Antifouling and anti-biofouling pe / ptfe composite fiber and preparation method thereof

Abstract

The application relates to the field of fiber materials, and particularly discloses a PE / PTFE composite fiber with antifouling and anti-bioadhesion and a preparation method thereof. The PE / PTFE composite fiber has a layered structure, the inner layer is a modified polyethylene fiber, and the outer layer is a PTFE coating layer. Due to the effect of the coating layer PTFE, the fiber surface has the characteristics of low surface energy, the water contact angle of the fiber surface is greater than or equal to 150 degrees, the adhesion of various algae and other organisms in water bodies can be effectively avoided, the fiber has high strength, anti-bioadhesion, high antifouling property and self-cleaning property, and the adhesion of organisms in water bodies is difficult or the adhesion force is very low. The fluorine-containing polyethylene modified polyethylene material is introduced through a modification process, the interfacial bonding force between the PTFE skin layer and the PE material is effectively improved, the overall strength of the fiber is increased, the wear resistance is effectively improved, and excellent antifouling and anti-bioadhesion performance are achieved.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of materials, more particularly, it relates to a PE / PTFE composite fiber for preventing fouling and biological attachment and a preparation method thereof. BACKGROUND

[0002] With the increasing demand for marine products, overfishing and human pollution of marine organisms have become increasingly serious. Against this background, the global net cage aquaculture industry has developed rapidly, but at the same time, it has also brought the problem of marine organisms attaching to the net cage and netting. These attached organisms can block the mesh, affect seawater convection, reduce dissolved oxygen and food supply, and cause the poor development or even death of farmed marine products, seriously affecting the yield and quality of aquaculture. Traditional manual or mechanical cleaning methods are labor-intensive, low-efficiency, and can easily damage the net cage and affect the aquaculture cycle.

[0003] Although the anti-fouling coatings on the market can slow down the attachment of marine organisms, they often contain metal ions that are harmful to the environment, and the anti-fouling effect lasts for a short time, which is not an environmentally friendly or sustainable solution. In addition, offshore facilities such as wind power floats, submarine cables, mooring systems, and aquaculture net cages are also affected by the attachment of marine organisms, which can change the physical and chemical properties of the materials, shorten their service life, and even cause ecological disasters, such as the green tide of Enteromorpha in the Yellow Sea. Traditional net cage aquaculture has several major problems: first, the net cage is easily attached by marine organisms such as barnacles and algae, leading to fouling of the net cage and formation of a fence effect; second, poor seawater flow and increased resistance can cause the net cage to be washed away; third, fish feed and fish excrement that are manually thrown into the water are difficult to be carried away by flowing seawater, which can lead to water pollution in the net cage, and further cause fish diseases and death.

[0004] Therefore, developing new, environmentally friendly, and long-lasting anti-fouling materials and technologies to address the problem of marine organism attachment and fouling is a key issue that needs to be addressed in the field of marine engineering. Such materials need to have good anti-attachment properties and mechanics, and be safe and sustainable for the marine environment to protect the marine ecosystem and extend the service life of offshore facilities. SUMMARY

[0005] To solve the above technical problems, the present application provides a PE / PTFE composite fiber for preventing fouling and biological attachment and a preparation method thereof.

[0006] The present application adopts the following technical solutions:

[0007] In a first aspect, the present application provides a PE / PTFE composite fiber for preventing fouling and biological attachment, which has a layered structure, an inner layer of modified polyethylene fiber, and an outer layer of PTFE coating layer, the mass percentage of the PTFE coating layer being 3-35wt%;

[0008] The tensile strength of the PE / PTFE composite fiber is above 5.8 cN / dtex, the surface biological adhesion amount is below 0.0012 g / m after being soaked in seawater for half a year, and the surface biological adhesion amount is below 0.0022 g / m after 5000 times of friction and being soaked in seawater for half a year.

[0009] Further, the modified polyethylene fiber is obtained by compounding and melt spinning polyethylene resin chips and fluorine-containing polyethylene resin chips, wherein the polyethylene resin is used as a core layer and the fluorine-containing polyethylene resin is used as a skin layer.

[0010] Further, in the modified polyethylene fiber, the core layer is 5-90 parts by weight and the skin layer is 25-95 parts by weight.

[0011] In the second aspect, the application provides a preparation method of the above-mentioned anti-fouling and anti-bioadhesion PE / PTFE composite fiber, which comprises the following steps:

[0012] After the PTFE resin is blended and softened with isoparaffin solvent oil, the modified polyethylene fiber is coated on the surface of the modified polyethylene fiber, and after cooling, the PTFE coating layer is formed by deoiling to obtain the PE / PTFE composite fiber.

[0013] Further, the softening process comprises that the PTFE resin is blended and melt softened with the isoparaffin solvent oil at 100-300℃ through a screw extruder.

[0014] Preferably, the deoiling temperature in the process of forming the PTFE coating layer is 80-250℃.

[0015] Further, the preparation method of the modified polyethylene fiber comprises the following steps:

[0016] The fluorine-containing acrylate, the benzophenone compound and the alkyl ester containing thio peroxide dicarbonate are dispersed in an organic solvent to obtain a modification liquid.

[0017] The polyethylene resin chips are added into the modification liquid, and a solid-liquid mixture is obtained by stirring under an inert atmosphere. The solid-liquid mixture is irradiated under ultraviolet light of 245-260 nm, and then continuously stirred and inert gas is introduced. Then, the fluorine-containing polyethylene resin chips are obtained by filtering and drying.

[0018] The polyethylene resin chips are compounded and melt spun with the fluorine-containing polyethylene resin chips, and the modified polyethylene fiber with the skin layer of fluorine-containing polyethylene resin and the core layer of unmodified polyethylene resin is prepared by hot drawing.

[0019] Further, the fluorine-containing acrylate includes one or a combination of 2-(perfluorobutyl)ethyl methacrylate, 2-(perfluorooctyl)ethyl methacrylate, 2-(perfluorohexyl)ethyl methacrylate, 2-(perfluorodecyl)ethyl methacrylate, 2-perfluorooctyl acrylate, 3-(perfluoro-5-methylhexyl)-2-hydroxypropyl methacrylate, 1,1,1,3,3,3-hexafluoroisopropyl acrylate, and 2-(perfluorododecyl)ethyl acrylate.

[0020] Further, in the modification liquid, the molar ratio of the fluorine-containing acrylate, the benzophenone compound, and the alkyl ester containing thio-peroxydicarbonic acid is (80-350):1:1.

[0021] Preferably, the benzophenone compound is (4-methoxyphenyl)(4-(trifluoromethyl)phenyl) ketone, and the alkyl ester containing thio-peroxydicarbonic acid is thio-peroxydicarbonic acid([(HS)C(S)]2S2)C,C'-octacosyl ester.

[0022] Further, in the preparation of fluorine-containing polyethylene resin chips, the temperature of the solid-liquid mixture is controlled to be 10-60℃, and the ultraviolet lamp irradiation time is 3-48h.

[0023] Further, in the composite melt spinning process, the spinning temperature is 100-240℃, the heat drawing temperature is 80-130℃, and the draw ratio is 3-15 times.

[0024] In summary, the present application has the following beneficial effects:

[0025] 1. The PE / PTFE composite fiber provided by the present application has a PTFE coating layer, i.e., a polytetrafluoroethylene coating layer. Fluorine-containing polymers generally have low surface energy and are not easy to adhere to other substances, so fluorine-containing materials are introduced to prepare anti-fouling and anti-attachment fibers. Currently, fluorine-containing polymers mainly include polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroalkoxy vinyl ether copolymer (PFA), and polyvinylidene fluoride (PVDF). Among these three materials, PTFE and PFA have higher fluorine content, and PVDF has relatively lower fluorine content. Therefore, PTFE and PFA have better anti-fouling and anti-bioattachment effects, and can be selected as anti-fouling and anti-bioattachment materials.

[0026] 2.However, due to the processing difficulty of PTFE and PFA, high price, and the mechanical properties of PTFE and PFA fibers are far lower than those of conventional polymer fibers such as polyethylene (PE), polypropylene (PP), polyester (PET), polyamide (PA) and the like. The shortcomings limit the application of PTFE and PFA fluoropolymers in the field of antifouling and biofouling prevention. The applicant prepares fibers by compounding PTFE fluoropolymers with PE, PP, PET and other traditional polymers, which theoretically can have the advantages of both materials, thereby ensuring the mechanical properties of the fibers while having antifouling and biofouling prevention properties.

[0027] 3.Due to the low surface energy of PFA and PTFE fluoropolymer materials, when compounded with non-fluorine-containing polymers, the two different types of polymers are incompatible, the interface interaction between them is low, and a good bonding interface cannot be formed, which greatly affects the performance of the material, causing shedding, delamination and other negative conditions. Therefore, the PE / PTFE composite fiber provided by the present application focuses on and solves the interface problem between the two types of materials when compounding fluoropolymer with non-fluoropolymer. By introducing fluorine-containing polyethylene, a modified polyethylene material, the interfacial bonding force between the PTFE coating layer and the PE material is effectively improved, the overall strength of the fiber is increased, and the wear resistance is also effectively improved, thereby prolonging the service life of the fiber and its products and the effective time of biofouling prevention.

[0028] 4.The tensile strength of the PE / PTFE fiber provided by the present application is greater than or equal to 5.8 cN / dtex. Due to the effect of the PTFE coating layer, the fiber surface has the characteristics of low surface energy, and the fiber surface water contact angle is greater than or equal to 150 degrees, which can effectively prevent the adhesion of various algae and other organisms in water, has high strength, biofouling prevention, high antifouling property and self-cleaning property, and the attached organisms in water are difficult to adhere or have very low adhesion. The amount of surface biological adhesion of the fiber after soaking in seawater for half a year is less than or equal to 0.0012 g / m, and the amount of surface biological adhesion of the fiber after 5000 times of friction in seawater for half a year is less than or equal to 0.0022 g / m, which has excellent biofouling prevention effect. Therefore, the thread, rope, cable, net and the like made of the composite fiber provided by the present application also have the corresponding excellent performance of the composite fiber, and have excellent biofouling prevention function in water. BRIEF DESCRIPTION OF DRAWINGS

[0029] Figure 1 The cross-sectional structure diagram of the PE / PTFE composite fiber provided by the present application. DETAILED DESCRIPTION

[0030] The embodiments of the present application will be described in detail below with examples, but those skilled in the art will understand that the following examples are only for illustration of the present application, and should not be regarded as limiting the scope of the present application. The specific conditions not noted in the examples are carried out according to the conventional conditions or the conditions recommended by the manufacturer, the reagents or instruments not noted the manufacturer are all the conventional products which can be purchased in the market.

[0031] The specific embodiments of the present application are described in detail below. It should be understood that the specific embodiments described herein are only for illustration and explanation of the present application, and are not intended to limit the present application.

[0032] Example 1

[0033] The present embodiment provides a PE / PTFE composite fiber for preventing fouling and biofouling, which has a layered structure, an inner layer is a modified polyethylene fiber, and an outer layer is a PTFE coating layer, and the cross-sectional structure is as shown in Figure 1

[0034] The preparation method of the PE / PTFE composite fiber includes the following steps:

[0035] Step 1: Dioxane is used as a solvent, a benzophenone compound with a structure as shown in formula 1, a thio-peroxy dicarbonate with a structure as shown in formula 2, and 2-(perfluorobutyl) ethyl methacrylate are mixed in a ratio of 1:1:105 to obtain a modified solution. A polyethylene resin chip with a weight average molecular weight of 100,000 is added to the modified solution, the mass ratio of the polyethylene resin chip to 2-(perfluorobutyl) ethyl methacrylate is 1:20, high-purity argon gas is introduced at 150 ml / min, and stirring is carried out for 60 minutes to obtain a solid-liquid mixture.

[0036] Step 2: The solid-liquid mixture obtained in step 1 is irradiated with ultraviolet light with a wavelength of 253 nm for 12 hours, stirring is continuously carried out and argon gas is introduced during the irradiation process, the amount of argon gas introduced is 200 ml / min, and the temperature of the solid-liquid mixture is controlled at 20℃. The irradiated solid-liquid mixture is filtered and dried at 60℃ for 3 hours to obtain a fluorine-containing polyethylene resin chip.

[0037] ​Step 3: The fluorine-containing polyethylene resin chips obtained in step 2 and polyethylene resin chips (weight average molecular weight of 100,000) are used as raw materials to perform composite melt spinning in a composite spinning machine; the composite spinning machine includes two single-screw extruders, the spinning temperature of the composite spinning machine is 230°C, the fluorine-containing polyethylene resin and the unmodified polyethylene resin are respectively added to different single-screw extruders to form melts, the melts are metered and conveyed to a composite spinning assembly through the respective metering pumps, and the melts are extruded through a composite spinneret to obtain a continuous melt with the fluorine-containing polyethylene resin as a skin layer and the unmodified polyethylene resin as a core layer; the fluorine-containing polyethylene resin accounts for 8 parts by mass in the continuous melt, and the unmodified polyethylene resin accounts for 92 parts by mass; after air cooling, solidification is performed, and after drawing 8 times at 90°C, a modified polyethylene fiber with the fluorine-containing polyethylene resin as the skin layer and the unmodified polyethylene resin as the core layer is prepared, and the skin layer accounts for 8 parts by mass and the core layer accounts for 92 parts by mass.

[0038] Step 4: The PTFE resin and isomeric alkane solvent oil are melted and softened at 130°C by using a double-screw extruder, coated on the surface of the modified polyethylene fiber obtained in step 3 by a melt coating process, then deoiled at 150°C to form a PTFE skin layer, and then cooled to obtain a PE / PTFE composite fiber, and the PTFE skin layer accounts for 15% of the total fiber mass.

[0039] Example 2

[0040] The embodiment provides a PE / PTFE composite fiber for preventing fouling and biofouling, and a preparation method thereof.

[0041] Step 1: Diphenyl ketone compound with a structure as shown in formula 1, thio peroxide dicarbonate with a structure as shown in formula 2, and 2-(perfluorooctyl) ethyl methacrylate are mixed in a mass ratio of 1:1:110 to obtain a modified solution, using dioxane as a solvent. Polyethylene resin chips with a weight average molecular weight of 80,000 are added to the modified solution, the mass ratio of the polyethylene resin chips to the 2-(perfluorooctyl) ethyl methacrylate is 1:30, 150 milliliters / minute of high-purity argon is introduced, and stirring is performed for 60 minutes to obtain a solid-liquid mixture.

[0042] Step 2: The solid-liquid mixture obtained in step 1 is irradiated with ultraviolet light with a wavelength of 253 nm for 14 hours, stirring is continuously performed during the irradiation, and argon is introduced at an amount of 300 milliliters / minute, and the temperature of the solid-liquid mixture is controlled at 25°C. The irradiated solid-liquid mixture is filtered and dried at 60°C for 4 hours to obtain fluorine-containing polyethylene resin chips.

[0043] Step 3: The fluorine-containing polyethylene resin chips obtained in step 2 and polyethylene resin chips (weight average molecular weight of 80,000) are used as raw materials to perform composite melt spinning in a composite spinning machine; the composite spinning machine includes two single-screw extruders, the spinning temperature of the composite spinning machine is 230 degrees Celsius, the fluorine-containing polyethylene resin and the unmodified polyethylene resin are respectively added to different single-screw extruders to form melts, the melts are metered and conveyed to a composite spinning assembly through respective metering pumps, and the melts are extruded through a composite spinneret to obtain a continuous melt with the fluorine-containing polyethylene resin as a skin layer and the unmodified polyethylene resin as a core layer; the fluorine-containing polyethylene resin accounts for 9.5 parts by mass in the continuous melt, and the unmodified polyethylene resin accounts for 90.5 parts by mass; after air cooling, solidification is performed, and after drawing 9 times at 110 degrees Celsius, a modified polyethylene fiber with the fluorine-containing polyethylene resin as a skin layer and the unmodified polyethylene resin as a core layer is prepared, and the skin layer accounts for 10 parts by mass and the core layer accounts for 90 parts by mass.

[0044] Step 4: The PTFE resin and isomeric alkane solvent oil are melted and softened at 150 degrees Celsius by using a double-screw extruder, coated on the surface of the modified polyethylene fiber obtained in step 3 by a melt coating process, then deoiled at 160 degrees Celsius to form a PTFE skin layer, and then cooled to obtain a PE / PTFE composite fiber, and the PTFE skin layer accounts for 17% of the total fiber mass.

[0045] Example 3

[0046] The embodiment provides a PE / PTFE composite fiber for preventing fouling and bioattachment, and a preparation method thereof.

[0047] Step 1: A benzophenone compound with a structure as shown in formula 1, a thio peroxide dicarbonate with a structure as shown in formula 2, and 2-(perfluorohexyl) ethyl methacrylate are mixed in a mass ratio of 1:1:120 to obtain a modified solution, with dioxane as a solvent. Polyethylene resin chips with a weight average molecular weight of 100,000 are added to the modified solution, the mass ratio of the polyethylene resin chips to the 2-(perfluorohexyl) ethyl methacrylate is 1:50, 150 milliliters / minute of high-purity argon is introduced, and stirring is performed for 60 minutes to obtain a solid-liquid mixture.

[0048] Step 2: The solid-liquid mixture obtained in step 1 is irradiated with ultraviolet light with a wavelength of 253 nm for 15 hours, stirring is continuously performed during the irradiation, and argon is introduced at an amount of 320 milliliters / minute, and the temperature of the solid-liquid mixture is controlled at 30 degrees Celsius. The irradiated solid-liquid mixture is filtered and dried at 65 degrees Celsius for 4 hours to obtain fluorine-containing polyethylene resin chips.

[0049] Step 3: The fluorine-containing polyethylene resin chips obtained in step 2 and polyethylene resin chips (weight average molecular weight of 100,000) are used as raw materials to perform composite melt spinning in a composite spinning machine; the composite spinning machine includes two single-screw extruders, the spinning temperature of the composite spinning machine is 230 degrees Celsius, the fluorine-containing polyethylene resin and the unmodified polyethylene resin are respectively added to different single-screw extruders to form melts, the melts are metered and conveyed to a composite spinning assembly through respective metering pumps, and the melts are extruded through a composite spinneret to obtain a continuous melt with the fluorine-containing polyethylene as a skin layer and the unmodified polyethylene resin as a core layer; the fluorine-containing polyethylene accounts for 10 parts by mass in the continuous melt, and the unmodified polyethylene resin accounts for 90 parts by mass; after air cooling, solidification is performed, and after drawing 10 times at 113 degrees Celsius, a modified polyethylene fiber with the fluorine-containing polyethylene resin as the skin layer and the unmodified polyethylene resin as the core layer is prepared, and the skin layer accounts for 10 parts by mass and the core layer accounts for 90 parts by mass.

[0050] Step 4: PTFE resin and isomeric alkane solvent oil are melted and softened at 180 degrees Celsius using a double-screw extruder, coated on the surface of the modified polyethylene fiber obtained in step 3 through a melt coating process, then deoiled at 160 degrees Celsius to form a PTFE skin layer, and then cooled to obtain a PE / PTFE composite fiber, and the PTFE skin layer accounts for 13.5% of the total fiber mass.

[0051] Example 4

[0052] The embodiment provides a PE / PTFE composite fiber for preventing fouling and biofouling, and a preparation method thereof.

[0053] Step 1: Diphenyl ketone compound with a structure as shown in formula 1, thio peroxide dicarbonate with a structure as shown in formula 2, and 2-(perfluorodecyl) ethyl methacrylate are mixed at a ratio of 1:1:140 to obtain a modified solution, using dioxane as a solvent. Polyethylene resin chips with a weight average molecular weight of 150,000 are added to the modified solution, the mass ratio of the polyethylene resin chips to the 2-(perfluorodecyl) ethyl methacrylate is 1:70, high-purity argon gas is introduced at a flow rate of 150 milliliters per minute, and stirring is performed for 60 minutes to obtain a solid-liquid mixture.

[0054] Step 2: The solid-liquid mixture obtained in step 1 is irradiated with ultraviolet light with a wavelength of 253 nm for 20 hours, stirring is continuously performed during the irradiation, argon gas is introduced at a flow rate of 450 milliliters per minute, and the temperature of the solid-liquid mixture is controlled at 40 degrees Celsius. The irradiated solid-liquid mixture is filtered and dried at 70 degrees Celsius for 5 hours to obtain fluorine-containing polyethylene resin chips.

[0055] Step 3: The fluorine-containing polyethylene resin chips obtained in Step 2 and polyethylene resin chips (weight average molecular weight of 150,000) were used as raw materials to perform composite melt spinning in a composite spinning machine; the composite spinning machine included two single-screw extruders, the spinning temperature was 230 degrees Celsius, the fluorine-containing polyethylene resin and the unmodified polyethylene resin were respectively added to different single-screw extruders to form melts, and the melts were metered and conveyed to a composite spinning assembly through respective metering pumps, and then extruded through a composite spinneret to obtain a continuous melt with the fluorine-containing polyethylene resin as the skin layer and the unmodified polyethylene resin as the core layer; the fluorine-containing polyethylene resin accounted for 12 parts by mass in the continuous melt, and the unmodified polyethylene resin accounted for 88 parts by mass; after air cooling, solidification was performed, and then drawing was performed at 125 degrees Celsius to obtain a modified polyethylene fiber with the fluorine-containing polyethylene resin as the skin layer and the unmodified polyethylene resin as the core layer; the skin layer accounted for 12 parts by mass, and the core layer accounted for 88 parts by mass.

[0056] Step 4: The PTFE resin and the isoparaffin solvent oil were melted and softened at 137 degrees Celsius using a double-screw extruder, and were coated on the surface of the modified polyethylene fiber obtained in Step 3 through a melt coating process, and then were deoiled at 158 degrees Celsius to form a PTFE skin layer, and then were cooled to obtain a PE / PTFE composite fiber; the skin layer PTFE accounted for 16.7% of the total fiber mass.

[0057] Comparative Example 1

[0058] The preparation method of the comparative example is as follows:

[0059] Step 1: Polyethylene chips with a weight average molecular weight of 100,000 were spun at 230 degrees Celsius, and then were drawn at 90 degrees Celsius to obtain a polyethylene fiber.

[0060] Step 2: The PTFE resin and the isoparaffin solvent oil were melted and softened at 180 degrees Celsius using a double-screw extruder, and were coated on the surface of the polyethylene fiber obtained in Step 1 through a melt coating process, and then were deoiled at 165 degrees Celsius to form a PTFE skin layer, and then were cooled to obtain a PE / PFA composite fiber; the skin layer PFA accounted for 13% of the total fiber mass.

[0061] Comparative Example 2

[0062] The preparation method of the comparative example is as follows:

[0063] Step 1: Polyethylene chips with a weight average molecular weight of 80,000 were spun at 220 degrees Celsius, and then were drawn at 110 degrees Celsius to obtain a polyethylene fiber.

[0064] Step 2: PTFE resin and isomeric alkane solvent oil were melted and softened by a twin-screw extruder at 135 degrees Celsius, coated on the surface of polyethylene fiber obtained in step 1 by a melt coating process, then deoiled at 180 degrees Celsius to form a PTFE skin layer, and cooled to obtain PE / PFA composite fiber, with the mass of the skin layer PFA accounting for 12% of the total mass of the fiber.

[0065] Comparative Example 3

[0066] The preparation method of the comparative example is as follows:

[0067] Step 1: Polyethylene chip with a weight average molecular weight of 100,000 was spun at 230 degrees Celsius, and then drawn 8 times at 90 degrees Celsius to obtain polyethylene fiber.

[0068] Comparative Example 4

[0069] The preparation method of the comparative example is as follows:

[0070] Polyethylene chip with a weight average molecular weight of 80,000 was spun at 220 degrees Celsius, and then drawn 10 times at 110 degrees Celsius to obtain polyethylene fiber.

[0071] Comparative Example 5

[0072] The difference between the comparative example and Example 1 is that the PTFE resin is replaced with an equal amount of polyvinylidene fluoride (PVDF).

[0073] Comparative Example 6

[0074] The difference between the comparative example and Example 1 is that the polyethylene resin chip with a weight average molecular weight of 100,000 is replaced with an equal amount of polypropylene (PP) with a weight average molecular weight of 100,000.

[0075] Comparative Example 7

[0076] The difference between the comparative example and Example 1 is that the polyethylene resin chip with a weight average molecular weight of 100,000 is replaced with an equal amount of polyamide (PA) with a weight average molecular weight of 100,000.

[0077] Performance test

[0078] The tensile properties of the composite fibers provided by each of the above examples and comparative examples were tested according to GB / T 14344-2022 "Chemical Fiber Filament Tensile Property Test Method", the surface bioadhesion amount of the composite fibers after immersion in seawater for half a year was calculated by weighing method, and the abrasion resistance was evaluated by rubbing the composite fibers on 500 mesh sandpaper. The test results are shown in Table 1:

[0079] Table 1: Fiber properties of each example and comparative example

[0080]

[0081]

[0082] From the above table, it can be seen that the PE / PTFE composite fiber prepared by the application has excellent tensile strength and wear resistance, which is significantly improved compared with the product obtained by the conventional method, especially in the wear resistance index, which shows that the method of the application can effectively improve the performance of the fiber.

[0083] In terms of surface biological adhesion amount after seawater immersion for half a year, examples 1 to 4, comparative example 1 and comparative example 2 coated with PTFE skin layer all show better anti-adhesion than comparative example 3 and comparative example 4, which is mainly due to the low surface energy of PTFE material. At the same time, the surface biological adhesion amount of the fiber coated with PVDF (comparative example 5) is also less than that of example 1, which shows that the low surface energy effect of PTFE material is better than that of PVDF.

[0084] After simulating the friction environment in daily use, due to the new improved process of the fibers of examples 1 to 4 of the application, the wear resistance can be effectively improved, and the PTFE coating layer of the fiber is retained, so the biological adhesion amount on the surface of the fiber is still very low, which shows excellent and durable anti-biological adhesion; while comparative example 1 and comparative example 2, due to the low interaction force between the core layer polyethylene and the skin layer PTFE, are easy to separate under the friction effect in daily use, the surface of the fiber will be damaged and roughened, causing the PTFE layer to fall off, thereby greatly affecting the original anti-biological adhesion effect, which is the reason why the biological adhesion amount on the surface of the fiber of comparative example 1 and comparative example 2 is significantly improved after friction. At the same time, compared with example 1, comparative example 7 and comparative example 8, due to the difference in core layer material, although they also undergo the same modification treatment, but the wear resistance and mechanical properties under the same conditions are very weak.

[0085] The specific embodiments are only an explanation of the application, and are not a limitation of the application, and those skilled in the art can make modifications to the embodiments without creative contribution after reading the specification, but as long as the modifications are within the scope of the claims of the application, they are protected by the patent law.

Claims

1. A PE / PTFE composite fiber for antifouling and anti-bioattachment, characterized by, The PE / PTFE composite fiber has a layered structure, the inner layer is a modified polyethylene fiber, and the outer layer is a PTFE coating layer, and the mass percentage of the PTFE coating layer is 3-35wt%. The tensile strength of the PE / PTFE composite fiber is above 5.8 cN / dtex, the surface biological adhesion amount after immersion in seawater for half a year is below 0.0012 g / m, and the surface biological adhesion amount after friction for 5000 times and immersion in seawater for half a year is below 0.0022 g / m. The preparation method of the modified polyethylene fiber comprises the following steps: The fluorine-containing acrylate, the benzophenone compound and the alkyl ester containing thio peroxide dicarbonate are dispersed in an organic solvent to obtain a modification liquid; The polyethylene resin chip is added into the modification liquid, and a solid-liquid mixture is obtained by stirring under an inert atmosphere; the solid-liquid mixture is irradiated under ultraviolet light of 245-260 nm, and then continuously stirred and inert gas is introduced; and the fluorine-containing polyethylene resin chip is obtained by filtering and drying. The polyethylene resin chip and the fluorine-containing polyethylene resin chip are compounded and melt-spun, and the modified polyethylene fiber with the skin layer being the fluorine-containing polyethylene resin and the core layer being the unmodified polyethylene resin is prepared by hot drawing.

2. The anti-fouling, anti-biofouling PE / PTFE composite fiber according to claim 1, characterized by, In the modified polyethylene fiber, the core layer is 5-90 parts by weight, and the skin layer is 25-95 parts by weight.

3. A method for producing the antifouling and anti-bioattachment PE / PTFE composite fiber according to claim 1 or 2, characterized by, It comprises: The PTFE resin is blended and softened with the isoparaffin solvent oil, and then coated on the surface of the modified polyethylene fiber to form a PTFE coating layer after cooling and deoiling, thereby obtaining the PE / PTFE composite fiber.

4. The method for producing a PE / PTFE composite fiber according to claim 3, characterized by, The softening process comprises that the PTFE resin is blended and melt-softened with the isoparaffin solvent oil at 100-300 DEG C through a screw extruder.

5. The method of producing a PE / PTFE composite fiber according to claim 3, characterized by, The deoiling temperature in the process of forming the PTFE coating layer is 80-250 DEG C.

6. The method of producing a PE / PTFE composite fiber according to claim 3, characterized by, The fluorine-containing acrylate comprises one or a combination of 2-(perfluorobutyl) ethyl methacrylate, 2-(perfluorooctyl) ethyl methacrylate, 2-(perfluorohexyl) ethyl methacrylate, 2-(perfluorodecyl) ethyl methacrylate, 2-perfluorooctyl acrylate, 3-(perfluoro-5-methylhexyl)-2-hydroxypropyl methacrylate, 1,1,1,3,3,3-hexafluoroisopropyl acrylate, and 2-(perfluorododecyl) ethyl acrylate.

7. The method of producing a PE / PTFE composite fiber according to claim 3, characterized by, In the modification liquid, the molar ratio of the fluorine-containing acrylate, the benzophenone compound and the alkyl ester containing thio peroxide dicarbonate is (80-350):1:

1.

8. The method for producing a PE / PTFE composite fiber according to claim 7, characterized by, The benzophenone compound is a compound shown in formula 1, and the alkyl ester containing thio peroxide dicarbonate is a compound shown in formula 2.

9. The method of producing a PE / PTFE composite fiber according to claim 3, characterized by, In the process of preparing the fluorine-containing polyethylene resin chip, the temperature of the solid-liquid mixture is controlled to be 10-60 DEG C, and the ultraviolet lamp irradiation time is 3-48 h.

10. The method of producing a PE / PTFE composite fiber according to claim 3, characterized by, In the process of the compound melt spinning, the spinning temperature is 100-240 DEG C, the hot drawing temperature is 80-130 DEG C, and the drawing ratio is 3-15 times.

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