 parts by weight, 9.5 parts by weight, 10 parts by weight, 10.5 parts by weight, 11 parts by weight, 11.5 parts by weight, 12 parts by weight, 12.5 parts by weight, 13 parts by weight, 13.5 parts by weight, 14 parts by weight , 14.5 parts by weight or 15 parts by weight.

In the anti-fouling material provided by the present invention, the auxiliary agent preferably includes one or more of a coupling agent, a dispersant, an antioxidant and a weather resistance agent; the content of the auxiliary agent in the raw material for preparation can be 0.6 parts by weight, 0.7 parts by weight, 0.8 parts by weight, 0.9 parts by weight, 1 part by weight, 1.1 parts by weight, 1.2 parts by weight, 1.3 parts by weight, 1.4 parts by weight, 1.5 parts by weight, 1.6 parts by weight, 1.7 parts by weight, 1.8 parts by weight Parts by weight, 1.9 parts by weight, 2 parts by weight, 2.1 parts by weight, 2.2 parts by weight, 2.3 parts by weight, 2.4 parts by weight, 2.5 parts by weight, 2.6 parts by weight, 2.7 parts by weight, 2.8 parts by weight, 2.9 parts by weight, 3 parts by weight , 3.1 parts by weight, 3.2 parts by weight, 3.3 parts by weight, 3.4 parts by weight, 3.5 parts by weight, 3.6 parts by weight, 3.7 parts by weight, 3.8 parts by weight, 3.9 parts by weight or 4 parts by weight.

In the anti-fouling material provided by the present invention, the coupling agent is a plastic additive that improves the interfacial properties of synthetic resins and inorganic fillers or reinforcing materials in plastic compounding, also known as a surface modifier, which is used in During plastic processing, it can reduce the viscosity of synthetic resin melt and improve the dispersion of fillers to improve processing performance. In the present invention, the coupling agent is preferably a silane coupling agent, more preferably a silane coupling agent KH550.

In the anti-fouling material provided by the present invention, the content of the coupling agent in the preparation raw materials is preferably 0.2 to 1.0 parts by weight, specifically 0.2 parts by weight, 0.25 parts by weight, 0.3 parts by weight, 0.35 parts by weight, 0.4 parts by weight Parts by weight, 0.45 parts by weight, 0.5 parts by weight, 0.55 parts by weight, 0.6 parts by weight, 0.65 parts by weight, 0.7 parts by weight, 0.75 parts by weight, 0.8 parts by weight, 0.85 parts by weight, 0.9 parts by weight, 0.95 parts by weight or 1 part by weight .

In the anti-fouling material provided by the present invention, the function of the dispersant is to reduce the friction between materials and the surface of materials and processing equipment during plastic processing, thereby reducing the flow resistance and viscosity of the melt and improving the viscosity of the melt. Fluidity and dispersant, to avoid melt-melt, melt-melt and equipment adhesion. In the present invention, the dispersant is preferably polyethylene wax and/or zinc stearate; the number average molecular weight of the polyethylene wax is preferably 2000 to 8000, more preferably 4000; the softening point of the polyethylene wax is Preferably it is 100-110 degreeC, More preferably, it is 105 degreeC.

In the anti-fouling material provided by the present invention, the content of the dispersant in the raw materials is preferably 0.2 to 2.0 parts by weight, specifically 0.2 parts by weight, 0.3 parts by weight, 0.4 parts by weight, 0.5 parts by weight, and 0.6 parts by weight Parts, 0.7 parts by weight, 0.8 parts by weight, 0.9 parts by weight, 1 parts by weight, 1.1 parts by weight, 1.2 parts by weight, 1.3 parts by weight, 1.4 parts by weight, 1.5 parts by weight, 1.6 parts by weight, 1.7 parts by weight, 1.8 parts by weight, 1.9 parts by weight or 2 parts by weight.

In the anti-fouling material provided by the invention, the antioxidant is preferably one or more of antioxidant 1010, antioxidant 1076 and antioxidant 168; in some embodiments provided by the invention , the antioxidant is preferably antioxidant 1010 and antioxidant 168, and the mass ratio of antioxidant 1010 to antioxidant 168 is preferably (1～3):(1～3), more preferably ( 2～3): (2～3), specifically 3:2 or 2:3; in some embodiments provided by the present invention, the antioxidant is preferably antioxidant 1076 and antioxidant 168, The antioxidant is preferably that the mass ratio of the antioxidant 1076 to the antioxidant 168 is preferably 1:(0.5-5), more preferably 1:(1-2).

In the anti-fouling material provided by the present invention, the content of the antioxidant in the preparation raw materials is preferably 0.1 to 0.5 parts by weight, specifically 0.1 parts by weight, 0.15 parts by weight, 0.2 parts by weight, 0.25 parts by weight, 0.3 parts by weight parts by weight, 0.35 parts by weight, 0.4 parts by weight, 0.45 parts by weight or 0.5 parts by weight.

In the anti-fouling material provided by the invention, the weather resistance agent is preferably one or more of weather resistance agent 770, weather resistance agent 944 and weather resistance agent UV-P; in some embodiments provided by the invention, the Described weathering agent is preferably weathering agent 944 and weathering agent UV-P, and the mass ratio of described weathering agent 944 and weathering agent UV-P is preferably (1～3):(1～3), specifically can be 1:1, 3:2 or 2:3; In some embodiments provided by the invention, the weathering agent is preferably weathering agent 770 and weathering agent UV-P, and the mass ratio of the weathering agent 770 and weathering agent UV-P is preferably (1-3):1, more preferably 2:1.

In the anti-fouling material provided by the present invention, the content of the weather resistance agent in the raw materials is preferably 0.1 to 0.5 parts by weight, specifically 0.1 parts by weight, 0.15 parts by weight, 0.2 parts by weight, 0.25 parts by weight, and 0.3 parts by weight part, 0.35 part by weight, 0.4 part by weight, 0.45 part by weight or 0.5 part by weight.

The present invention also provides a preparation method of the anti-fouling material described in the above technical solution, comprising the following steps:

The preparation raw materials are melted, blended and extruded to obtain the anti-biological adhesion material.

In the preparation method provided by the present invention, the specific preparation process of the anti-fouling material preferably includes:

a) Polyolefin thermoplastic elastomer, nano zinc oxide, 2-(methoxycarbamoyl) benzimidazole, zinc pyrithione, hydrophobic white carbon black, coupling agent, dispersant, antioxidant and weather resistance Compounding, extruding and pelletizing to obtain functional masterbatch;

b) Melting, blending and extruding the functional masterbatch, high-density polyethylene and copper ion fibers to obtain an anti-biological adhesion material.

In the preparation method provided by the present invention, in step a), the banburying is preferably carried out in an internal mixer; the temperature of the banburying is preferably 150-230°C, specifically 150°C, 160°C, 170°C , 180°C, 190°C, 200°C, 210°C, 220°C or 230°C; the rotational speed of the banburying is preferably 120 to 200rpm, specifically 120rpm, 130rpm, 140rpm, 150rpm, 160rpm, 170rpm, 180rpm, 190rpm or 200 rpm; the banburying time is preferably 30-60 min, specifically 30 min, 35 min, 40 min, 45 min, 50 min, 55 min or 60 min; the pelletizing method is preferably underwater pelletizing.

In the preparation method provided by the present invention, in step b), the melt blending extrusion is preferably carried out in an extruder; the extrusion speed of the extruder is preferably 30-60rpm, specifically 30rpm, 35rpm , 40rpm, 45rpm, 50rpm, 55rpm or 60rpm; the temperature of zone 1 of the extruder is preferably 150-200°C, specifically 150°C, 155°C, 160°C, 165°C, 170°C, 175°C, 180°C , 185°C, 190°C, 195°C or 200°C; and the temperature of other zones and head of the extruder is preferably 180-230°C, specifically 180°C, 185°C, 190°C, 195°C, 200°C, 205°C, 210°C, 215°C, 220°C, 225°C or 230°C.

In the preparation method provided by the present invention, after the preparation raw materials are melted, blended and extruded, they are preferably granulated to obtain the anti-fouling granules.

The present invention also provides an anti-bio-fouling floating body, the surface material of the anti-bio-fouling floating body is the anti-bio-fouling material described in the above technical solution.

The technical solution provided by the invention obtains a material with good anti-bioadhesion ability by optimizing the raw material formula of the polymer material, which can effectively prevent bio-adhesion for a long time, and overcomes the poor anti-bioadhesion and short validity period of existing materials And other issues. When the material is used as a floating body material, it can effectively reduce the manual cleaning of the surface of the floating body, thereby avoiding the negative impact of frequent manual cleaning on the floating body, and has a good application prospect in the field of floating body materials for offshore photovoltaic power generation.

For more clarity, the following examples and comparative examples are described in detail below.

Example 1

This embodiment prepares a kind of anti-fouling floating body material, including the following raw materials in parts by weight:

High-density polyethylene (melt flow rate (190°C, load 2.16kg) is 15g/10min, environmental stress cracking resistance time F ₅₀ (50°C, 10% Igepal) is 5000h) 65.0 parts, polyolefin thermoplastic elastomer (door Ni viscosity ML (1+4) 121 ℃ is 18MU, tear strength 30kN/m, glass transition temperature -59 ℃) 15.0 parts, nano-zinc oxide (particle size 10nm) 3.0 parts, 2-(methoxyaminomethyl Acyl)benzimidazole 2.0 parts, pyrithione zinc 2.0 parts, hydrophobic white carbon black (specific surface area 400m ² /g, water contact angle 151°) 2.0 parts, silane coupling agent KH5500.5 parts, dispersant polyethylene Wax (number average molecular weight 4000, softening point 105°C) 0.5 parts, antioxidant 10100.3 parts, antioxidant 1680.2 parts, weather resistance agent 9440.2 parts, weather resistance agent UV-P 0.3 parts, copper ion fiber (polyether ether ketone matrix, Copper element content 50000ppm, diameter 5μm, aspect ratio 200, tensile strength 720MPa) 9.0 parts.

Concrete preparation steps are as follows:

a) Put the polyolefin thermoplastic elastomer into the internal mixer to melt and plasticize, and then add nano-zinc oxide, 2-(methoxycarbamoyl)benzimidazole, zinc pyrithione, and hydrophobic white carbon black according to the proportion , coupling agent, dispersant, antioxidant and weather resistance agent, the banbury temperature is 180°C, the banbury speed is 150rpm, and the banbury time is 45min. After the banbury is uniform, it is extruded and pelletized underwater to obtain the functional masterbatch material;

b) Melt, blend and extrude the functional masterbatch obtained in step a) with high-density polyethylene and copper ion fibers in an extruder. The temperature of the head is 210° C., and granulation is carried out after extrusion to obtain the anti-biological adhesion floating body material.

Example 2

This embodiment prepares a kind of anti-fouling floating body material, including the following raw materials in parts by weight:

High-density polyethylene (melt flow rate (190°C, load 2.16kg) is 15g/10min, environmental stress cracking resistance time F ₅₀ (50°C, 10% Igepal) is 5000h) 60.0 parts, polyolefin thermoplastic elastomer (door Ni viscosity ML (1+4) 121 ℃ is 18MU, tear strength 30kN/m, glass transition temperature -59 ℃) 10.0 parts, nano zinc oxide (particle size 10nm) 2.0 parts, 2-(methoxyaminomethyl Acyl)benzimidazole 3.0 parts, pyrithione zinc 3.0 parts, hydrophobic white carbon black (specific surface area 400m ² /g, water contact angle 151°) 3.0 parts, silane coupling agent KH5501.0 parts, dispersant polyethylene Wax (number average molecular weight 4000, softening point 105°C) 2.0 parts, antioxidant 10100.2 parts, antioxidant 1680.3 parts, weather resistance agent 9440.3 parts, weather resistance agent UV-P 0.2 parts, copper ion fiber (polyether ether ketone matrix, Copper element content 50000ppm, diameter 0.5μm, aspect ratio 150, tensile strength 820MPa) 15.0 parts.

Concrete preparation steps are as follows:

a) Put the polyolefin thermoplastic elastomer into the internal mixer to melt and plasticize, and then add nano-zinc oxide, 2-(methoxycarbamoyl)benzimidazole, zinc pyrithione, and hydrophobic white carbon black according to the proportion , coupling agent, dispersant, antioxidant and weather resistance agent, the banbury temperature is 230°C, the banbury speed is 200rpm, and the banbury time is 60min. After banburying evenly, extrude and pelletize underwater to obtain the functional masterbatch material;

b) Melt, blend and extrude the functional masterbatch obtained in step a) with high-density polyethylene and copper ion fibers in an extruder. The temperature of the head is 230° C., granulation is carried out after extrusion, and an anti-biological adhesion floating body material is obtained.

Example 3

This embodiment prepares a kind of anti-fouling floating body material, including the following raw materials in parts by weight:

High-density polyethylene (melt flow rate (190°C, load 2.16kg) is 10g/10min, environmental stress cracking resistance time F ₅₀ (50°C, 10% Igepal) is 5000h) 60.0 parts, polyolefin thermoplastic elastomer (door Ni viscosity ML (1+4) 121 ℃ is 18MU, tear strength 30kN/m, glass transition temperature -59 ℃) 25.0 parts, nano zinc oxide (particle size 10nm) 0.5 parts, 2-(methoxyaminomethyl Acyl)benzimidazole 0.5 part, pyrithione zinc 0.5 part, hydrophobic white carbon black (specific surface area 400m ² /g, water contact angle 151°) 0.5 part, silane coupling agent KH5500.2 part, dispersant stearin Zinc acid 0.4 part, antioxidant 10760.1 part, antioxidant 1680.1 part, weather resistance agent 9440.1 part, weather resistance agent UV-P 0.1 part, copper ion fiber (polyetheretherketone matrix, copper element content 50000ppm, diameter 1μm, long diameter Ratio 150, tensile strength 800MPa) 12.0 parts.

Concrete preparation steps are as follows:

a) Put the polyolefin thermoplastic elastomer into the internal mixer to melt and plasticize, and then add nano-zinc oxide, 2-(methoxycarbamoyl)benzimidazole, zinc pyrithione, and hydrophobic white carbon black according to the proportion , coupling agent, dispersant, antioxidant and weather resistance agent, the banbury temperature is 180°C, the banbury speed is 150rpm, and the banbury time is 45min. After the banbury is uniform, it is extruded and pelletized underwater to obtain the functional masterbatch material;

b) Melt, blend and extrude the functional masterbatch obtained in step a) with high-density polyethylene and copper ion fibers in an extruder. The temperature of the head is 230° C., granulation is carried out after extrusion, and an anti-biological adhesion floating body material is obtained.

Example 4

This embodiment prepares a kind of anti-fouling floating body material, including the following raw materials in parts by weight:

High-density polyethylene (melt flow rate (190°C, load 2.16kg) is 20g/10min, environmental stress cracking resistance time F ₅₀ (50°C, 10% Igepal) is 5000h) 75.0 parts, polyolefin thermoplastic elastomer (door Ni viscosity ML (1+4) 121 ℃ is 18MU, tear strength 30kN/m, glass transition temperature -59 ℃) 10.0 parts, nano-zinc oxide (particle size 10nm) 0.5 parts, 2-(methoxyaminomethyl Acyl)benzimidazole 0.5 part, pyrithione zinc 0.5 part, hydrophobic white carbon black (specific surface area 400m ² /g, water contact angle 151°) 0.5 part, silane coupling agent KH5500.2 part, dispersant stearin Zinc acid 0.2 part, antioxidant 10760.1 part, antioxidant 1680.2 part, weathering agent 7700.2 part, weathering agent UV-P 0.1 part, copper ion fiber (polyether ether ketone matrix, copper element content 50000ppm, diameter 2μm, long diameter Ratio 150, tensile strength 780MPa) 12.0 parts.

Concrete preparation steps are as follows:

a) Put the polyolefin thermoplastic elastomer into the internal mixer to melt and plasticize, and then add nano-zinc oxide, 2-(methoxycarbamoyl)benzimidazole, zinc pyrithione, and hydrophobic white carbon black according to the proportion , coupling agent, dispersant, antioxidant and weather resistance agent, the banbury temperature is 200℃, the banbury speed is 180rpm, and the banbury time is 45min. Masterbatch;

b) Melt, blend and extrude the functional masterbatch obtained in step a) with high-density polyethylene and copper ion fibers in an extruder. The temperature of the head is 220° C., granulation is carried out after extrusion, and an anti-biological adhesion floating body material is obtained.

Example 5

This embodiment prepares a kind of anti-fouling floating body material, including the following raw materials in parts by weight:

High-density polyethylene (melt flow rate (190°C, load 2.16kg) is 20g/10min, environmental stress cracking resistance time F ₅₀ (50°C, 10% Igepal) is 5000h) 60.9 parts, polyolefin thermoplastic elastomer (door Ni viscosity ML (1+4) 121 ℃ is 18MU, tear strength 30kN/m, glass transition temperature -59 ℃) 25.0 parts, nano zinc oxide (particle size 10nm) 5.0 parts, 2-(methoxyaminomethyl Acyl)benzimidazole 2.5 parts, pyrithione zinc 2.5 parts, hydrophobic white carbon black (specific surface area 400m ² /g, water contact angle 151°) 2.5 parts, silane coupling agent KH5500.2 parts, dispersant polyethylene Wax (number average molecular weight 4000, softening point 105°C) 0.2 parts, antioxidant 1680.1 parts, weather resistance agent 9440.1 parts, copper ion fiber (polyetheretherketone matrix, copper element content 50000ppm, diameter 10μm, aspect ratio 100, pull Tensile strength 660MPa) 5.0 parts.

Concrete preparation steps are as follows:

a) Put the polyolefin thermoplastic elastomer into the internal mixer to melt and plasticize, and then add nano-zinc oxide, 2-(methoxycarbamoyl)benzimidazole, zinc pyrithione, and hydrophobic white carbon black according to the proportion , coupling agent, dispersant, antioxidant and weather resistance agent, the banbury temperature is 150°C, the banbury speed is 120rpm, and the banbury time is 30min. material;

b) Melt, blend and extrude the functional masterbatch obtained in step a) with high-density polyethylene and copper ion fibers in an extruder. The temperature of the head is 180° C., granulation is carried out after extrusion, and an anti-biological adhesion floating body material is obtained.

Comparative example 1

This comparative example has prepared a kind of floating body material, comprises the raw material of following parts by weight:

High-density polyethylene (melt flow rate (190°C, load 2.16kg) is 15g/10min, environmental stress cracking resistance time F ₅₀ (50°C, 10% Igepal) is 5000h) 75.0 parts, polyolefin thermoplastic elastomer (door Nickel viscosity ML (1+4) 121°C is 18MU, tear strength 30kN/m, glass transition temperature -59°C) 21.0 parts, silane coupling agent KH5501.0 parts, dispersant polyethylene wax (number average molecular weight 4000 , softening point 105 ℃) 2.0 parts, antioxidant 10100.2 parts, antioxidant 1680.3 parts, weather resistance agent 9440.3 parts, weather resistance agent UV-P 0.2 parts.

Concrete preparation steps are as follows:

a) Put the polyolefin thermoplastic elastomer into the internal mixer to melt and plasticize, and then add coupling agent, dispersant, antioxidant and weather resistance agent according to the proportion. , The banburying time is 45min, after the banburying is uniform, it is extruded, pelletized under water, and the functional masterbatch is obtained;

b) Melt, blend and extrude the functional masterbatch and high-density polyethylene obtained in step a) in an extruder, the extruder speed is 60rpm, the temperature in zone 1 is 200°C, and the temperature in other zones and dies is 230°C, granulate after extrusion to obtain a floating body material.

Comparative example 2

This comparative example prepared a kind of anti-fouling floating body material, including the following raw materials in parts by weight:

High-density polyethylene (melt flow rate (190°C, load 2.16kg) is 15g/10min, environmental stress cracking resistance time F ₅₀ (50°C, 10% Igepal) is 5000h) 69.0 parts, polyolefin thermoplastic elastomer (door Nickel viscosity ML (1+4) 121°C is 18MU, tear strength 30kN/m, glass transition temperature -59°C) 10.0 parts, nano zinc oxide (particle size 10nm) 2.0 parts, silane coupling agent KH550 1.0 parts , dispersant polyethylene wax (number average molecular weight 4000, softening point 105 ℃) 2.0 parts, antioxidant 10100.2 parts, antioxidant 1680.3 parts, weather resistance agent 9440.3 parts, weather resistance agent UV-P 0.2 part, copper ion fiber (polyethylene Ether ether ketone matrix, copper element content 50000ppm, diameter 0.5μm, aspect ratio 150, tensile strength 820MPa) 15.0 parts.

Concrete preparation steps are as follows:

a) Put the polyolefin thermoplastic elastomer into the internal mixer to melt and plasticize, and then add nano-zinc oxide, coupling agent, dispersant, antioxidant and weather resistance agent according to the proportion. The internal mixing temperature of the internal mixer is 230°C, The refining speed is 200rpm, and the banburying time is 60min. After the banburying is uniform, it is extruded, pelletized under water, and the functional masterbatch is obtained;

b) Melt, blend and extrude the functional masterbatch obtained in step a) with high-density polyethylene and copper ion fibers in an extruder. The temperature of the head is 230° C., granulation is carried out after extrusion, and an anti-biological adhesion floating body material is obtained.

Comparative example 3

This comparative example prepared a kind of anti-fouling floating body material, including the following raw materials in parts by weight:

High-density polyethylene (melt flow rate (190°C, load 2.16kg) is 15g/10min, environmental stress cracking resistance time F ₅₀ (50°C, 10% Igepal) is 5000h) 75.0 parts, polyolefin thermoplastic elastomer (door Ni viscosity ML (1+4) 121 ℃ is 18MU, tear strength 30kN/m, glass transition temperature -59 ℃) 12.0 parts, 2-(methoxycarbamoyl) benzimidazole 3.0 parts, pyrithione 3.0 parts of zinc, 3.0 parts of hydrophobic white carbon black (specific surface area 400m ² /g, water contact angle 151°), 1.0 parts of silane coupling agent KH550, dispersant polyethylene wax (number average molecular weight 4000, softening point 105°C ) 2.0 parts, 10100.2 parts of antioxidant, 1680.3 parts of antioxidant, 9440.3 parts of weathering agent, 0.2 part of weathering agent UV-P.

Concrete preparation steps are as follows:

a) Put the polyolefin thermoplastic elastomer into the internal mixer to melt and plasticize, and then add 2-(methoxycarbamoyl)benzimidazole, zinc pyrithione, hydrophobic white carbon black, and coupling agent according to the proportion , dispersant, antioxidant and weather resistance agent, the banbury temperature is 230°C, the banbury speed is 200rpm, the banbury time is 60min, the banbury is evenly extruded, and the underwater granulation is obtained to obtain the functional masterbatch;

b) Melt, blend and extrude the functional masterbatch and high-density polyethylene obtained in step a) in an extruder, the extruder speed is 30rpm, the temperature in zone 1 is 200°C, and the temperature in other zones and dies is 230°C, granulation after extrusion to obtain the anti-biological adhesion floating body material.

Performance Testing:

1. Melt flow rate: refer to GB/T 3682.1-2018, test temperature 190°C, weight 2.16kg;

2. Bending modulus: refer to GB/T 9341-2008, the thickness of the bending spline is 4mm, the span is 64mm, and the deflection is 6mm;

3. Weight ratio of attachments: make samples of the above-mentioned floating body materials into floating bodies, conduct field tests in the ocean, collect surface attachments on the surface of floating body samples after 12 months, measure the weight in a dry state, and the weight ratio of the floating body to the weight of the floating body is the attachment weight ratio.

4. Antifouling period of validity: The above-mentioned floating body material is prepared into a floating body, and the field test is carried out in the ocean. The antifouling valid period is defined as the period when the area of marine organisms attached to the surface of the floating body is less than 10%.

The performance of the floating body material obtained in Examples 1 to 5 and Comparative Examples 1 to 3 is tested according to the above-mentioned performance testing method, and the results are as shown in Table 1:

The performance test data of the floating body material obtained in table 1 embodiment 1～5 and comparative examples 1～3

It can be seen from Table 1 that compared with Comparative Examples 1-3, multiple organic antibacterial components and multiple inorganic antibacterial components, nano-zinc oxide and copper ion fibers were added to the anti-fouling floating body materials of Examples 1-5. The introduction of 2-(methoxycarbamoyl)benzimidazole and zinc pyrithione solves the problem of short anti-fouling time when 2-(methoxycarbamoyl)benzimidazole and zinc pyrithione are added alone, and improves the long-term anti-fouling performance of the floating body. High strength endows the float material with excellent rigidity. The anti-biological attachment floating body materials provided in Examples 1-5 have excellent performances, which can effectively reduce the manual cleaning of the surface of the floating body, thereby avoiding the negative impact of frequent manual cleaning on the floating body, and can meet the requirements for the use of offshore photovoltaic power generation. The field of floating body materials for power generation has good application prospects.

The above is only a preferred embodiment of the present invention, it should be pointed out that, for those of ordinary skill in the art, without departing from the principle of the present invention, some improvements and modifications can also be made, and these improvements and modifications can also be made. It should be regarded as the protection scope of the present invention.

Claims (10)

1. an anti-biological adhesion material, is characterized in that, in parts by weight, the preparation raw material of described anti-biological adhesion material comprises:

2. The anti-fouling material according to claim 1, characterized in that, the polymer base material comprises high-density polyethylene and polyolefin thermoplastic elastomer. 3. The anti-fouling material according to claim 2, characterized in that, the melt flow rate of the high-density polyethylene under the conditions of 190°C and 2.16kg load is 10-20g/10min; The environmental stress cracking resistance time F ₅₀ of ethylene at 50°C and 10% Igepal is ≥2000h; the Mooney viscosity ML(1+4) of the polyolefin thermoplastic elastomer is ≤20MU at 121°C; the polyolefin thermoplastic elastomer The tear strength of the elastomer is ≥25kN/m; the glass transition temperature of the polyolefin thermoplastic elastomer is ≤-55°C. 4. The anti-fouling material according to claim 1, characterized in that, the particle size of the nano zinc oxide is 5-20 nm. 5. The anti-fouling material according to claim 1, characterized in that, the specific surface area of the hydrophobic white carbon black is 300-500m ² /g; the water contact angle of the hydrophobic white carbon black is ≥150 °. 6. The anti-biological adhesion material according to claim 1, wherein the base material of the copper ion fiber is one or more of polyethylene terephthalate, polyamide and polyether ether ketone The content of copper element in the copper ion fiber is 5000-50000ppm; the diameter of the copper ion fiber is 0.5-10 μm; the aspect ratio of the copper ion fiber is ≥100. 7. The anti-fouling material according to claim 1, characterized in that, the auxiliary agent includes one or more of a coupling agent, a dispersant, an antioxidant and a weather resistance agent. 8. The anti-fouling material according to claim 1, characterized in that, in parts by weight, the preparation raw materials include:

9. A preparation method of the anti-fouling material according to any one of claims 1 to 8, characterized in that it comprises the following steps: The preparation raw materials are melted, blended and extruded to obtain the anti-biological adhesion material. 10. An anti-fouling body, characterized in that the surface material of the anti-fouling body is the anti-fouling material according to any one of claims 1-8.