Marine antifouling and long afterglow polypropylene special for fishing net thread and preparation method thereof

Abstract

The application discloses a kind of marine anti-fouling, long afterglow luminescent polypropylene special for fishing net thread and a preparation method thereof, comprising the following components, polypropylene resin 55~80 parts, reinforcing resin 6~35 parts, compatibilizer 5~20 parts, antioxidant 0.5~1.5 parts, nucleating agent 0.1~0.8 parts, lubricant 1.2~6 parts, rigidifying agent 0~5 parts, luminous agent 5~18 parts, anti-bioadsorption composite agent 5~24 parts.The marine anti-fouling, long afterglow luminescent polypropylene prepared by the method has excellent luminescent performance and long-term anti-bioadsorption, and it still has good mechanical strength, good comprehensive performance, and great application value and market competitiveness.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of polymer modification, and particularly relates to a marine antifouling and long-afterglow luminescent polypropylene special for fishing net lines and a preparation method thereof. BACKGROUND

[0002] Fishing nets are important production tools for cultivating, capturing and harvesting various aquatic products in modern fisheries, which are mainly made of polyethylene, polyvinyl chloride, polypropylene or nylon line materials. The fishing nets are usually required to have good tensile strength, creep resistance and toughness.

[0003] With the development and diversification of aquatic farming, people not only require fishing nets to have good mechanical properties, but also to meet the needs of some special scene applications. The fishing nets need to be soaked in water for a long time during use, and the surface of the fishing nets is easy to attach and grow algae, moss, fungi, barnacles, mussels, oysters and other organisms, which will cause the fishing nets to be biologically eroded, thus increasing the drag resistance of fishing gear during operation, and easily leading to accelerated aging and shortened service life of the fishing nets. Therefore, it is of great significance to functionalize the anti-bioabsorption of fishing nets. Meanwhile, many fish species exhibit positive phototaxis, i.e. they have a certain attraction to light. Aquatic economic animals with positive phototaxis include barracuda, Japanese sardine, fat-eye herring, red-backed round herring, mackerel, bamboo laughing fish, spotted shiner, Pacific squid, piper, jade muscle fish, green scale fish, Japanese prawn, crab, Japanese barracuda, silverfish, jaw needle fish, Japanese single barracuda, three-line fish, tuna, bonito, etc. Self-luminescent fishing nets can selectively capture fish species at night or in deep sea areas, improve fishing efficiency, and have important development value.

[0004] CN109023585A reports an antibacterial clean fishing net and a preparation method thereof, in which tetraethyl orthosilicate is used to modify nano-titanium dioxide and aluminum borate whiskers to improve the mechanical properties of the fishing net material, and the nano-silicon dioxide and nano-titanium dioxide synergistically improve the antibacterial properties. CN112341805A reports a polyethylene-based fishing net composite material, which uses polyamide chips as the main material, adds antifouling fillers, modified polyethylene fibers and other auxiliary agents, and utilizes the special physical and chemical properties of graphene and elorite to make the composite material have good mechanical properties, high antifouling performance and aging resistance. CN106435806A reports a nylon luminescent fiber for weaving fishing nets, in which the added fluorescent powder component can emit light at night, and the woven fishing nets improve the catching effect. The luminescent fishing net materials in the prior art usually do not have the anti-bioabsorption property, and the attached biological and algal species will be adsorbed on the surface of the fishing nets during the sea immersion operation, resulting in a decrease in the light intensity and light efficiency of the fishing nets. In addition, the anti-bioabsorption agent in the existing anti-bioabsorption fishing net material will quickly migrate and lose into the water phase during long-term immersion operation, resulting in a rapid weakening or loss of the anti-bioabsorption effect of the fishing net material. SUMMARY

[0005] In order to solve the problems of the prior art, to endow the fishing net material with good self-luminous performance, to improve the fishing efficiency, and to solve the problem of the decline of the service life of the material caused by the growth of bio-adsorption during the process of the fishing net being immersed in the sea, the application provides a marine antifouling and long-afterglow luminous polypropylene special for fishing net lines and a preparation method thereof, a marine antifouling and long-afterglow luminous polypropylene special for fishing net lines is prepared through carrier adsorption and compatibility modification, the problem of rapid loss of the anti-bio-adsorption agent is overcome, and the material is endowed with the self-luminous characteristic, so that the fishing net material has the long-acting anti-bio-adsorption effect, the long-afterglow self-luminous characteristic and excellent mechanical performance.

[0006] To achieve the above-mentioned purpose, the application adopts the following technical scheme:

[0007] The marine antifouling and long-afterglow luminous polypropylene special for fishing net lines is prepared from the following raw materials in parts by weight: polypropylene resin 55-80 parts, reinforcing resin 6-35 parts, compatibilizer 5-20 parts, antioxidant 0.5-1.5 parts, nucleating agent 0.1-0.8 parts, lubricant 1.2-6 parts, rigidifying agent 0-5 parts, luminous agent 5-18 parts, and anti-bio-adsorption composite agent 5-24 parts.

[0008] Further, the polypropylene resin is one or more of homopolymer polypropylene, ethylene-propylene copolymer, propylene-butylene copolymer and ethylene-propylene-butylene copolymer, the melt index (230 DEG C, 2.16 Kg) of which is 2.5-150 g / 10 min, the flexural modulus is greater than 800 MPa, and the tensile yield strength is greater than 28 MPa.

[0009] Further, the reinforcing resin is one or more of UWMPE, PA6, PC, TPU, PET or COC.

[0010] Further, the compatibilizer is maleic anhydride grafted polypropylene, maleic anhydride grafted ethylene-vinyl acetate copolymer, maleic anhydride grafted ternary ethylene-propylene rubber, glycidyl methacrylate grafted polypropylene, butyl methacrylate grafted polypropylene or maleic anhydride grafted ethylene-octene copolymer.

[0011] Further, the antioxidant includes primary antioxidant and secondary antioxidant; the primary antioxidant is one or more of hindered phenolic antioxidant and hindered amine antioxidant; the secondary antioxidant is one or more of phosphite antioxidant, thioester antioxidant, thio-bisphenol antioxidant and sulfide type phenolic antioxidant; and the mass ratio of the primary antioxidant to the secondary antioxidant is 1:0.2-0.4.

[0012] Further, the nucleating agent is one or more of sorbitol acetal nucleating agent, phosphate nucleating agent, amide nucleating agent, carboxylate nucleating agent.

[0013] Further, the lubricant is one or more of polyethylene wax, paraffin wax, stearic acid, hydroxystearic acid, n-butyl stearate, calcium stearate, magnesium stearate, zinc stearate, silicone, erucamide, stearamide, oleamide.

[0014] Further, the rigidifying agent is one or more of aluminum borate whisker, nano-titanium dioxide, nano-montmorillonite, nano-talc powder, wollastonite fiber, calcium carbonate whisker.

[0015] Further, the luminescent agent is ZnS:Cu 2+ , ZnS:Mn 2+ , CaS:Eu 2+ , Dy 3+ , CaAl2O4:Eu 2+ , Nd 3+ , SrAl2O4:Eu 2+ , Dy 3+ , Sr2MgSi2O7:Eu 2+ , Sr4Al 14 O 25 :Eu 2+ , Dy 3+ , CaAl2O4:Ce 3+ , Tb 3+ , Sr3Al2O6:Eu 3+ , SrAl2O4:Eu 2+ , SrAl2O4:Ce 3+ , CaLaAl3O7:Tb 3+ , CaYAl3O7:Ce 3+ , Ca2MgSi2O7:Eu 2+ , Ba2MgSi2O7:Eu 2 + , ZnCaOS:Mn 2+ , MgSiO3:Mn 2+ , Eu 2+ , Dy 3+ , ZnGa2O4:Cr 3+ , ZnGa2O4:Tb 3+ , ZnGa2O4:Mn 2+ , ZnGa2O4:Bi 3+ , CaZnOS-ZnS:Dy 3+ , CaZnOS-ZnS:Er 3+ , and CaZnOS-ZnS:Eu2+ one or more of the following:

[0016] Further, the preparation steps of the anti-bio adsorption complexing agent are as follows:

[0017] (1) Dissolve the anti-bio adsorption agent in a mixed solvent of EtOH / DMSO to obtain an anti-adsorption agent solution with a concentration of 0.1-1 g / mL;

[0018] (2) Weigh 5-20 g of nano-mesoporous silica and disperse it in 100 mL of EtOH, stir until evenly dispersed, then add 10-200 mL of the anti-adsorption agent solution prepared above, set the loading temperature to 30-50°C, continue stirring for 24-48 h, then place the sample in a centrifuge at 3000-6000 r / min for 5 min, collect the precipitate after centrifugation, and dry it at 80-110°C under reduced pressure to obtain the anti-bio adsorption complexing agent.

[0019] Preferably, the anti-bio adsorption agent in step (1) is one or more of the following: 6-bromoindole-3-formaldehyde, 2,5,6-tribromo-1-methyl-3-dimethylaminoindole, 4,5-dichloro-2-n-octyl-4-isothiazolinone-3, 2-(p-chlorophenyl)-3-cyano-4-bromo-5-trifluoromethyl-pyrrole, 2-(p-chlorophenyl)-3-cyano-4-bromo-5-trifluoromethyl-pyrrole, N-(2,4,6-trichlorophenyl) maleimide, 2-tert-butylamino-4-cyclopropylamino-6-methylthio-s-triazine, pyridine triphenyl boron, or 2,4,5,6-tetrachloro-1,3-benzenedicarbonitrile.

[0020] Preferably, the nano-mesoporous silica in step (2) is one or more of the following: HMSNs, MCM-41, SBA-15, KIT-6.

[0021] The preparation method of the marine anti-fouling and long-afterglow polypropylene special for fishing net line comprises the following steps:

[0022] (1) Mix polypropylene resin, reinforcing resin, compatibilizer, antioxidant, nucleating agent, lubricant, rigidifying agent, luminous agent, and anti-bio adsorption complexing agent in a high-speed mixer according to the proportions to obtain a premix;

[0023] (2) Melt-extrude the premix obtained in step (1) through a twin-screw extruder, with a screw rotation speed of 20-200 rpm, a temperature of 170-180°C in the first zone, a temperature of 190-200°C in the second zone, a temperature of 200-210°C in the third zone, a temperature of 210-230°C in the fourth zone, a temperature of 210-230°C in the fifth zone, a temperature of 210-230°C in the sixth zone, and a die temperature of 200-210°C, and then cool and pelletize to obtain marine anti-fouling and long-afterglow polypropylene granules special for fishing net line.

[0024] (3) The marine anti-fouling and long afterglow luminescent polypropylene particles for fishing net line in step (2) are subjected to melt extrusion through a double screw extruder and a spinning metering pump. The extruded fibers are cooled in a water tank at 20-30 DEG C, and the draw ratio is 3-10 times. After winding, monofilaments are obtained.

[0025] The present application has the advantages that, compared with the prior art, the present application provides a preparation method of marine anti-fouling and long afterglow luminescent polypropylene for fishing net line. First, the mesoporous silica is loaded with an anti-biofouling agent and then dispersed into polypropylene, which effectively prevents the rapid migration and loss of the anti-biofouling agent in long-period sea operation, prolonging the anti-biofouling life of the fishing net material. Second, the long afterglow luminescent agent is doped in the polypropylene-based fishing net material, which endows the material with self-luminescent function, so that the prepared fishing net can emit light for a long time when used at night or in the middle layer of the sea, achieving the purpose of trapping fish and improving the fishing efficiency. In addition, on the basis of long-term anti-biofouling and long self-luminescent life of the polypropylene-based fishing net material, the material also has excellent mechanical properties. BRIEF DESCRIPTION OF DRAWINGS

[0026] Figure 1 The physical picture of the polypropylene particles of Example 5. DETAILED DESCRIPTION

[0027] In order to make the content of the present application more convenient to understand, the technical solutions of the present application will be further described below in combination with specific embodiments, but the present application is not limited thereto.

[0028] In the examples, the experimental methods used are conventional methods unless otherwise specified; the materials, reagents, etc. used are commercially available unless otherwise specified.

[0029] Example 1

[0030] In a 200 mL beaker, 100 mL of EtOH / DMSO (V / V = 2:8) was added and preheated in an ultrasonic cleaner. The water temperature of the ultrasonic cleaner was set to 55 DEG C. 30 g of 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one (DCOIT) was added in three batches, and continuous stirring and ultrasonic treatment were required during each addition process until the anti-biofouling agent was completely dissolved. A solution of DCOIT was prepared.

[0031] In a 500 mL single-necked flask, 8 g of SBA-15 mesoporous silica and 40 mL of EtOH were added, and then transferred to a constant-temperature water bath, the temperature of the constant-temperature water bath was set to 50°C, and the stirring speed was set to 400 rpm. Then, 100 mL of the above-mentioned DCOIT solution was added dropwise, and the heating and stirring was continued for 24 h. Subsequently, the sample was centrifuged at a speed of 4000 r / min for 5 min, and the precipitate was collected and dried at 100°C under reduced pressure to obtain mesoporous silica loaded with DCOIT.

[0032] Example 2

[0033] In a 200 mL beaker, 100 mL of EtOH / DMSO (V / V = 2:8) was added and preheated in an ultrasonic cleaner, the water temperature of the ultrasonic cleaner was set to 55°C, and 30 g of 2-tert-butylamino-4-cyclopropylamino-6-methylthio-s-triazine (CDMTD) was added in three batches, and each time the stirring and ultrasonic treatment was continued until the antibioadsorbent was completely dissolved to prepare a solution of CDMTD.

[0034] In a 500 mL single-necked flask, 8 g of SBA-15 mesoporous silica and 40 mL of EtOH were added, and then transferred to a constant-temperature water bath, the temperature of the constant-temperature water bath was set to 50°C, and the stirring speed was set to 400 rpm. Then, 100 mL of the above-mentioned CDMTD solution was added dropwise, and the heating and stirring was continued for 24 h. Subsequently, the sample was centrifuged at a speed of 4000 r / min for 5 min, and the precipitate was collected and dried at 100°C under reduced pressure to obtain mesoporous silica loaded with CDMTD.

[0035] Example 3

[0036] In a 200 mL beaker, 100 mL of EtOH / DMSO (V / V = 2:8) was added and preheated in an ultrasonic cleaner, the water temperature of the ultrasonic cleaner was set to 55°C, and 30 g of N-(2,4,6-trichlorophenyl) maleimide (TCPM) was added in three batches, and each time the stirring and ultrasonic treatment was continued until the antibioadsorbent was completely dissolved to prepare a solution of TCPM.

[0037] In a 500 mL single-necked flask, 8 g of SBA-15 mesoporous silica and 40 mL of EtOH were added, and then transferred to a constant-temperature water bath, the temperature of the constant-temperature water bath was set to 50°C, and the stirring speed was set to 400 rpm. Then, 100 mL of the above-mentioned TCPM solution was added dropwise, and the heating and stirring was continued for 24 h. Subsequently, the sample was centrifuged at a speed of 4000 r / min for 5 min, and the precipitate was collected and dried at 100°C under reduced pressure to obtain mesoporous silica loaded with TCPM.

[0038] Example 4

[0039] 75 parts of homopolymer polypropylene, 25 parts of UWMPE, 15 parts of maleic anhydride modified polypropylene, 0.9 parts of antioxidant 1010, 0.3 parts of antioxidant 168, 0.2 parts of nucleating agent 3988, 0.5 parts of calcium stearate, 1.5 parts of erucamide, 3 parts of nano titanium dioxide, 10 parts of luminous agent CaAl2O4:Eu 2+ ,Nd 3+ and 10 parts of mesoporous silica supported DCOIT obtained in Example 1 were placed in a high-speed mixer, the rotation speed was set to 500 rpm, the mixing time was 20 min, and after uniform mixing, a premix was obtained.

[0040] The above premix was melt-extruded through a twin-screw extruder, the screw rotation speed was 100 rpm, the temperature of the first zone was 170°C, the temperature of the second zone was 190°C, the temperature of the third zone was 210°C, the temperature of the fourth zone was 230°C, the temperature of the fifth zone was 230°C, the temperature of the sixth zone was 230°C, and the die temperature was 200°C. After cooling and pelletizing, the marine antifouling and long-afterglow polypropylene pellets special for fishing net lines were obtained.

[0041] The above marine antifouling and long-afterglow polypropylene pellets special for fishing net lines were melt-extruded through a twin-screw extruder and a spinning metering pump, and the melt temperature was controlled at 230°C. The extruded fibers were cooled in a water tank at 20°C. The cooled fibers were subjected to four-stage stretching, and the stretching conditions were as follows: first stage, stretching temperature 75°C, stretching ratio 10 times; second stage, stretching temperature 90°C, stretching ratio 7 times; third stage, stretching temperature 95°C, stretching ratio 5 times; and fourth stage, stretching temperature 100°C, stretching ratio 3 times. The stretched fibers were subjected to sizing and winding to obtain monofilaments.

[0042] Example 5

[0043] 75 parts of homopolymer polypropylene, 25 parts of UWMPE, 15 parts of maleic anhydride modified polypropylene, 0.9 parts of antioxidant 1010, 0.3 parts of antioxidant 168, 0.2 parts of nucleating agent 3988, 0.5 parts of calcium stearate, 1.5 parts of erucamide, 3 parts of nano titanium dioxide, 10 parts of luminous agent SrAl2O4:Eu 2+ ,Dy 3+ and 10 parts of mesoporous silica supported DCOIT obtained in Example 1 were placed in a high-speed mixer, the rotation speed was set to 500 rpm, the mixing time was 20 min, and after uniform mixing, a premix was obtained.

[0044] The above-mentioned pre-mixed material is melt-extruded through a twin-screw extruder, the screw rotation speed is 100 rpm, the temperature of the first zone is 170°C, the temperature of the second zone is 190°C, the temperature of the third zone is 210°C, the temperature of the fourth zone is 230°C, the temperature of the fifth zone is 230°C, the temperature of the sixth zone is 230°C, the die temperature is 200°C, and the fishnet line special marine antifouling and long-afterglow polypropylene granules are obtained after cooling and granulation.

[0045] The above-mentioned fishnet line special marine antifouling and long-afterglow polypropylene granules are melt-extruded through a twin-screw extruder and a spinning metering pump, the melt temperature is controlled at 230°C, and the extruded fibers are cooled in a water tank at 20°C; the cooled fibers are subjected to four-stage stretching, and the stretching conditions are as follows: first stage: stretching temperature 75°C, stretching ratio 10 times, second stage: stretching temperature 90°C, stretching ratio 7 times, third stage: stretching temperature 95°C, stretching ratio 5 times, and fourth stage: stretching temperature 100°C, stretching ratio 3 times; the stretched fibers are subjected to setting and winding to obtain monofilaments. The physical map of the polypropylene granules is shown in Figure 1 .

[0046] Example 6

[0047] 75 parts of homopolymer polypropylene, 25 parts of UWMPE, 15 parts of maleic anhydride modified polypropylene, 0.9 parts of antioxidant 1010, 0.3 parts of antioxidant 168, 0.2 parts of nucleating agent 3988, 0.5 parts of calcium stearate, 1.5 parts of erucamide, 3 parts of nano-titanium dioxide, 10 parts of luminescent agent Sr2MgSi2O7:Eu 2+ and 10 parts of mesoporous silica loaded DCOIT obtained in Example 1 are placed in a high-speed mixer, the rotation speed is set at 500 rpm, the mixing time is 20 min, and the pre-mixed material is obtained after uniform mixing.

[0048] The above-mentioned pre-mixed material is melt-extruded through a twin-screw extruder, the screw rotation speed is 100 rpm, the temperature of the first zone is 170°C, the temperature of the second zone is 190°C, the temperature of the third zone is 210°C, the temperature of the fourth zone is 230°C, the temperature of the fifth zone is 230°C, the temperature of the sixth zone is 230°C, the die temperature is 200°C, and the fishnet line special marine antifouling and long-afterglow polypropylene granules are obtained after cooling and granulation.

[0049] The above-mentioned marine anti-fouling and long-afterglow polypropylene particles special for fishing net line are melted and melt-extruded through a double-screw extruder and a spinning metering pump, with the melt temperature controlled at 230°C. The extruded fibers are cooled in a water tank at 20°C. The cooled fibers are subjected to four-stage stretching, with the stretching conditions being: first stage, stretching temperature 75°C, stretching ratio 10 times; second stage, stretching temperature 90°C, stretching ratio 7 times; third stage, stretching temperature 95°C, stretching ratio 5 times; and fourth stage, stretching temperature 100°C, stretching ratio 3 times. The stretched fibers are subjected to setting and winding to obtain monofilaments.

[0050] Example 7

[0051] 80 parts of homopolymer polypropylene, 20 parts of PA6, 15 parts of maleic anhydride modified polypropylene, 0.9 parts of antioxidant 1010, 0.3 parts of antioxidant 168, 0.2 parts of nucleating agent 3988, 0.5 parts of calcium stearate, 1.5 parts of erucamide, 3 parts of nano-titanium dioxide, 10 parts of luminescent agent SrAl2O4:Eu 2+ ,Dy 3+ and 10 parts of mesoporous silica loaded DCOIT obtained in Example 1 are placed in a high-speed mixer, with the rotation speed set at 500 rpm and the mixing time set at 20 min. After uniform mixing, a premix is obtained.

[0052] The above-mentioned premix is melt-extruded through a double-screw extruder, with the screw rotation speed being 100 rpm, the temperature of the first zone being 170°C, the temperature of the second zone being 190°C, the temperature of the third zone being 210°C, the temperature of the fourth zone being 230°C, the temperature of the fifth zone being 230°C, the temperature of the sixth zone being 230°C, and the die temperature being 200°C. After cooling and granulation, marine anti-fouling and long-afterglow polypropylene particles special for fishing net line are obtained.

[0053] The above-mentioned marine anti-fouling and long-afterglow polypropylene particles special for fishing net line are melted and melt-extruded through a double-screw extruder and a spinning metering pump, with the melt temperature controlled at 230°C. The extruded fibers are cooled in a water tank at 20°C. The cooled fibers are subjected to four-stage stretching, with the stretching conditions being: first stage, stretching temperature 75°C, stretching ratio 10 times; second stage, stretching temperature 90°C, stretching ratio 7 times; third stage, stretching temperature 95°C, stretching ratio 5 times; and fourth stage, stretching temperature 100°C, stretching ratio 3 times. The stretched fibers are subjected to setting and winding to obtain monofilaments.

[0054] Example 8

[0055] 75 parts of homopolymer polypropylene, 25 parts of UWMPE, 15 parts of maleic anhydride modified polypropylene, 0.9 parts of antioxidant 1010, 0.3 parts of antioxidant 168, 0.2 parts of nucleating agent 3988, 0.5 parts of calcium stearate, 1.5 parts of erucamide, 3 parts of nano titanium dioxide, 15 parts of luminous agent SrAl2O4:Eu 2+ ,Dy 3+ and 10 parts of mesoporous silica supported DCOIT obtained in Example 1 were placed in a high-speed mixer, the rotation speed was set to 500 rpm, the mixing time was 20 min, and after uniform mixing, a premix was obtained.

[0056] The above premix was melt-extruded through a twin-screw extruder, the screw rotation speed was 100 rpm, the temperature of the first zone was 170°C, the temperature of the second zone was 190°C, the temperature of the third zone was 210°C, the temperature of the fourth zone was 230°C, the temperature of the fifth zone was 230°C, the temperature of the sixth zone was 230°C, and the die temperature was 200°C. After cooling and pelletizing, the marine antifouling and long-afterglow polypropylene pellets special for fishing net lines were obtained.

[0057] The above marine antifouling and long-afterglow polypropylene pellets special for fishing net lines were melt-extruded through a twin-screw extruder and a spinning metering pump, and the melt temperature was controlled at 230°C. The extruded fibers were cooled in a water tank at 20°C. The cooled fibers were subjected to four-stage stretching, and the stretching conditions were as follows: first stage, stretching temperature 75°C, stretching ratio 10 times; second stage, stretching temperature 90°C, stretching ratio 7 times; third stage, stretching temperature 95°C, stretching ratio 5 times; and fourth stage, stretching temperature 100°C, stretching ratio 3 times. The stretched fibers were subjected to setting and winding to obtain monofilaments.

[0058] Example 9

[0059] 75 parts of homopolymer polypropylene, 25 parts of UWMPE, 15 parts of maleic anhydride modified polypropylene, 0.9 parts of antioxidant 1010, 0.3 parts of antioxidant 168, 0.2 parts of nucleating agent 3988, 0.5 parts of calcium stearate, 1.5 parts of erucamide, 3 parts of nano titanium dioxide, 18 parts of luminous agent SrAl2O4:Eu 2+ ,Dy 3+ and 10 parts of mesoporous silica supported DCOIT obtained in Example 1 were placed in a high-speed mixer, the rotation speed was set to 500 rpm, the mixing time was 20 min, and after uniform mixing, a premix was obtained.

[0060] The above-mentioned pre-mixed material is melt-extruded through a double-screw extruder, the screw rotation speed is 100 rpm, the temperature of the first zone is 170°C, the temperature of the second zone is 190°C, the temperature of the third zone is 210°C, the temperature of the fourth zone is 230°C, the temperature of the fifth zone is 230°C, the temperature of the sixth zone is 230°C, the die temperature is 200°C, and the fishnet line special marine antifouling and long-afterglow polypropylene granules are obtained after cooling and granulation.

[0061] The above-mentioned fishnet line special marine antifouling and long-afterglow polypropylene granules are melt-extruded through a double-screw extruder and a spinning metering pump, the melt temperature is controlled at 230°C, and the extruded fibers are cooled in a water tank at 20°C; the cooled fibers are subjected to four-stage stretching, and the stretching conditions are as follows: first stage: stretching temperature 75°C, stretching ratio 10 times, second stage: stretching temperature 90°C, stretching ratio 7 times, third stage: stretching temperature 95°C, stretching ratio 5 times, and fourth stage: stretching temperature 100°C, stretching ratio 3 times; the stretched fibers are subjected to setting and winding to obtain monofilaments.

[0062] Example 10

[0063] By mass parts, 75 parts of homopolymer polypropylene, 25 parts of UWMPE, 15 parts of maleic anhydride modified polypropylene, 0.9 parts of antioxidant 1010, 0.3 parts of antioxidant 168, 0.2 parts of nucleating agent 3988, 0.5 parts of calcium stearate, 1.5 parts of erucamide, 3 parts of nano titanium dioxide, 10 parts of luminescent agent SrAl2O4:Eu 2+ ,Dy 3+ and 5 parts of mesoporous silica loaded DCOIT obtained in Example 1 are placed in a high-speed mixer, the rotation speed is set at 500 rpm, the mixing time is 20 min, and the pre-mixed material is obtained after uniform mixing.

[0064] The above-mentioned pre-mixed material is melt-extruded through a double-screw extruder, the screw rotation speed is 100 rpm, the temperature of the first zone is 170°C, the temperature of the second zone is 190°C, the temperature of the third zone is 210°C, the temperature of the fourth zone is 230°C, the temperature of the fifth zone is 230°C, the temperature of the sixth zone is 230°C, the die temperature is 200°C, and the fishnet line special marine antifouling and long-afterglow polypropylene granules are obtained after cooling and granulation.

[0065] The above-mentioned marine anti-fouling and long-afterglow luminescent polypropylene pellets special for fishing net line are melted and melt-extruded through a double-screw extruder and a spinning metering pump, with the melt temperature controlled at 230°C. The extruded fibers are cooled in a water tank at 20°C. The cooled fibers are subjected to four-stage stretching, with the stretching conditions being: first stage, stretching temperature 75°C, stretching ratio 10 times; second stage, stretching temperature 90°C, stretching ratio 7 times; third stage, stretching temperature 95°C, stretching ratio 5 times; and fourth stage, stretching temperature 100°C, stretching ratio 3 times. The stretched fibers are subjected to setting and winding to obtain monofilaments.

[0066] Example 11

[0067] 75 parts of homopolymer polypropylene, 25 parts of UWMPE, 15 parts of maleic anhydride modified polypropylene, 0.9 parts of antioxidant 1010, 0.3 parts of antioxidant 168, 0.2 parts of nucleating agent 3988, 0.5 parts of calcium stearate, 1.5 parts of erucamide, 3 parts of nano-titanium dioxide, 10 parts of luminescent agent SrAl2O4:Eu 2+ ,Dy 3+ and 20 parts of mesoporous silica loaded CDMTD obtained in Example 2 are placed in a high-speed mixer, with the rotating speed set at 500 rpm and the mixing time set at 20 min. After uniform mixing, a premix is obtained.

[0068] The above-mentioned marine anti-fouling and long-afterglow luminescent polypropylene pellets special for fishing net line are melted and melt-extruded through a double-screw extruder and a spinning metering pump, with the melt temperature controlled at 230°C. The extruded fibers are cooled in a water tank at 20°C. The cooled fibers are subjected to four-stage stretching, with the stretching conditions being: first stage, stretching temperature 75°C, stretching ratio 10 times; second stage, stretching temperature 90°C, stretching ratio 7 times; third stage, stretching temperature 95°C, stretching ratio 5 times; and fourth stage, stretching temperature 100°C, stretching ratio 3 times. The stretched fibers are subjected to setting and winding to obtain monofilaments.

[0069] The above-mentioned marine anti-fouling and long-afterglow luminescent polypropylene pellets special for fishing net line are melted and melt-extruded through a double-screw extruder and a spinning metering pump, with the melt temperature controlled at 230°C. The extruded fibers are cooled in a water tank at 20°C. The cooled fibers are subjected to four-stage stretching, with the stretching conditions being: first stage, stretching temperature 75°C, stretching ratio 10 times; second stage, stretching temperature 90°C, stretching ratio 7 times; third stage, stretching temperature 95°C, stretching ratio 5 times; and fourth stage, stretching temperature 100°C, stretching ratio 3 times. The stretched fibers are subjected to setting and winding to obtain monofilaments.

[0070] Comparative Example 1

[0071] Take 75 parts of homopolymer polypropylene, 25 parts of UWMPE, 15 parts of maleic anhydride modified polypropylene, 0.9 parts of antioxidant 1010, 0.3 parts of antioxidant 168, 0.2 parts of nucleating agent 3988, 0.5 parts of calcium stearate, 1.5 parts of erucic acid amide by mass fraction, put into a high-speed mixer, set the rotating speed to 500 rpm, the mixing time is 20 min, uniformly mixed to get the premix.

[0072] The above premix is melt extruded through a twin-screw extruder, the screw rotating speed is 100 rmp, the temperature of zone 1 is 170℃, the temperature of zone 2 is 190℃, the temperature of zone 3 is 210℃, the temperature of zone 4 is 230℃, the temperature of zone 5 is 230℃, the temperature of zone 6 is 230℃, the die temperature is 200℃, and the modified polypropylene pellets are obtained after cooling and granulating.

[0073] The above modified polypropylene pellets are melt extruded through a twin-screw extruder and a spinning metering pump, the melt temperature is controlled at 230℃, and the fiber after extrusion is cooled in a water tank at 20℃; the cooled fiber is stretched by four stages, and the stretching conditions are as follows: first stage: stretching temperature 75℃, stretching ratio 10 times, second stage: stretching temperature 90℃, stretching ratio 7 times, third stage: stretching temperature 95℃, stretching ratio 5 times, fourth stage: stretching temperature 100℃, stretching ratio 3 times; the stretched fiber is fixed and wound to obtain a monofilament.

[0074] Comparative Example 2

[0075] Take 80 parts of homopolymer polypropylene, 20 parts of PA6, 15 parts of maleic anhydride modified polypropylene, 0.9 parts of antioxidant 1010, 0.3 parts of antioxidant 168, 0.2 parts of nucleating agent 3988, 0.5 parts of calcium stearate, 1.5 parts of erucic acid amide by mass fraction, put into a high-speed mixer, set the rotating speed to 500 rpm, the mixing time is 20 min, uniformly mixed to get the premix.

[0076] The above premix is melt extruded through a twin-screw extruder, the screw rotating speed is 100 rmp, the temperature of zone 1 is 170℃, the temperature of zone 2 is 190℃, the temperature of zone 3 is 210℃, the temperature of zone 4 is 230℃, the temperature of zone 5 is 230℃, the temperature of zone 6 is 230℃, the die temperature is 200℃, and the modified polypropylene pellets are obtained after cooling and granulating.

[0077] The modified polypropylene pellets are melt-extruded through a double-screw extruder and a spinning metering pump, the melt temperature is controlled at 230 DEG C, and the extruded fibers are cooled in a water tank at 20 DEG C; the cooled fibers are drawn through four stages, the drawing conditions are as follows: first stage, drawing temperature 75 DEG C, drawing ratio 10 times; second stage, drawing temperature 90 DEG C, drawing ratio 7 times; third stage, drawing temperature 95 DEG C, drawing ratio 5 times; fourth stage, drawing temperature 100 DEG C, drawing ratio 3 times; the drawn fibers are fixed and wound to obtain monofilaments.

[0078] Table 1 shows the release of the anti-bioadhesion composite prepared in Examples 1-3 in water at 30 DEG C.

[0079] Table 1

[0080]

[0081] As shown in Table 1, the prepared anti-bioadhesion composite has good sustained-release function.

[0082] Mechanical property test method: GBT 19975-2005 high-strength fiber filament tensile property test method.

[0083] Luminescent property test method: the prepared sample board 100mm*100mm is placed in a D65 light source box for continuous irradiation for 30min at a distance of 15cm, and then the luminescent intensity is tested in a dark room using a colorimeter. The irradiance is 1.25W / (m 2 nm)@420nm; the black mark temperature is (100±2) DEG C, and the relative humidity is (50±5) %.

[0084] Algae adhesion rate test method: algae antifouling test is to place the fishing net composite material in a water tank containing Chui's No. 10 culture solution containing algae, observe the growth of algae on the surface of the fishing net, and judge the antifouling effect.

[0085] Table 2

[0086]

[0087]

[0088] As shown in Table 2, compared with Comparative Examples 1-2, the algae adhesion rate of each example is significantly lower than that of the comparative examples, which shows that the introduction of the anti-bioadhesion composite can effectively improve the long-acting anti-bioadhesion performance of the polypropylene fishing net; compared with the comparative examples, each example shows strong luminescent intensity and afterglow time, and at the same time has excellent mechanical properties.

[0089] The above only describes the preferred embodiments of the present application, and any equivalent changes and modifications made within the scope of the present application should be included in the scope of the present application.

Claims

1. A marine antifouling, long afterglow luminescent polypropylene for fishing net line, characterized by, The polypropylene resin is one or more of homopolymer polypropylene, ethylene-propylene copolymer, propylene-butylene copolymer, ethylene-propylene-butylene copolymer, and the melt index thereof at 230 DEG C, 2.16 Kg is 2.5-150 g / 10 min, the bending modulus is greater than 800 MPa, and the tensile yield strength is greater than 28 MPa. The luminescent agent is one or more of ZnS:Cu 2+ , ZnS:Mn 2+ , CaS:Eu 2+ , Dy 3+ , CaAl2O4:Eu 2+ , Nd 3+ , SrAl2O4:Eu 2+ , Dy 3+ , Sr2MgSi2O7:Eu 2+ , Sr4Al 14 O 25 :Eu 2+ , Dy 3+ , CaAl2O4:Ce 3+ , Tb 3+ , Sr3Al2O6:Eu 3+ , SrAl2O4:Eu 2+ , SrAl2O4:Ce 3+ , CaLaAl3O7:Tb 3+ , CaYAl3O7:Ce 3+ , Ca2MgSi2O7:Eu 2+ , Ba2MgSi2O7:Eu 2+ , ZnCaOS:Mn 2 + , MgSiO3:Mn 2+ , Eu 2+ , Dy 3+ , ZnGa2O4:Cr 3+ , ZnGa2O4:Tb 3+ , ZnGa2O4:Mn 2+ , ZnGa2O4:Bi 3+ , CaZnOS-ZnS:Dy 3+ , CaZnOS-ZnS:Er 3+ and CaZnOS-ZnS:Eu 2+ . The preparation method of the anti-bio adsorption composite agent comprises the following steps: (1) dissolving the anti-bio adsorption agent in a mixed solvent of EtOH / DMSO to obtain an anti-bio adsorption agent solution with a concentration of 0.1-1 g / mL, wherein the anti-bio adsorption agent is one or more of 6-bromoindole-3-formaldehyde, 2,5,6-tribromo-1-methyl-3-dimethylaminoindole, 2-(p-chlorophenyl)-3-cyano-4-bromo-5-trifluoromethyl-pyrrole, N-(2,4,6-trichlorophenyl) maleimide, 2-tert-butylamino-4-cyclopropylamino-6-methylthio-s-triazine, pyridine triphenyl boron or 2,4,5,6-tetrachloro-1,3-benzene dicyanide; (2) weighing 5-20 g of nano-mesoporous silica and dispersing in 40 mL of EtOH, stirring until uniform, then adding 10-200 mL of the anti-bio adsorption agent solution prepared above dropwise, setting the loading temperature to 30-50 DEG C, continuously stirring for 24-48 h, then placing the sample in a centrifuge at 3000-6000 r / min for 5 min, collecting the precipitate after centrifugation, drying it at 80-110 DEG C under reduced pressure to obtain the anti-bio adsorption composite agent.

2. The marine antifouling, long afterglow luminescent polypropylene for fishing net line according to claim 1, characterized in that, The polypropylene resin is one or more of homopolymer polypropylene, ethylene-propylene copolymer, propylene-butylene copolymer, ethylene-propylene-butylene copolymer, and the melt index thereof at 230 DEG C, 2.16 Kg is 2.5-150 g / 10 min, the bending modulus is greater than 800 MPa, and the tensile yield strength is greater than 28 MPa.

3. The marine antifouling, long afterglow luminescent polypropylene for fishing net line according to claim 1, characterized in that, The reinforcing resin is one or more of UWMPE, PA6, PC, TPU, PET or COC.

4. The marine antifouling, long afterglow luminescent polypropylene for fishing net line according to claim 1, characterized in that, The compatibilizer is one or more of maleic anhydride grafted polypropylene, maleic anhydride grafted ethylene-vinyl acetate copolymer, maleic anhydride grafted ternary ethylene-propylene rubber, glycidyl methacrylate grafted polypropylene, butyl methacrylate grafted polypropylene, and maleic anhydride grafted ethylene-octene copolymer.

5. The marine antifouling, long-persistent polypropylene light-emitting fishing net line according to claim 1, characterized in that, The antioxidant includes primary and secondary antioxidants; the primary antioxidant is one or more of hindered phenolic antioxidants and hindered amine antioxidants; the secondary antioxidant is one or more of phosphite antioxidants, thioester antioxidants, thio-bisphenol antioxidants and sulfide type phenolic antioxidants; and the mass ratio of the primary antioxidant to the secondary antioxidant is 1:0.2-0.

4.

6. The marine antifouling, long-persistent polypropylene light-emitting fishing net line according to claim 1, characterized in that, The nucleating agent is one or more of sorbitol acetal nucleating agents, phosphate nucleating agents, amide nucleating agents and carboxylate nucleating agents.

7. The marine antifouling, long-persistent polypropylene light-emitting fishing net line according to claim 1, characterized in that, The lubricant is one or more of polyethylene wax, paraffin wax, stearic acid, hydroxystearic acid, n-butyl stearate, calcium stearate, magnesium stearate, zinc stearate, silicone, erucic amide, stearamide and oleic amide.

8. The marine antifouling, long-persistent luminescence polypropylene dedicated for fishing net line according to claim 1, characterized in that, The rigidifying agent is one or more of aluminum borate whisker, nano titanium dioxide, nano montmorillonite, nano talcum powder, wollastonite fiber, calcium carbonate whisker.

9. A method for preparing a long afterglow luminous polypropylene for a fishing net line, which is characterized by, The method comprises the following steps: (1) uniformly mixing polypropylene resin, reinforcing resin, compatibilizer, antioxidant, nucleating agent, lubricant, rigidifying agent, luminous agent and anti-bio adsorption composite agent in a high-speed mixer according to proportions to obtain a premix; (2) melt-extruding the premix in step (1) through a double-screw extruder, wherein the screw rotation speed is 20-200 rmp, the temperature of the first zone is 170-180 DEG C, the temperature of the second zone is 190-200 DEG C, the temperature of the third zone is 200-210 DEG C, the temperature of the fourth zone is 210-230 DEG C, the temperature of the fifth zone is 210-230 DEG C, the temperature of the sixth zone is 210-230 DEG C, and the die temperature is 200-210 DEG C, and then cooling and granulating to obtain the marine antifouling and long-afterglow luminous polypropylene special for fishing net line.

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