SBS (styrene-butadiene-styrene) thermoplastic elastomer antibacterial mildew-proof master batch as well as preparation method and preparation device thereof

Abstract

The invention relates to the technical field of high polymer materials, in particular to an SBS thermoplastic elastomer antibacterial mildew-proof master batch as well as a preparation method and a preparation device thereof. The SBS thermoplastic elastomer antibacterial and mildewproof master batch is prepared from the following components: SBS resin particles, an inorganic composite guanidine salt polymer anti-harmful microorganism material, a main antioxidant, an auxiliary antioxidant, a dispersing agent and FAU type molecular sieve raw powder. The SBS thermoplastic elastomer antibacterial and mildewproof master batch has excellent and lasting anti-dissolution and antibacterial and mildewproof effects, has safety and silver-free performance, can be applied to preparation of an SBS resin product with antibacterial and mildewproof functions, and has the addition ratio of 2-10%, and the prepared antibacterial and mildewproof SBS resin product has the advantages of safety, broad spectrum, dissolution resistance, lasting antibacterial and mildewproof effects and the like. Wide market prospects and commercial values are realized; the preparation method of the antibacterial and mildew-proof SBS thermoplastic elastomer master batch provided by the invention is simple in process flow and easy to prepare, and meets the requirements of large-batch production and manufacturing.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer materials, and particularly relates to an antibacterial and mildew-proof masterbatch of SBS thermoplastic elastomer, a preparation method thereof, and a preparation device thereof. Background Art

[0002] SBS thermoplastic elastomer is an important thermoplastic elastomer material. It is a copolymer with a styrene-butadiene-styrene triblock structure prepared by anionic polymerization of styrene and butadiene monomers using alkyllithium as a catalyst. Structurally, it has a rubbery soft segment "butadiene (B) segment" and a plastic hard segment "styrene (S) segment". Whether the SBS thermoplastic elastomer has a linear or star structure, the ends of the central "soft segment" polybutadiene molecular chains are all inlaid with "hard segment" polystyrene chain segments. It has excellent tensile strength, small permanent deformation, large surface friction coefficient, good low-temperature performance, excellent electrical properties, good processing performance, and has rubber elasticity without the need for vulcanization. It has advantages in processing applications that thermosetting rubber cannot match: 1) It can be processed and formed using thermoplastic processing equipment, such as extrusion, injection, blow molding, etc., and the molding speed is faster than the traditional vulcanized rubber process; 2) It does not require vulcanization, so the sulfurization process in the processing of general thermosetting rubber can be omitted. Therefore, the equipment investment is small, the production energy consumption is low, the process is simple, the production efficiency is high, and the processing cost is low; 3) The scraps can be recycled multiple times, saving resources and being beneficial to environmental protection. Due to the above good properties of SBS thermoplastic elastomer, it has a wide range of applications in the shoe-making industry, polymer modification, asphalt modification, wire and cable, automotive parts, medical device parts, household appliances, toys, furniture, sports equipment, waterproof coatings, liquid sealing materials, office automation, and adhesives. However, SBS thermoplastic elastomer itself does not have antibacterial and mildew-proof properties. When objective conditions such as temperature and humidity are suitable, harmful microorganisms such as bacteria and molds will grow and spread on SBS thermoplastic elastomer products, which not only seriously affects people's daily life and health, but also causes damage to the material itself. Therefore, developing antibacterial and mildew-proof SBS thermoplastic elastomer materials has good economic value and social significance.

[0003] An antibacterial and mildew-proof masterbatch is a concentrate in which additives with antibacterial and mildew-proof functions are evenly dispersed in a carrier resin. It has the advantages of flexible application, easy storage, and can promote the more uniform dispersion of antibacterial and mildew-proof additives in plastic substrates. Antibacterial agents containing guanidine salt polymers have low toxicity, good high-temperature resistance, and excellent antibacterial and mildew-proof performance, so they are considered to have great development potential. Guanidine salt polymers are cationic polyelectrolytes with guanidine salt groups. It mainly forms electrostatic adsorption through the cations in the molecule and the anionic parts on the surface of bacterial cells, hinders the action of harmful microbial cell lysing enzymes, deforms the surface structure of the cells, and destroys the cell membrane, thereby achieving the effect of inhibiting and killing microorganisms; Guanidine salt polymers have the advantages of good water solubility, photo-thermal stability, high-efficiency and broad-spectrum antibacterial properties, safety, low toxicity, no irritation, no bacterial drug resistance, non-volatile, no heavy metals and phenols, no corrosion to various treated surfaces, and environmental friendliness, and have been widely used in medical disinfection, sterilization and disinfection of food and other daily necessities. Since the guanidine group is a hydrophilic group, most guanidine salt polymers have strong water solubility. At present, it is mainly used in the surface disinfection treatment of products and the post-antibacterial finishing of textiles in the form of an aqueous solution of guanidine salt polymers. However, when guanidine salt polymers are blended and modified with plastics or rubbers, the products will gradually lose their antibacterial properties due to poor water resistance because they are soluble in water; Therefore, how to improve the water resistance of rubber and plastic products containing guanidine salt polymers while maintaining the advantages of guanidine salt polymers in resisting harmful microorganisms is a very worthy research topic. Patent CN 110066459 introduces a slow-release antibacterial masterbatch containing guanidine salt polymers and its preparation method. This patent prepares an SBS antibacterial masterbatch containing guanidine salt polymers by a blending and granulation method. The antibacterial products made from this masterbatch achieve antibacterial functions by slowly releasing guanidine salt polymers and zinc particles. This patented technology can only slow down the loss of guanidine salt polymers but cannot prevent the loss of guanidine salt polymer antibacterial agents. Especially under water-related use conditions, the loss of guanidine salt polymers will also accelerate, making the products weaken or even lose their antibacterial functions.

[0004] Therefore, it is necessary to develop an anti-dissolution, long-lasting antibacterial and mildew-proof effect, safe, SBS thermoplastic elastomer antibacterial and mildew-proof masterbatch based on guanidine salt polymers, which has broad market prospects. Summary of the Invention

[0005] To solve the above problems, the present invention provides an SBS thermoplastic elastomer antibacterial and mildew-proof masterbatch, its preparation method and preparation device. This SBS thermoplastic elastomer antibacterial and mildew-proof masterbatch is used in the manufacture of SBS resin products with antibacterial and mildew-proof functions, and the addition ratio is 2-10%. The prepared antibacterial and mildew-proof SBS resin products have excellent antibacterial, mildew-proof, anti-dissolution, long-lasting antibacterial and mildew-proof effects, and safety and other excellent properties.

[0006] The technical solution adopted by the present invention is:

[0007] The SBS thermoplastic elastomer antibacterial and mildew-proof masterbatch of the present invention is composed of the following components in parts by weight:

[0008]

[0009] The inorganic composite guanidine salt polymer anti-harmful microorganism material is prepared by compounding silica white functionalized with epoxy groups, guanidine salt polymer, polyether polyol, methyl silicone oil and zinc ricinoleate;

[0010] The silica white functionalized with epoxy groups is the silica white grafted with epoxy groups on the surface of silica white powder through chemical reaction by 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;

[0011] The polyether polyol is selected from one or more of polyoxypropylene polyol, polyoxyethylene polyol, polytriethylene glycol, polytetrahydrofuran and their copolymer polyether diols;

[0012] In the inorganic composite guanidine salt polymer anti-harmful microorganism material, the mass content of the polyether polyol is 3% - 35%, the mass content of the methyl silicone oil is 0.5% - 10%, the mass 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;

[0013] The main antioxidant is selected from at least one of antioxidant 1010 (pentaerythritol tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]), antioxidant 264 (2,6-di-tert-butyl-p-cresol), antioxidant 1076 (octadecyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate);

[0014] The auxiliary antioxidant is selected from at least one of antioxidant DLTP (dilauryl thiodipropionate), antioxidant 168 (tris(2,4-di-tert-butylphenyl) phosphite), antioxidant TNP (tris(nonylphenyl) phosphite);

[0015] The dispersant is selected from at least one of N,N'-ethylenebisstearamide, polyethylene wax, ethylene bislauramide, N,N'-ethylene oleamide.

[0016] 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.

[0017] 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.

[0018] Based on the same inventive concept, the present application also provides a method for preparing the above-mentioned SBS thermoplastic elastomer antibacterial and mildew-proof masterbatch, which comprises the following preparation steps:

[0019] S1: Prepare an inorganic composite guanidine salt polymer anti-harmful microorganism material for later use;

[0020] S2: Mix SBS resin pellets, the inorganic composite guanidine salt polymer anti-harmful microorganism material, a primary antioxidant, a secondary antioxidant, a dispersant, and FAU-type molecular sieve raw powder evenly according to the ratio, and then add them to a twin-screw extruder;

[0021] S3: Protect with nitrogen, set the temperature of the twin-screw extruder to 170°C to 210°C, set the rotation speed to 130 to 180 rpm, evacuate and introduce nitrogen for protection;

[0022] 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 SBS thermoplastic elastomer antibacterial and mildew-proof masterbatch.

[0023] Further, the specific preparation steps of the inorganic composite guanidine salt polymer anti-harmful microorganism material in S1 are as follows:

[0024] S10. Add the silica white functionalized with epoxy groups, guanidinium salt polymer, polyether polyol, and methyl silicone oil into a kneader equipped with an ultrasonic generator. Protect it by introducing an inert gas at normal pressure. 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 silica white functionalized with epoxy groups. At the same time, start the ultrasonic generator of the kneader. Under the action of ultrasonic waves, promote the full dispersion of the silica white functionalized with epoxy groups in the molten materials for reaction, so that the amine groups with reactive activity in the molecular chain of the guanidinium salt polymer fully undergo chemical reactions with the epoxy groups on the surface of the silica white powder functionalized with epoxy groups, and maintain the reaction temperature of 100-200°C for 1-8 hours. In this way, the high molecular chain of the guanidinium salt polymer can be bonded to the surface of the silica white powder particles through strong chemical bonds. 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 the inert gas to normal pressure, add zinc ricinoleate, and continue stirring for 0.5-2 hours under the protection of the inert gas. The added zinc ricinoleate can effectively remove the peculiar smell generated during the above reaction process;

[0025] 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 guanidinium salt polymer anti-harmful microorganism material.

[0026] The inorganic composite guanidinium salt polymer anti-harmful microorganism material provided by this application binds the high molecular chain of the guanidinium salt polymer to the surface of inorganic silica white powder particles through a chemical bond bonding method. Utilizing the property that the silica white powder particles are insoluble in water, the prepared inorganic composite guanidinium salt polymer anti-harmful microorganism material also has the property of being insoluble in water, solving the problem of poor water solubility resistance of the guanidinium salt polymer added in the high molecular material. Moreover, due to the property of being insoluble in water, after the inorganic composite guanidinium salt polymer anti-harmful microorganism material prepared by the present invention is added to the high molecular material, it has the properties of anti-leaching and long-lasting antibacterial and antifungal effects.

[0027] Based on the same inventive concept, this application also provides a preparation device for the above preparation method, including an ultrasonic kneading component and a twin-screw extrusion component;

[0028] 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 body. 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. 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;

[0029] The twin-screw extrusion component includes an extruder body and a hopper. The extruder body is provided with multiple sections of cylinders, and the multiple sections of cylinders are installed on the extruder body and are rotationally and meshingly connected in parallel and in the same direction. The hopper is installed on the extruder body and is arranged close to the cylinders.

[0030] Further, there are thirteen sections of cylinders. The section close to the hopper is the first section;

[0031] Vacuum exhaust structures are provided on the cylinders at the 5th, 9th, and 12th section positions;

[0032] Nitrogen inlet components are provided on the cylinders at the 2 - 4th, 6 - 8th, and 10 - 11th section positions;

[0033] The hopper is provided with a cover plate, and a nitrogen discharge component is provided on the cover plate.

[0034] Further, the nitrogen inlet pipe component is provided with a first pipe valve, a pressure regulating component, and a gas volume regulating component;

[0035] The nitrogen discharge component is provided with a second pipe valve.

[0036] Further, the frequencies of multiple groups of ultrasonic generators are respectively set to 20 kHz, and the power adjustment range of a single ultrasonic generator in multiple groups of ultrasonic generators is 0 - 500 W.

[0037] The beneficial effects of the present invention are as follows:

[0038] 1. The SBS thermoplastic elastomer antibacterial and mildew-proof masterbatch provided by the present application has high antibacterial efficiency, anti-dissolution, long-lasting antibacterial and mildew-proof effects, and the properties of being safe and non-silvering. It can be applied to the preparation of SBS thermoplastic elastomer products with antibacterial and mildew-proof functions, and the addition ratio is 2 - 10%. The prepared antibacterial and mildew-proof SBS resin products have the advantages of being safe, broad-spectrum, anti-dissolution, and having long-lasting antibacterial and mildew-proof effects, and have broad market prospects and commercial value;

[0039] 2. The preparation method of the SBS thermoplastic elastomer antibacterial and mildew-proof masterbatch provided by the present application has a simple process flow and is easy to prepare, meeting the requirements of mass production and manufacturing.

[0040] 3. The preparation device provided by the present application has a simple structure and 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

[0041] Figure 1 It is a schematic structural diagram of the ultrasonic kneading component in the present application;

[0042] Figure 2Schematic structural diagram of the twin-screw extrusion component in the present application;

[0043] Figure 3 Schematic cross-sectional view of the barrel of the twin-screw extrusion component in the present application (specifically, the cross-section at the position where the nitrogen inlet component is provided);

[0044] 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 manners

[0045] The present invention will be further described below in conjunction with preferred embodiments.

[0046] Embodiment 1:

[0047] The SBS thermoplastic elastomer antibacterial and antifungal masterbatch provided in this embodiment is prepared by the following steps:

[0048] S1. Prepare the inorganic composite guanidine salt polymer anti-harmful microorganism material powder 1# for standby;

[0049] S10. Add 1000 g of fumed silica 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 evenly 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 by suction, 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%;

[0050] 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;

[0051] 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 obtain the inorganic composite guanidine salt polymer anti-harmful microorganism material powder 1# of Example 1;

[0052] S2. Add 1850.0 g of SBS thermoplastic elastomer particle material (brand Globalprene 1485, Formosa Plastics Corporation, Taiwan, China), 500.0 g of the inorganic composite guanidine salt polymer anti-harmful microorganism material 1#, 5.0 g of antioxidant 1010, 10.0 g of antioxidant 168, 80.0 g of N,N'-ethylenebisstearamide, and 55 g of ultrastable USY molecular sieve raw powder (relative crystallinity 79 - 88%, Na2O 0.065 - 0.1 wt%, D50 2.5 - 5.2 μm, D90 5.6 - 7.2 μm, Bet 695 m2 / g) into a mixer and stir evenly. Add them to the hopper of a twin-screw extruder that can be protected by nitrogen. Cover the hopper cover, open the stainless steel tube valve for introducing nitrogen at the head cover. Set the temperature of the barrel of the parallel co-rotating intermeshing twin-screw extrusion to 170 °C - 210 °C, the screw speed to 150 rpm. Open 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 to protect with nitrogen, and start the vacuum system. Set up vacuum exhaust chambers on the 5th, 9th, and 12th barrels from the feed inlet for vacuum degassing. After the blended materials are melt-blended through the twin-screw extruder, granulate them through an air-cooled die face granulation device, and use nitrogen air cooling for protection at the die head of the machine head to obtain the SBS thermoplastic elastomer antibacterial and mildew-proof masterbatch 1#.

[0053] Take 15.0 g of the SBS thermoplastic elastomer antibacterial and mildew-proof masterbatch 1# prepared in this example and 485.0 g of SBS thermoplastic elastomer particles (brand: Globalprene 1485, Formosa Plastics Corporation, Taiwan, China), stir them evenly in a mixer, and then use an injection molding machine to inject them into an antibacterial and mildew-proof SBS resin test sample with dimensions of 50 mm * 50 mm * 3 mm for testing the antibacterial and mildew-proof performance.

[0054] Example 2:

[0055] The SBS thermoplastic elastomer antibacterial and mildew-proof masterbatch 2# was prepared in this example.

[0056] The inorganic composite guanidine salt polymer anti-harmful microorganism material used in its preparation raw materials is 2#. Except for replacing 750 g of polyhexamethylene guanidine hydrochloride with 750 g of polyhexamethylene guanidine propionate (average molecular weight 10,000), the rest is the same as the powder 1# in Example 1.

[0057] The test sample was prepared in the same way as in Example 1 for testing the antibacterial and mildew-proof performance.

[0058] Comparative Example 1

[0059] Except for replacing 500.0 g of the inorganic composite guanidine salt polymer anti-harmful microorganism material 1# with 500 g of polyhexamethylene guanidine hydrochloride (average molecular weight 10,000), the rest is the same as in Example 1, and the SBS thermoplastic elastomer antibacterial and mildew-proof masterbatch 3# of Comparative Example 1 was prepared.

[0060] The test sample was prepared in the same way as in Example 1 for testing the antibacterial and mildew-proof performance.

[0061] Comparative Example 2

[0062] Except for replacing 500.0 g of the inorganic composite guanidine salt polymer anti-harmful microorganism material 1# with 500 g of polyhexamethylene guanidine propionate (average molecular weight 10,000), the rest is the same as in Example 2, and the SBS thermoplastic elastomer antibacterial and mildew-proof masterbatch 4# of Comparative Example 2 was prepared.

[0063] The test sample was prepared in the same way as in Example 1 for testing the antibacterial and mildew-proof performance.

[0064] The test standards in Examples 1 - 2 and Comparative Examples 1 - 2 are as follows:

[0065] 1. Antibacterial test standard: GB / T 31402 - 2015 "Plastics - Test Method for Antibacterial Properties of Plastic Surfaces", test bacteria: Staphylococcus aureus ATCC 6538P, Escherichia coli ATCC 8739.

[0066] 2. Mildew-proof level test standard: GB 21551.2-2010 "Special Requirements for Antibacterial Materials with Antibacterial, Bactericidal, and Purification Functions for Household and Similar Electrical Appliances".

[0067] 3. Test standard for the anti-dissolution property of antibacterial substances (width of inhibition zone): GB 21551.1 "Special Requirements for Antibacterial Materials with Antibacterial, Bactericidal, and Purification Functions for Household and Similar Electrical Appliances".

[0068] 4. Test water immersion treatment standard for the anti-dissolution property of the sample of SBS thermoplastic elastomer antibacterial and mildew-proof masterbatch: The test method specified in JC / T939-2004 "Antibacterial Performance of Antibacterial Plastic Pipes for Building Use". First, immerse the sample in a distilled water bath at a temperature of (50±2°C) for 16h, and then test the antibacterial and mildew-proof performance.

[0069] The test results are shown in Table 1 below.

[0070] Table 1 Test Results of Antibacterial and Mildew-proof Performance of Examples 1-2 and Comparative Examples 1-2

[0071]

[0072] As can be seen from the above table, the SBS thermoplastic elastomer antibacterial and mildew-proof masterbatch provided by this application itself has good antibacterial and mildew-proof performance. The products made from this antibacterial and mildew-proof masterbatch have excellent and lasting anti-dissolution, antibacterial, and mildew-proof effects, and have safe and non-silvering properties. It can be applied to the preparation of SBS resin products with antibacterial and mildew-proof functions, and the addition ratio is 2-10%. The prepared antibacterial and mildew-proof SBS resin products have the advantages of safety, broad spectrum, anti-dissolution, and lasting antibacterial and mildew-proof effects, and have broad market prospects and commercial value.

[0073] 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;

[0074] 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. 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;

[0075] 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.

[0076] Specifically, there are thirteen sections of cylinders 230. The section closest to the hopper 220 is the first section;

[0077] Vacuum exhaust structures 240 are provided on the cylinders 230 at the 5th, 9th, and 12th positions;

[0078] Nitrogen inlet assemblies 250 are provided on the cylinders 230 at the 2nd - 4th, 6th - 8th, and 10th - 11th positions;

[0079] The hopper 220 is provided with a cover plate, and a nitrogen discharge assembly 260 is provided on the cover plate.

[0080] Specifically, the nitrogen inlet pipe fitting assembly is provided with a first pipe valve, a pressure regulating assembly, and a gas volume regulating assembly;

[0081] The nitrogen discharge assembly 260 is provided with a second pipe valve.

[0082] 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.

[0083] 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.

[0084] The above embodiments only represent several implementation manners of the present invention. The description is relatively specific and detailed, but it cannot 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. A SBS thermoplastic elastomer antibacterial and anti-mildew masterbatch, characterized in that: It is composed of the following components in parts by weight: 100 parts of SBS resin particles; 10-40 parts of inorganic composite guanidine salt polymer anti-harmful microbial material; Primary antioxidant 0.1-1.0 part; Auxiliary antioxidant 0.1-1.0 part; Dispersant 0.2-5.0 parts; 0.5-5.0 parts of FAU molecular sieve powder; The inorganic composite guanidine salt polymer anti-harmful microorganism material is composited by 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-harmful microbial material, the mass content of the polyether polyol is 3% to 35%, the mass content of the methyl silicone oil is 0.5% to 10%, the mass 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 primary antioxidant is selected from at least one of antioxidant 1010 (pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate), antioxidant 264 (2,6-di-tert-butyl-p-methylphenol), and antioxidant 1076 (octadecylβ-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate); The auxiliary antioxidant is selected from at least one of the antioxidant DLTP (dilauryl thiodipropionate), antioxidant 168 (tris(2,4-di-tert-butylphenyl) phosphite), and antioxidant TNP (tris(nonylphenyl) phosphite); The dispersant is selected from at least one of N,N'-ethylene bisstearamide, polyethylene wax, ethylene bislauramide and N,N'-ethylene oleamide.

2. The SBS thermoplastic elastomer antibacterial and anti-mildew masterbatch 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 SBS thermoplastic elastomer antibacterial and anti-mildew masterbatch 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 SBS thermoplastic elastomer antibacterial and anti-mildew masterbatch according to any one of claims 1 to 3, characterized in that: The preparation steps include: S1: preparing inorganic composite guanidine salt polymer anti-harmful microbial material for standby use; S2: SBS resin particles, inorganic composite guanidine salt polymer anti-harmful microbial material, primary antioxidant, auxiliary antioxidant, dispersant, and FAU molecular sieve raw powder are mixed evenly according to the proportion, and then added into the twin-screw extruder; S3: nitrogen protection, the temperature of the twin-screw extruder is set to 170°C to 210°C, the speed is set to 130 to 180 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 SBS thermoplastic elastomer antibacterial and mildew-proof masterbatch.

5. The method for preparing the SBS thermoplastic elastomer antibacterial and anti-mildew masterbatch according to claim 4, characterized in that: The specific preparation steps of the inorganic composite guanidine salt polymer anti-harmful microorganism material in S1 are as follows: S10: adding epoxy functionalized silica, guanidine salt polymer, polyether polyol and methyl silicone oil to a kneader with an ultrasonic generator, passing inert gas protection at normal pressure, starting stirring at room temperature to mix the materials evenly, then raising the temperature and stirring to melt the polymer material and mix it evenly with the epoxy functionalized silica, at the same time, starting the kneader ultrasonic generator, under the action of ultrasonic waves, causing the epoxy functionalized silica to be fully dispersed in the molten material for reaction, and maintaining the reaction temperature of 100-200° C. for 1-8 hours, then maintaining the original reaction temperature of the kneader, the agitator and the ultrasonic generator, turning off the inert gas, vacuum degassing for 1-3 hours, passing inert gas to normal pressure, adding zinc ricinoleate, and continuing stirring for 0.5-2 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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