Anti-algae master batch for ultra-high molecular weight polyethylene seawater net cage netting fiber as well as preparation method and preparation device of anti-algae master batch

Abstract

The invention relates to an anti-algae master batch for ultra-high molecular weight polyethylene seawater net cage netting fibers as well as a preparation method and a preparation device of the anti-algae master batch. The anti-algae master batch is prepared from the following components: ultra-high molecular weight polyethylene, high-density polyethylene, a fluorine-containing polymer processing aid PPA, high-density oxidized polyethylene wax OPE, a composite antioxidant, FAU type molecular sieve raw powder and an inorganic composite guanidine salt polymer anti-algae agent. The anti-algae master batch has the advantages of high anti-algae efficiency, dissolution resistance and lasting anti-algae effect, is safe to fish and shrimps in aquaculture, has no pollution to the environment, can be applied to ultra-high molecular weight polyethylene fibers which are prepared by adopting a melt spinning method and are used for the anti-algae function of marine aquaculture net cages and nettings, and has the addition amount of 5%-10%. The prepared anti-algae ultra-high molecular weight polyethylene net cage netting has the advantages of safety, environmental protection, dissolution resistance, lasting anti-algae effect and the like, and has wide market prospect and commercial value; the preparation method is simple in technological process and meets the large-batch production and manufacturing requirements.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer materials, and particularly to an anti-algal masterbatch for ultra-high molecular weight polyethylene seawater cage netting fibers, a preparation method thereof, and a preparation device thereof. Background Art

[0002] In the past two or three decades, the utilization of marine biological resources represented by the seawater aquaculture industry has been rapidly rising, which not only enriches the dietary nutrition supply of Chinese residents, but also plays a crucial role in stabilizing food security and other aspects. Due to the poor water exchange of ordinary cages, after long-term high-density aquaculture, it will cause the deterioration of the bottom sediment and water quality in the aquaculture sea area, resulting in slow growth and frequent diseases of fish, and also making it difficult for ordinary cage aquaculture to develop sustainably. In order to change the current situation of cage aquaculture, China strongly supports the research and development and application of domestic deep-water cages, which has made remarkable progress in China's seawater cage aquaculture technology. However, there are still problems of netting anti-fouling that need to be solved urgently, which seriously restricts the healthy development of the cage aquaculture industry. Marine fouling organisms refer to the general term of organisms that attach to or inhabit marine facilities such as cages, have an adverse impact on human activities, and bring negative benefits to investors. The fouling organisms on the cage netting include algae, barnacles, hydroids, ascidians, and bivalves, etc. Ordinary cage netting has the characteristics of non-toxicity, many pores, and a large surface area, which is suitable for the attachment of fouling organisms. At the same time, the aquaculture water body of the cage is rich in nutrients and aquaculture wastes, which provides sufficient nutrition for fouling organisms and is conducive to the growth of fouling organisms. The attachment of fouling organisms on the netting of the cage will reduce the volume of the net, lower the permeability of the net, and increase the mass of the net, resulting in blocked water flow exchange and insufficient oxygen supply, thus seriously affecting the quality of aquaculture organisms and even possibly leading to the death of aquaculture organisms. When fouling organisms multiply in large numbers and are not removed in time, it will cause great harm to the cage aquaculture production. Therefore, the problem of netting anti-fouling has attracted extensive attention from the aquaculture industry and professionals.

[0003] The netting is an important part of the seawater cage. According to the netting material, it can be divided into metal netting, polyethylene (PE) netting, polyamide (PA) netting, composite fiber netting, ultra-high molecular weight polyethylene (UHMWPE) netting, and semi-rigid polyester monofilament netting, etc.

[0004] UHMWPE nets are made of UHMWPE fibers. UHMWPE nets are new cage net materials with low density, high strength, good wear resistance, low elongation, good aging resistance and high price. As cages develop towards offshore, deep sea and large-scale, their application in cages will be more extensive. In recent years, research and development and application of high-performance flexible nets such as UHMWPE nets have been carried out at home and abroad, but they are also easily attached by marine fouling organisms in seawater. Existing cage net defense technologies include: manual removal method, antifouling coating method, mechanical removal method, metal alloy net antifouling method, box rotation antifouling method, biological antifouling method, net intrinsic antifouling method, etc. In high sea conditions aquaculture environment, the antifouling coating on the cage net is prone to shedding and failure, which has become one of the main problems restricting the industrial application of the antifouling coating method. In order to solve the above problems, people have comprehensively applied new composite material technologies, compounded high-efficiency antifouling agents suitable for spinning into special spinning raw materials, and created composite fibers and net materials with intrinsic and long-lasting antifouling functions, which can greatly simplify the tedious antifouling work of net cages and avoid the problems of antifouling agents falling off the nets and becoming ineffective. It is particularly suitable for net cage applications in high sea conditions such as the East my country Sea. In addition to meeting the spinning requirements, the antifouling agents used in the net intrinsic antifouling method are also required to have good light stability, safety and environmental friendliness, low toxicity, no heavy metals and phenolic substances, anti-dissolution, and long-lasting anti-algae performance. In addition, during the processing, they have good processability, dispersibility in the resin matrix, and thermal stability.

[0005] Guanidine polymers have low toxicity and good high temperature resistance. In addition to excellent antibacterial and antifungal properties, they also have good anti-algae properties. They are widely used as algaecides in pools abroad, so they are considered to have great development potential. Guanidine polymers are cationic polyelectrolytes with guanidine groups; guanidine polymers have good water solubility, light and heat stability, high efficiency and broad-spectrum antibacterial properties, good anti-algae properties, safety, low toxicity, no irritation, no bacterial resistance, non-volatile, no heavy metals and phenols, no corrosion to various treated surfaces, and environmental friendliness. They have been widely used in medical disinfection, food and other daily necessities sterilization and disinfection. Since the guanidine group is a hydrophilic group, most guanidine polymers are highly water-soluble. At present, they are mainly used in the form of aqueous solutions of guanidine polymers for surface disinfection of products, post-antibacterial finishing of textiles, and anti-algae treatment of pools. However, when guanidine polymers are blended and modified with plastics or rubbers, they will gradually lose their antibacterial and anti-algae properties due to their poor water resistance because they are soluble in water.

[0006] Therefore, it is necessary to develop an anti-algae masterbatch for seawater cage net fiber based on guanidine polymer, which is resistant to dissolution, has good anti-algae effect and is durable, safe and low-toxic, and has not only high economic value but also good social value. Summary of the invention

[0007] To solve the above problems, the present invention provides an anti-algal masterbatch for ultra-high molecular weight polyethylene seawater cage netting fibers, a preparation method thereof, and a preparation device. The anti-algal masterbatch for ultra-high molecular weight polyethylene seawater cage netting fibers is applied to manufacture ultra-high molecular weight polyethylene seawater cage netting fibers with anti-algal function, and the addition amount is 5-10%. The prepared ultra-high molecular weight polyethylene seawater cage netting fibers have excellent properties such as excellent anti-dissolution, good anti-algal performance, and long-lasting effect.

[0008] The technical solution adopted by the present invention is as follows:

[0009] The anti-algal masterbatch for ultra-high molecular weight polyethylene seawater cage netting fibers of the present invention is composed of the following components in parts by weight:

[0010]

[0011]

[0012] The inorganic composite guanidine salt polymer anti-algal agent is compounded from silica white functionalized with epoxy groups, guanidine salt polymer, polyether polyol, methyl silicone oil, and zinc ricinoleate;

[0013] The silica white functionalized with epoxy groups is silica white functionalized by grafting epoxy groups on the surface of silica white powder through chemical reaction using epoxy group silane coupling agent, and the organic part of the silica white functionalized with epoxy groups accounts for 10%-30% of the total mass of the silica white functionalized with epoxy groups after being calcined at a high temperature above 600°C;

[0014] The polyether polyol is selected from one or more of polyoxypropylene polyol, polyoxyethylene polyol, polytrimethylene ether glycol, or polytetrahydrofuran and its copolymer ether glycol;

[0015] In the inorganic composite guanidine salt polymer anti-algal agent material, the content of the polyether polyol is 3%-35%, the content of the methyl silicone oil is 0.5%-10%, the content of the zinc ricinoleate is 1%-10%, and the mass ratio of the silica white functionalized with epoxy groups to the guanidine salt polymer is 1:2-10:1;

[0016] The viscosity-average molecular weight of the ultra-high molecular weight polyethylene UHMW-PE is 1×10 6 ~5×10 6 ;

[0017] The melt flow rate MFR of the high-density polyethylene HDPE is 0.8-20 g / min;

[0018] The compound antioxidant is prepared by compounding a hindered phenol main antioxidant and a phosphite auxiliary antioxidant with a mass ratio of 1:2.

[0019] Further, the epoxy group-containing silane coupling agent is selected from one or more of γ-glycidoxypropyltrimethoxysilane, 3-(2,3-epoxypropoxy)propylmethyldimethoxysilane, γ-glycidoxypropyltriethoxysilane, β-(3,4-epoxycyclohexyl)ethyltriethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, or 3-(2,3-epoxypropoxy)propylmethyldiethoxysilane.

[0020] Further, the guanidine salt polymer is selected from one or more of polyhexamethylene guanidine hydrochloride, polyhexamethylene biguanide hydrochloride, polyhexamethylene guanidine propionate, polyhexamethylene biguanide propionate, polyhexamethylene guanidine nitrate, polyhexamethylene biguanide nitrate, polyhexamethylene guanidine phosphate, polyhexamethylene biguanide phosphate, polyhexamethylene guanidine carbonate, or polyhexamethylene biguanide carbonate.

[0021] Based on the same inventive concept, the present application also provides a method for preparing the above-mentioned anti-algal masterbatch for ultra-high molecular weight polyethylene seawater cage netting fibers, which comprises the following preparation steps:

[0022] S1: Prepare an inorganic composite guanidine salt polymer anti-algal agent for standby;

[0023] S2: Mix ultra-high molecular weight polyethylene (UHMW-PE), high-density polyethylene (HDPE), inorganic composite guanidine salt polymer anti-algal agent, fluorine-containing polymer processing aid (PPA), high-density oxidized polyethylene wax (OPE), compound antioxidant, and FAU-type molecular sieve raw powder evenly according to the ratio, place them in a hot air dryer and dry at 70°C to 80°C for 3 to 5 hours, and then add them to a twin-screw extruder;

[0024] S3: Under nitrogen protection, set the temperature of the twin-screw extruder to 160°C to 300°C, set the rotation speed to 150 to 250 rpm, evacuate and introduce nitrogen for protection;

[0025] S4: After melting and blending the mixed raw materials through the twin-screw extruder, use an air-cooled die face pelletizing device for pelletizing, and protect the pelletizing process with nitrogen air cooling to obtain the above-mentioned anti-algal masterbatch for ultra-high molecular weight polyethylene seawater cage netting fibers.

[0026] Further, the specific preparation steps of the inorganic composite guanidine salt polymer anti-algal agent in S1 are as follows:

[0027] S10. Add fumed silica functionalized with epoxy groups, guanidine salt polymer, polyether polyol, and methyl silicone oil into a kneader equipped with an ultrasonic generator. Under normal pressure, introduce inert gas for protection. Start stirring at room temperature to mix the materials evenly. Then, raise the temperature and stir to melt the polymer materials and mix them evenly with the fumed silica functionalized with epoxy groups. At the same time, start the ultrasonic generator of the kneader. Under the action of ultrasonic waves, promote the fumed silica functionalized with epoxy groups to be fully dispersed in the molten materials for reaction, and maintain the reaction temperature of 100 - 200 °C for 1 - 8 hours. Then, while maintaining the original reaction temperature of the kneader, the action of the stirrer, and the ultrasonic generator, close the inert gas, perform vacuum degassing for 1 - 3 hours, then introduce inert gas to normal pressure, add zinc ricinoleate, and continue stirring for 0.5 - 2 hours under the protection of inert gas introduction;

[0028] S11. After the reaction in step S10 is completed, cool the molten product to room temperature, and then crush the cooled solid product into powder to prepare an inorganic composite guanidine salt polymer anti - harmful microorganism material.

[0029] The inorganic composite guanidine salt polymer anti - algal agent provided by this application binds the guanidine salt polymer high - molecular chain to the surface of inorganic fumed silica powder particles through chemical bond bonding. Utilizing the property that the fumed silica powder particles are insoluble in water, the prepared inorganic composite guanidine salt polymer anti - algal agent also has the property of being insoluble in water, solving the problem of poor water solubility resistance of the guanidine salt polymer added in the ultra - high molecular weight polyethylene fiber resin. Moreover, due to the property of being insoluble in water, after the inorganic composite guanidine salt polymer anti - algal agent prepared by the present invention is added to ultra - high molecular weight polyethylene, it has the properties of anti - leaching and long - lasting anti - algal effect.

[0030] Based on the same inventive concept, this application also provides a preparation device for the above - mentioned preparation method, including an ultrasonic kneading component and a twin - screw extrusion component;

[0031] The ultrasonic kneading component is provided with a cylinder body, multiple groups of ultrasonic generators, inert gas pipes, and vacuum pipes. The cylinder body is provided with a feeding port, and the feeding port is provided with a sealing cover. Multiple groups of the ultrasonic generators are arranged on the side of the cylinder body. The inert gas pipes are installed on the cylinder body for introducing or discharging inert gas, and the vacuum pipes are installed on the cylinder body for pumping out the air in the cylinder body. Control valves are respectively installed on the inert gas pipes and the vacuum pipes;

[0032] The twin - screw extrusion component includes an extruder body and a hopper. The extruder body is provided with multiple sections of cylinders. Multiple sections of the cylinders are installed on the extruder body and are meshed and connected in parallel and rotating in the same direction. The hopper is installed on the extruder body and is arranged close to the cylinders.

[0033] Further, the cylinder body is provided with thirteen sections, and the section close to the hopper is the 1st section;

[0034] Vacuum exhausting structures are provided on the cylinder body at the 5th, 9th, and 12th section positions;

[0035] Nitrogen inlet components are provided on the cylinder body at the 2nd - 4th, 6th - 8th, and 10th - 11th section positions;

[0036] The hopper is provided with a cover plate, and a nitrogen discharging component is provided on the cover plate.

[0037] Further, a first pipe valve, a pressure regulating component, and a gas flow regulating component are provided on the inlet pipe fitting component;

[0038] A second pipe valve is provided on the nitrogen discharging component.

[0039] Further, the frequencies of multiple groups of the ultrasonic generators are respectively set to 20 kHz, and the power adjustment range of a single ultrasonic generator in multiple groups of the ultrasonic generators is 0 - 500 W.

[0040] The beneficial effects of the present invention are as follows:

[0041] 1. The anti - algae masterbatch for ultra - high molecular weight polyethylene seawater cage netting fibers provided by the present application has high anti - algae efficiency, anti - dissolution, long - lasting anti - algae effect, is safe for fish and shrimp in aquaculture, and is pollution - free to the environment. It can be applied to ultra - high molecular weight polyethylene fibers for anti - algae function of seawater aquaculture cage netting prepared by the melt spinning method, with an addition amount of 5% - 10%. The prepared anti - algae ultra - high molecular weight polyethylene cage netting has the advantages of safety, environmental protection, anti - dissolution, and long - lasting anti - algae effect, and has broad market prospects and commercial value.

[0042] 2. The preparation method of the anti - algae masterbatch for ultra - high molecular weight polyethylene netting fibers provided by the present application has a simple technological process and is easy to prepare, meeting the requirements of mass production. The preparation method of the antibacterial and mildew - proof masterbatch for polyethylene pipes has a simple technological process and is easy to prepare, meeting the requirements of mass production.

[0043] 3. The preparation device provided by the present application has a simple structure, reasonable design, is convenient for vacuum adjustment and introduction of inert gas protection during the preparation process, and has good application effects. Description of the Drawings

[0044] Figure 1 It is a schematic structural diagram of the ultrasonic kneading component in the present application;

[0045] Figure 2 It is a schematic structural diagram of the twin - screw extrusion component in the present application;

[0046] Figure 3 Schematic cross-sectional view of the barrel of the twin-screw extrusion component in this application (specifically, the cross-section where the nitrogen inlet component is provided);

[0047] Explanation of reference numerals: ultrasonic kneading component 100, cylinder block 110, multiple groups of ultrasonic generators 120, inert pipe fittings 130, vacuum pipe fittings 140, twin-screw extrusion component 200, extruder body 210, hopper 220, barrel 230, vacuum exhaust structure 240, nitrogen inlet component 250, nitrogen outlet component 260. Detailed implementation mode

[0048] The present invention will be further described below in conjunction with preferred embodiments.

[0049] Embodiment 1:

[0050] The anti-algal masterbatch for ultra-high molecular weight polyethylene seawater cage netting fibers provided in this embodiment is prepared by the following steps:

[0051] S1. Prepare the inorganic composite guanidine salt polymer anti-algal agent powder 1# for standby;

[0052] S10. Add 1000 g of fumed silica that has been pre-dried at 120°C for 5 hours to an aqueous solution of 30 L of absolute ethanol (mass ratio of absolute ethanol to distilled water is 3:1), adjust the pH value to 4-5 with hydrochloric acid, start stirring and assist with an ultrasonic environment to make it uniformly dispersed for 30 min, then slowly drop 200 g of γ-glycidoxypropyltrimethoxysilane (CAS No.: 2530-83-8), then raise the temperature to 70°C, keep stirring at a constant temperature for 10 hours, after filtering the fumed silica suspension, wash it 3 times with absolute ethanol, and after drying and grinding, obtain epoxy group-functionalized fumed silica for storage and standby. Take a sample and place it for a high-temperature test at 600°C for 5 hours, and the weight loss rate is 10.2%;

[0053] Add 600 g of the above-prepared epoxy group-functionalized silica, 750 g of polyhexamethylene guanidine hydrochloride (average molecular weight 10,000), 90 g of polypropylene triol (hydroxyl value 53 - 59), and 45 g of methyl silicone oil into the cylinder of a kneader equipped with an ultrasonic generator. Cover the cylinder head. After several vacuum replacements with nitrogen, open the stainless steel gas valve, and introduce nitrogen at atmospheric pressure for protection. Start stirring at room temperature to mix the materials evenly. Raise the temperature and stir to melt the polymer materials and then mix them evenly with the epoxy group-functionalized silica. At the same time, start the ultrasonic generator on the side of the kneader cylinder. Under the action of ultrasonic waves, promote the full dispersion of the epoxy group-functionalized silica in the molten materials for reaction, and maintain the reaction temperature of 180 °C for 3 hours. Then, while maintaining the original reaction temperature of the kneader, the action of the stirrer and the ultrasonic generator, close the inert gas inlet and outlet valves on the kneader cylinder head, open the vacuum tube valve on the cylinder head and start the vacuum. After vacuum degassing for 1.5 hours, relieve the vacuum in the cylinder, introduce nitrogen to atmospheric pressure, open the solid feeding port on the cylinder head, add 15 g of zinc ricinoleate, and continue stirring for 1.5 hours under nitrogen protection;

[0054] S11. After the reaction in step S10 ends, cool the molten product to room temperature, and then crush the cooled solid product into powder to prepare the inorganic composite guanidine salt polymer anti-algal agent powder 1# of Example 1;

[0055] S2. Add 1325 g of ultra-high molecular weight polyethylene (UHMWPE) (viscosity-average molecular weight 1.5×10 6 ) powder, 565 g of high-density polyethylene (HDPE) (melt index MFR is 8 g / 10 min), 500 g of inorganic composite guanidine salt polymer anti-algal agent 1#, 13 g of fluorine-containing polymer processing aid PPA, 35 g of high-density oxidized polyethylene wax OPE, 4.0 g of antioxidant 1010, 8.0 g of antioxidant 168, and ultra-stable USY molecular sieve raw powder (relative crystallinity 79 - 88%, Na2O 0.065 - 0.1 wt%, D50 2.5 - 5.2 um, D90 5.6 - 7.2 um, Bet 695m 250 g was thoroughly stirred in a mixer and added to the hopper of a nitrogen - purged twin - screw extruder. The cover of the hopper was closed, and the stainless - steel pipe valve for purging nitrogen through the cover of the feed head was opened. The temperature of the barrel of the parallel co - rotating intermeshing twin - screw extruder was set to 160 °C - 300 °C, the screw speed was 150 rpm. The stainless - steel gas - path valves for introducing nitrogen through the nitrogen inlet nozzles at the center of the top of the 2nd - 4th, 6th - 8th, and 10th - 11th barrels from the feed inlet were opened to introduce nitrogen for protection, and the vacuum system was started. Vacuum degassing was carried out through the vacuum exhaust chambers opened on the 5th, 9th, and 12th barrels from the feed inlet. After the blended materials were melt - blended by the twin - screw extruder, they were pelletized by an air - cooled die - face pelletizing device, and nitrogen air - cooling was used for protection at the die of the head to obtain the anti - algal masterbatch 1# for ultra - high - molecular - weight polyethylene seawater cage netting fibers.

[0056] 150 g of the anti - algal masterbatch 1# for ultra - high - molecular - weight polyethylene seawater cage netting fibers prepared in this example, 1850 g of ultra - high - molecular - weight polyethylene pellet (viscosity - average molecular weight 1.5×10 6 ) and 4 g of antioxidant 1010 were thoroughly stirred in a mixer and then added to a twin - screw extruder for extrusion granulation at 90 °C - 290 °C to obtain modified ultra - high - molecular - weight polyethylene anti - algal pellet; then, a single - screw extruder was used to melt - extrude the modified ultra - high - molecular - weight polyethylene anti - algal pellet at 130 °C - 260 °C to obtain a nascent filament with a diameter of 2.8 mm, and then it was stretched on a spinning tester to obtain an ultra - high - molecular - weight polyethylene anti - algal fiber with a diameter of 1 mm. The breaking strength and breaking elongation of the fiber were measured using a universal electronic materials testing machine; then, about 5 g of the obtained ultra - high - molecular - weight polyethylene anti - algal fiber with a diameter of 1 mm was wound into a ball, and it was molded in a molding press using a fixed mold at 210 °C and 10 MPa and then cooled under pressure to 60 °C to obtain an ultra - high - molecular - weight polyethylene anti - algal sheet. Finally, it was cut into sample sizes that met the requirements of GB / T 24127 "Test Method for Anti - algal Performance of Plastics" and sample sizes that met the anti - dissolution test standard of antibacterial substances in GB 21551.1 "Special Requirements for Antibacterial, Bactericidal, and Purification Functions of Antibacterial Materials for Household and Similar Electrical Appliances" for testing anti - algal performance and anti - dissolution performance.

[0057] Example 2:

[0058] The anti - algal masterbatch 2# for ultra - high - molecular - weight polyethylene seawater cage netting fibers was prepared in this example.

[0059] The inorganic composite guanidine salt polymer anti - algal agent used in its preparation raw materials was No. 2. Except that 750 g of polyhexamethylene guanidine propionate (average molecular weight 10000) was used to replace 750 g of polyhexamethylene guanidine hydrochloride, the other powder No. 1 was the same as in Example 1.

[0060] The test samples were prepared in the same manner as in Example 1, and the anti-algal performance and anti-dissolution performance were tested.

[0061] Comparative Example 1

[0062] Except that 500 g of polyhexamethylene guanidine hydrochloride (average molecular weight 10,000) was used to replace 500.0 g of the inorganic composite guanidine salt polymer anti-algal agent 1#, the rest was the same as in Example 1, and the anti-algal masterbatch 3# for ultra-high molecular weight polyethylene seawater cage netting fibers of Comparative Example 1 was prepared.

[0063] The test samples were prepared in the same manner as in Example 1, and the anti-algal performance and anti-dissolution performance were tested.

[0064] Comparative Example 2

[0065] Except that 500 g of polyhexamethylene guanidine propionate (average molecular weight 10,000) was used to replace 500.0 g of the inorganic composite guanidine salt polymer anti-algal agent 1#, the rest was the same as in Example 2, and the anti-algal masterbatch 4# for ultra-high molecular weight polyethylene seawater cage netting fibers of Comparative Example 2 was prepared.

[0066] The test samples were prepared in the same manner as in Example 1, and the anti-algal performance and anti-dissolution performance were tested.

[0067] The test methods in Examples 1-2 and Comparative Examples 1-2 are as follows:

[0068] 1. Anti-algal test standard: GB / T 24127-2009 "Test Method for Anti-algal Performance of Plastics";

[0069] 2. Test method for anti-dissolution of the inorganic composite guanidine salt polymer anti-algal agent (width of inhibition zone): Since the inorganic composite guanidine salt polymer anti-algal agent used in the present invention also has antibacterial function, therefore, the width of the inhibition zone was tested by using the standard GB 21551.1 "Special Requirements for Antibacterial Materials with Antibacterial, Bactericidal and Purifying Functions for Household and Similar Electrical Appliances" to test the anti-dissolution property;

[0070] 3. Water immersion treatment method for testing the anti-dissolution of the anti-algal masterbatch sample for ultra-high molecular weight polyethylene seawater cage netting fibers: Referring to the test method specified in JC / T 939-2004 "Antibacterial Performance of Antibacterial Plastic Pipes for Building Use", the sample was first immersed in distilled water bath at a temperature of (50 ± 2 °C) for 72 h, and then the anti-algal performance was tested.

[0071] 4. Mechanical property tests of the fibers of the ultra-high molecular weight polyethylene seawater cage netting, such as breaking strength and elongation at break: Use a universal electronic materials testing machine to measure the breaking strength and elongation at break of the fibers. The experimental conditions are as follows: the sample length is 1000 mm, the effective sample length is 500 mm, the tensile rate is 300 mm / min, and the pre-tension is the weight of the fiber with a length of (250 ± 25) m. During the test, it should be ensured that the fiber breaks within the effective length range, and the number of valid data is at least 10 times, and the average value is taken. The calculation formula for breaking strength:

[0072] σ = F * L / (9 * 9.8 * M) Equation (1)

[0073] Where: σ is in denier, g / D;

[0074] L is the sample length, m;

[0075] M is the sample mass, g.

[0076] The test results are shown in Table 1 below:

[0077] Table 1 Test results of antibacterial and mildew-proof properties of Examples 1-2 and Comparative Examples 1-2

[0078]

[0079] As can be seen from the above table, the anti-algal masterbatch for the ultra-high molecular weight polyethylene seawater cage netting fibers provided by this application has good anti-algal performance, and the anti-dissolution and anti-algal effects are persistent. It can be applied to the preparation of ultra-high molecular weight polyethylene fibers with anti-algal function for seawater aquaculture cage netting prepared by the melt spinning method, and the addition amount is 5% - 10%. The prepared anti-algal ultra-high molecular weight polyethylene cage netting fibers meet the requirements in terms of mechanical properties and anti-algal performance, and have the advantages of safety, environmental protection, anti-dissolution, and persistent anti-algal effects, and have broad market prospects and commercial value.

[0080] See the appendix Figures 1-3 As shown, the preparation device provided by this application includes an ultrasonic kneading component 100 and a twin-screw extrusion component 200;

[0081] The ultrasonic kneading component 100 is provided with a cylinder body 110, multiple groups of ultrasonic generators 120, inert pipe fittings 130, and vacuum pipe fittings 140. The cylinder body 110 is provided with a feeding port, and the feeding port is provided with a sealing cover body. Multiple groups of ultrasonic generators 120 are arranged on the side of the cylinder body 110. The inert pipe fittings 130 are installed on the cylinder body 110 for introducing or discharging inert gas, and the vacuum pipe fittings 140 are installed on the cylinder body 110 for pumping out the air in the cylinder body 110. Control valves are respectively installed on the inert pipe fittings 130 and the vacuum pipe fittings 140;

[0082] The twin-screw extrusion component 200 includes an extruder body 210 and a hopper 220. The extruder body 210 is provided with multiple sections of cylinders 230. The multiple sections of cylinders 230 are installed on the extruder body 210 and are rotationally meshed and connected in parallel and in the same direction. The hopper 220 is installed on the extruder body 210 and is arranged close to the cylinders 230.

[0083] Specifically, there are thirteen sections of cylinders 230, and the section close to the hopper 220 is the first section;

[0084] Vacuum discharge structures 240 are provided on the cylinders 230 at the 5th, 9th, and 12th positions;

[0085] Nitrogen inlet components 250 are provided on the cylinders 230 at the 2-4th, 6-8th, and 10-11th positions;

[0086] The hopper 220 is provided with a cover plate, and a nitrogen discharge component 260 is provided on the cover plate.

[0087] Specifically, the nitrogen inlet pipe fitting assembly is provided with a first pipe valve, a pressure regulating component, and a gas volume regulating component;

[0088] The nitrogen discharge component 260 is provided with a second pipe valve.

[0089] Specifically, the frequencies of multiple groups of ultrasonic generators 120 are respectively set to 20 kHz, and the power adjustment range of a single ultrasonic generator in multiple groups of ultrasonic generators 120 is 0-500 W.

[0090] The preparation device provided by this application has a simple structure, reasonable design, is convenient for vacuum adjustment and introduction of inert gas protection during the preparation process, and has good application effects.

[0091] The above embodiments only represent several implementation manners of the present invention. The description is relatively specific and detailed, but it should not be construed as a limitation on the scope of the patent of the present invention. It should be noted that for those of ordinary skill in the art, without departing from the concept of the present invention, several deformations and improvements can still be made, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention should be subject to the appended claims.

Claims

1. An anti-algae masterbatch for ultra-high molecular weight polyethylene seawater cage net fiber, characterized in that: It is composed of the following components in parts by weight: The inorganic composite guanidine salt polymer anti-algae agent is prepared by compositely forming epoxy functionalized white carbon black, guanidine salt polymer, polyether polyol, methyl silicone oil and ricinoleate zinc; The epoxy-functionalized silica is a silica functionalized by grafting epoxy groups on the surface of silica powder by chemical reaction using an epoxy silane coupling agent, and the epoxy-functionalized silica can be burned at a high temperature above 600° C., and the organic part accounts for 10% to 30% of the total mass of the epoxy-functionalized silica; The polyether polyol is selected from one or more of polyoxypropylene polyol, polyoxyethylene polyol, polytrimethyl ether glycol or polytetrahydrofuran and copolyether glycol thereof; In the inorganic composite guanidine salt polymer anti-algae agent material, the content of the polyether polyol is 3% to 35%, the content of the methyl silicone oil is 0.5% to 10%, the content of the zinc ricinoleate is 1% to 10%, and the mass ratio of the epoxy group functionalized white carbon black to the guanidine salt polymer is 1:2 to 10:1; The viscosity average molecular weight of the ultra-high molecular weight polyethylene UHMW-PE is 1×10 6 ~5×10 6 ; The high-density polyethylene (HDPE) has a melt index (MFR) of 0.8 to 20 g / min; The composite antioxidant is prepared by compounding a hindered phenol main antioxidant and a phosphite auxiliary antioxidant in a mass ratio of 1:

2.

2. The anti-algae masterbatch for ultra-high molecular weight polyethylene seawater cage net fiber according to claim 1, characterized in that: The epoxysilane coupling agent is selected from one or more of γ-glycidyloxypropyltrimethoxysilane, 3-(2,3-epoxypropyloxy)propylmethyldimethoxysilane, γ-glycidyloxypropyltriethoxysilane, β-(3,4-epoxycyclohexyl)-ethyltriethoxysilane, β-(3,4-epoxycyclohexyl)-ethyltrimethoxysilane or 3-(2,3-epoxypropyloxy)propylmethyldiethoxysilane.

3. The anti-algae masterbatch for ultra-high molecular weight polyethylene seawater cage net fiber according to claim 1, characterized in that: The guanidine polymer is selected from one or more of polyhexamethyleneguanidine hydrochloride, polyhexamethylenebiguanidine hydrochloride, polyhexamethyleneguanidine propionate, polyhexamethylenebiguanidine propionate, polyhexamethyleneguanidine nitrate, polyhexamethylenebiguanidine nitrate, polyhexamethyleneguanidine phosphate, polyhexamethylenebiguanidine phosphate, polyhexamethyleneguanidine carbonate or polyhexamethylenebiguanidine carbonate.

4. The method for preparing the anti-algae masterbatch for ultra-high molecular weight polyethylene seawater cage net fiber according to any one of claims 1 to 3, characterized in that: The preparation steps include: S1: preparing an inorganic composite guanidine salt polymer anti-algae agent for use; S2: Ultra-high molecular weight polyethylene UHMW-PE, high-density polyethylene HDPE, inorganic composite guanidine salt polymer anti-algae agent, fluorine-containing polymer processing aid PPA, high-density oxidized polyethylene wax OPE, composite antioxidant, FAU type molecular sieve raw powder are mixed evenly according to the proportion, placed in a hot air dryer at 70°C to 80°C for 3 to 5 hours, and then added to the twin-screw extruder; S3: nitrogen protection, the temperature of the twin-screw extruder is set to 160°C to 300°C, the speed is set to 150 to 250 rpm, vacuum is drawn and nitrogen is introduced for protection; S4: After the mixed raw materials are melt-blended through a twin-screw extruder, they are granulated using an air-cooled die face pelletizing device, and the granulation process is protected by nitrogen air cooling to obtain the anti-algae masterbatch for ultra-high molecular weight polyethylene seawater cage net fiber.

5. The method for preparing the anti-algae masterbatch for ultra-high molecular weight polyethylene seawater cage net fiber according to claim 4, characterized in that: The specific preparation steps of the inorganic composite guanidine salt polymer antialgae agent in S1 are as follows: S10. Add epoxy functionalized silica, guanidine polymer, polyether polyol and methyl silicone oil to a kneader with an ultrasonic generator, pass inert gas protection at normal pressure, start stirring at room temperature to mix the materials evenly, then increase the temperature and stir to melt the polymer material and mix it evenly with the epoxy functionalized silica, at the same time, start the kneader ultrasonic generator, under the action of ultrasonic waves, promote the epoxy functionalized silica to be fully dispersed in the molten material for reaction, and maintain the reaction temperature of 100 to 200° C. for 1 to 8 hours, then, maintain the original reaction temperature of the kneader, the agitator and the ultrasonic generator, turn off the inert gas, vacuum degas for 1 to 3 hours, pass inert gas to normal pressure, add zinc ricinoleate, and continue stirring for 0.5 to 2 hours under the protection of inert gas; S11. After the reaction in step S10 is completed, the molten product is cooled to room temperature, and the cooled solid product is crushed into powder to prepare an inorganic composite guanidine salt polymer anti-harmful microbial material.

6. A preparation device for the preparation method according to claim 4 or 5, characterized in that: It includes an ultrasonic kneading component and a twin-screw extrusion component; The ultrasonic kneading component is provided with a cylinder body, multiple groups of ultrasonic generators, inert pipe fittings and vacuum pipe fittings. The cylinder body is provided with a feeding port, and the feeding port is provided with a sealing cover body. Multiple groups of ultrasonic generators are arranged on the side of the cylinder body. The inert pipe fittings are installed on the cylinder body and used to pass inert gas in or out. The vacuum pipe fittings are installed on the cylinder body and used to extract air in the cylinder body. Control valves are installed on the inert pipe fittings and the vacuum pipe fittings respectively. The twin-screw extruder component comprises an extruder body and a hopper. The extruder body is provided with a multi-section barrel, which is mounted on the extruder body and meshedly connected to rotate in the same direction in parallel. The hopper is mounted on the extruder body and arranged close to the barrel.

7. The preparation device according to claim 6, characterized in that: The cylinder is provided with thirteen sections, and the first section is close to the hopper; A vacuum exhaust structure is provided on the cylinder located at the 5th, 9th and 12th sections; A nitrogen introduction assembly is provided on the cylinder located at the 2nd-4th, 6th-8th and 10th-11th sections; The hopper is provided with a cover plate, and a nitrogen exhaust component is provided on the cover plate.

8. The preparation device according to claim 7, characterized in that: The inlet pipe assembly is provided with a first pipe valve, an air pressure regulating assembly and an air volume regulating assembly; The nitrogen exhaust component is provided with a second pipe valve.

9. The preparation device according to claim 6, characterized in that: The frequencies of the multiple groups of ultrasonic generators are respectively set to 20kHz, and the power adjustment range of a single ultrasonic generator in the multiple groups of ultrasonic generators is 0 to 500W.

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