High-impact polystyrene antibacterial mildew-proof master batch as well as preparation method and preparation device thereof

Abstract

The invention relates to a high-impact polystyrene antibacterial and mildew-proof master batch as well as a preparation method and a preparation device thereof. The antibacterial and mildew-proof master batch is prepared from the following components: high-impact polystyrene resin, an inorganic composite guanidine salt polymer anti-harmful microorganism material, a composite antioxidant, a dispersing agent and FAU type molecular sieve raw powder. The high-impact polystyrene antibacterial and mildew-proof master batch has the advantages of high antibacterial efficiency, dissolution resistance, lasting antibacterial and mildew-proof effects, safety and no silvering performance, can be applied to preparation of high-impact polystyrene resin products with antibacterial and mildew-proof functions, has the addition amount of 2-10%, and is suitable for industrial production. The prepared antibacterial and mildew-proof high-impact polystyrene resin product has the advantages of safety, broad spectrum, dissolution resistance, lasting antibacterial and mildew-proof effects and the like, and has wide market prospect and commercial value; the preparation method of the high-impact polystyrene antibacterial and mildew-proof master batch provided by the invention is simple in technological process 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 to a high impact polystyrene antibacterial and antifungal masterbatch, a preparation method thereof, and a preparation device thereof. Background Art

[0002] Due to the advantages of plastics such as light weight, non-corrosion, and comprehensive performance that can meet various application scenarios, their applications are becoming increasingly widespread. However, in people's living environments, various harmful pathogenic bacteria and molds survive and reproduce on the surfaces of daily-use plastic products, spreading various diseases that affect people's health and lives. With the improvement of people's living standards and the enhancement of health awareness, people have put forward higher requirements for the surrounding environment, and antibacterial plastics have developed into a type of functional polymer material for preventing and inhibiting the reproduction of harmful microorganisms.

[0003] High impact polystyrene (HIPS) is one of the materials with the lowest cost in the engineering plastic family, and is prepared by adding butadiene to polystyrene (PS) to improve its impact strength. It has good impact toughness, dimensional stability, and excellent processing performance, and is widely used in the fields of packaging, toys, furniture, electrical appliances, and construction. However, high impact polystyrene resin itself does not have the function of inhibiting harmful microorganisms such as pathogenic bacteria, molds, and viruses. Therefore, developing HIPS resin with antibacterial and antifungal functions has good economic value and social significance.

[0004] The high-impact polystyrene antibacterial and mildew-proof masterbatch is a concentrate in which additives with antibacterial and mildew-proof functions are evenly dispersed in a high-impact polystyrene carrier resin. It has the advantages of being easy to store and promoting the more uniform dispersion of antibacterial and mildew-proof additives in the high-impact polystyrene resin substrate. Antibacterial agents containing guanidine salt polymers have low toxicity, good high-temperature resistance, and excellent antibacterial and mildew-proof performance. Therefore, they are considered to have great development potential. Guanidine salt polymers are cationic polyelectrolytes with guanidine salt groups. They mainly form electrostatic adsorption through the cations in the molecule with the anionic sites on the surface of bacterial cells, hinder the action of harmful microbial cell lysing enzymes, and deform the surface structure of the cells to damage the cell membrane, thereby achieving the effect of inhibiting and killing microorganisms; Guanidine salt polymers have good water solubility, photothermal stability, high-efficiency and broad-spectrum antibacterial properties, safety, low toxicity, no irritation, no bacterial drug resistance, no volatilization, no heavy metals and phenols, no corrosion to various treated surfaces, and environmental friendliness, etc. They 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, they are mainly used in the surface disinfection treatment of products and the post-antibacterial finishing of textiles in the form of aqueous solutions 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 antibacterial and mildew-proof rubber and plastic products containing guanidine salt polymers while maintaining the advantages of guanidine salt polymers against harmful microorganisms is a very worthy research topic.

[0005] Therefore, it is necessary to develop a high-impact polystyrene antibacterial and mildew-proof masterbatch based on guanidine salt polymers with high antibacterial efficiency, anti-dissolution, long-lasting antibacterial and mildew-proof effects, safety, and silver-free properties, which not only has high economic value but also has good social value. Summary of the Invention

[0006] To solve the above problems, the present invention provides a high-impact polystyrene antibacterial and mildew-proof masterbatch, its preparation method and preparation device. The high-impact polystyrene antibacterial and mildew-proof masterbatch has high antibacterial efficiency, anti-dissolution, long-lasting antibacterial and mildew-proof effects, and safety and silver-free properties. It can be applied to the preparation of high-impact polystyrene resin products with antibacterial and mildew-proof functions, and the addition amount is 2-10%. The prepared antibacterial and mildew-proof high-impact polystyrene resin products have the advantages of safety, broad-spectrum, anti-dissolution, and long-lasting antibacterial and mildew-proof effects.

[0007] The technical solution adopted by the present invention is:

[0008] The high-impact polystyrene antibacterial and mildew-proof masterbatch of the present invention is composed of the following components in parts by weight:

[0009] 100 parts of high-impact polystyrene resin;

[0010] 10 - 30 parts of inorganic composite guanidine salt polymer anti - harmful microorganism material;

[0011] 0.2 - 1.0 part of compound antioxidant;

[0012] 0.2 - 1.5 part of dispersant;

[0013] 0.5 - 5.0 parts of FAU - type molecular sieve raw powder;

[0014] The inorganic composite guanidine salt polymer anti - algal agent is made by compounding silica white functionalized with epoxy groups, guanidine salt polymer, polyether polyol, methyl silicone oil and zinc ricinoleate;

[0015] 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 - based 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;

[0016] The polyether polyol is selected from one or more of polyoxypropylene polyol, polyoxyethylene polyol, polytrimethyl ether glycol, polytetrahydrofuran and their copolymer ether diols;

[0017] 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;

[0018] The compound antioxidant is compounded from a hindered phenol main antioxidant and a phosphite auxiliary antioxidant with a mass ratio of 1:2;

[0019] The dispersant is at least one of ethylene bisstearamide, polyethylene wax and liquid paraffin.

[0020] Furthermore, the epoxy - based 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.

[0021] 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.

[0022] Based on the same inventive concept, the present application also provides a method for preparing the above-mentioned high impact polystyrene antibacterial and mildew-proof masterbatch, comprising the following preparation steps:

[0023] S1: Prepare an inorganic composite guanidine salt polymer anti-harmful microorganism material for later use;

[0024] S2: Mix high impact polystyrene, inorganic composite guanidine salt polymer anti-harmful microorganism material, composite antioxidant, dispersant, 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;

[0025] S3: Under nitrogen protection, set the temperature of the twin-screw extruder to 180°C to 220°C, set the rotation speed to 200 to 350 rpm, evacuate and introduce nitrogen for protection;

[0026] S4: After melting and blending the mixed raw materials through a 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 high impact polystyrene antibacterial and mildew-proof masterbatch.

[0027] Further, the specific preparation steps of the inorganic composite guanidine salt polymer anti-algae agent in S1 are as follows:

[0028] S10. Add epoxy group-functionalized silica, guanidine salt polymer, polyether polyol, and methyl silicone oil to a kneader equipped with an ultrasonic generator, protect with inert gas under 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 epoxy group-functionalized silica. At the same time, start the ultrasonic generator of the kneader, and under the action of ultrasonic waves, promote the full dispersion of epoxy group-functionalized silica in the molten materials for reaction, and maintain the reaction temperature of 100°C to 200°C for 1 to 8 hours. Then, keep the original reaction temperature of the kneader, the agitator, and the ultrasonic generator working, turn off the inert gas, perform vacuum degassing for 1 to 3 hours, then introduce inert gas to normal pressure, add zinc ricinoleate, and continue stirring for 0.5 to 2 hours under inert gas protection;

[0029] 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 obtain an inorganic composite guanidine salt polymer anti-harmful microorganism material.

[0030] The inorganic composite guanidine salt polymer anti-harmful microorganism material provided by this application is bonded through chemical bonds to combine the high molecular chain of guanidine salt polymer onto the surface of inorganic silica powder particles. Utilizing the property that silica powder particles are insoluble in water, the prepared inorganic composite guanidine salt polymer anti-harmful microorganism material also has the characteristic of being insoluble in water, solving the problem of poor water solubility resistance of guanidine salt polymer added in polymer materials. Moreover, due to the characteristic of being insoluble in water, after the inorganic composite guanidine salt polymer anti-harmful microorganism material prepared by the present invention is added to polymer materials, it has anti-dissolution property and long-lasting antibacterial and mildew-proof effects.

[0031] 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;

[0032] 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 the ultrasonic generators are arranged on the side of the cylinder body. The inert pipe fittings are installed on the cylinder body for introducing or discharging inert gas, and the vacuum pipe fittings are installed on the cylinder body for pumping out the air in the cylinder body. Control valves are respectively installed on the inert pipe fittings and the vacuum pipe fittings;

[0033] The twin-screw extrusion component includes an extruder body and a hopper. The extruder body is provided with multiple sections of cylinders, and multiple sections of the cylinders are installed on the extruder body and are connected in parallel and rotated and meshed in the same direction. The hopper is installed on the extruder body and is arranged close to the cylinders.

[0034] Further, the cylinder is provided with thirteen sections, and the section close to the hopper is the 1st section;

[0035] Vacuum exhaust structures are provided on the cylinders at the 5th, 9th and 12th positions;

[0036] Nitrogen inlet components are provided on the cylinders at the 2-4th, 6-8th and 10-11th positions;

[0037] The hopper is provided with a cover plate, and a nitrogen discharge component is provided on the cover plate.

[0038] Further, the nitrogen inlet pipe fitting component is provided with a first pipe valve, a pressure regulating component and a gas volume regulating component;

[0039] A second pipe valve is provided on the nitrogen discharge component.

[0040] 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.

[0041] The beneficial effects of the present invention are as follows:

[0042] 1. The high-impact polystyrene antibacterial and mildew-proof masterbatch provided by the present application has high antibacterial efficiency, anti-dissolution, long-lasting antibacterial and mildew-proof effects, and is safe and silver-free. It can be applied to the preparation of high-impact polystyrene products with antibacterial and mildew-proof functions, and the addition amount is 2 - 10%. The prepared antibacterial and mildew-proof high-impact polystyrene products have the advantages of safety, broad spectrum, anti-dissolution, and long-lasting antibacterial and mildew-proof effects, and have broad market prospects and commercial value;

[0043] 2. The preparation method of the high-impact polystyrene 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.

[0044] 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

[0045] Figure 1 It is a schematic structural diagram of the ultrasonic kneading component in the present application;

[0046] Figure 2 It is a schematic structural diagram of the twin-screw extrusion component in the present application;

[0047] Figure 3 It is a 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);

[0048] Description of the reference numerals: ultrasonic kneading component 100, cylinder body 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 Embodiments

[0049] The present invention will be further described below in conjunction with preferred embodiments.

[0050] Embodiment 1:

[0051] The high-impact polystyrene antibacterial and mildew-proof masterbatch provided in this embodiment is prepared through the following steps:

[0052] S1. Prepare the inorganic composite guanidine salt polymer anti-harmful microorganism material powder 1# for standby;

[0053] S10. Add 1000 g of fumed silica that has been pre-dried at 120 °C for 5 hours into 30 L of an aqueous solution of absolute ethanol (the 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 and stir at a constant temperature for 10 hours. After filtering the fumed silica suspension by suction, wash it 3 times with absolute ethanol. After drying and grinding, obtain epoxy group-functionalized fumed silica for storage. 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%;

[0054] Add 600 g of the above-prepared epoxy group-functionalized fumed silica, 750 g of polyhexamethylene guanidine hydrochloride (average molecular weight 10000), 90 g of polyoxypropylene 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 vacuum-displacing nitrogen several times, open the stainless steel gas valve and introduce nitrogen at atmospheric pressure for protection. Start stirring at room temperature to make the materials mix evenly. Raise the temperature and stir to melt the polymer materials and then mix them evenly with the epoxy group-functionalized fumed 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 fumed 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;

[0055] 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-harmful microorganism material powder 1# of Example 1;

[0056] S2. Weigh 1920.0 g of high impact polystyrene resin (melt flow rate 5.5 g / 10 min, test method ASTM-D1238), 500.0 g of inorganic composite guanidine salt polymer anti-harmful microorganism material 1#, 4.0 g of antioxidant 1010, 8.0 g of antioxidant 626, 18.0 g of ethylene bisstearamide, and 50 g of ultra-stable USY zeolite powder (relative crystallinity 79 - 88%, Na2O 0.065 - 0.1 wt%, D50 2.5 - 5.2 um, D90 5.6 - 7.2 um, Bet 695 m2 / g). Stir them evenly in a mixer, then 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 nitrogen injection at the head cover, set the barrel temperature of the parallel co-rotating intermeshing twin-screw extrusion to 180°C - 220°C, the screw speed to 200 rpm. Open the stainless steel gas path valves for nitrogen inlet at the 2nd - 4th, 6th - 8th, and 10th - 11th barrel sections from the feed inlet through the nitrogen inlet nozzles at the center of the barrel top to introduce nitrogen for protection, and start the vacuum system. Set up vacuum degassing chambers at the 5th, 9th, and 12th barrel sections from the feed inlet to degas the blended materials. After the blended materials are melt-blended through the twin-screw extruder, granulate them through an air-cooled die face pelletizing device, and use nitrogen air cooling for protection at the die head to obtain high impact polystyrene antibacterial and mildew-proof masterbatch 1#.

[0057] Weigh 15.0 g of the high impact polystyrene antibacterial and mildew-proof masterbatch 1# prepared in this example and 485.0 g of high impact polystyrene resin (melt flow rate 5.5 g / 10 min, test method ASTM-D1238), stir them evenly in a mixer, and then use an injection molding machine to inject them into an antibacterial and mildew-proof high impact polystyrene test sample of 50 mm * 50 mm * 3 mm at an injection temperature of 220°C for the test of antibacterial and mildew-proof performance.

[0058] Example 2:

[0059] The high impact polystyrene antibacterial and mildew-proof masterbatch 2# is prepared in this example.

[0060] 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 10000), the rest is the same as powder 1# in Example 1.

[0061] The preparation of the test sample is the same as that in Example 1 for the test of antibacterial and mildew-proof performance.

[0062] Comparative Example 1

[0063] 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-harmful microorganism material 1#, the rest was the same as in Example 1, and the high-impact polystyrene antibacterial and mildew-proof masterbatch 3# of Comparative Example 1 was prepared.

[0064] The test sample was prepared in the same way as in Example 1, and the antibacterial and mildew-proof performance was tested.

[0065] Comparative Example 2

[0066] 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-harmful microorganism material 1#, the rest was the same as in Example 2, and the high-impact polystyrene antibacterial and mildew-proof masterbatch 4# of Comparative Example 2 was prepared.

[0067] The test sample was prepared in the same way as in Example 1, and the antibacterial and mildew-proof performance was tested.

[0068] Among them, the test methods in Examples 1-2 and Comparative Examples 1-2 are as follows:

[0069] 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.

[0070] 2. Mildew-proof grade test standard: GB 21551.2-2010 "Special Requirements for Antibacterial Materials with Antibacterial, Bactericidal and Purification Functions for Household and Similar Electrical Appliances".

[0071] 3. Antibacterial substance anti-dissolution test standard (width of inhibition zone): GB 21551.1 "Special Requirements for Antibacterial Materials with Antibacterial, Bactericidal and Purification Functions for Household and Similar Electrical Appliances".

[0072] 4. Water immersion treatment standard for anti-dissolution test of high-impact polystyrene antibacterial and mildew-proof masterbatch samples: The test method specified in JC / T 939-2004 "Antibacterial Performance of Antibacterial Plastic Pipes for Building Use". First, soak the sample in a distilled water water bath at a temperature of (50 ± 2°C) for 16 h, and then test the antibacterial and mildew-proof performance.

[0073] The test results are shown in Table 1 below:

[0074] Table 1 Test Results of Antibacterial and Mildew-proof Performance of Examples 1-2 and Comparative Examples 1-2

[0075]

[0076] As can be seen from the above table, the high impact polystyrene antibacterial and mildew-proof masterbatch provided by this application has good antibacterial and mildew-proof performance, with high antibacterial and mildew-proof efficiency, anti-dissolution, and long-lasting antibacterial and mildew-proof effects. It can be used in the preparation of high impact polystyrene products with antibacterial and mildew-proof functions, and the addition amount is 2-10% of the high impact polystyrene base material. The mildew-proof grade of the prepared antibacterial and mildew-proof high impact polystyrene products reaches the highest grade 0, which can better meet the application requirements, and has the advantages of safety, broad spectrum, anti-dissolution, and long-lasting antibacterial and mildew-proof effects, with broad market prospects and commercial value.

[0077] 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;

[0078] The ultrasonic kneading component 100 is provided with a cylinder body 110, multiple groups of ultrasonic generators 120, an inert pipe fitting 130, and a vacuum pipe fitting 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 fitting 130 is installed on the cylinder body 110 for introducing or discharging inert gas, and the vacuum pipe fitting 140 is installed on the cylinder body 110 for extracting the air in the cylinder body 110. Control valves are respectively installed on the inert pipe fitting 130 and the vacuum pipe fitting 140;

[0079] 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 barrel bodies 230. The multiple sections of barrel bodies 230 are installed on the extruder body 210 and are connected in parallel and rotated in the same direction by meshing. The hopper 220 is installed on the extruder body 210 and is arranged close to the barrel body 230.

[0080] Specifically, there are thirteen sections of barrel bodies 230, and the one close to the hopper 220 is the first section;

[0081] Vacuum discharge structures 240 are provided on the barrel bodies 230 at the 5th, 9th, and 12th positions;

[0082] Nitrogen inlet components 250 are provided on the barrel bodies 230 at the 2-4th, 6-8th, and 10-11th positions;

[0083] The hopper 220 is provided with a cover plate, and a nitrogen discharge component 260 is provided on the cover plate.

[0084] Specifically, the nitrogen inlet pipe fitting assembly is provided with a first pipe valve, a pressure regulating component, and a gas volume regulating component;

[0085] The nitrogen discharge component 260 is provided with a second pipe valve.

[0086] Specifically, the frequencies of multiple groups of ultrasonic generators 120 are set to 20 kHz respectively, and the power adjustment range of a single ultrasonic generator in multiple groups of ultrasonic generators 120 is 0 to 500 W.

[0087] 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.

[0088] The above embodiments only represent several implementation manners of the present invention. The description thereof 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 modifications 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 shall be subject to the appended claims.

Claims

1. A high impact polystyrene antibacterial and mildew proof masterbatch, characterized in that: It is composed of the following components in parts by weight: 100 parts of high impact polystyrene resin; 10-30 parts of inorganic composite guanidine salt polymer anti-harmful microbial material; 0.2-1.0 part of compound antioxidant; Dispersant 0.2-1.5 parts; 0.5-5.0 parts of FAU molecular sieve powder; 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 composite antioxidant is prepared by compounding a hindered phenol main antioxidant and a phosphite auxiliary antioxidant in a mass ratio of 1:2; The dispersant is at least one of ethylene bisstearamide, polyethylene wax and liquid paraffin.

2. The high-impact polystyrene 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 high-impact polystyrene 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 high-impact polystyrene 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: High-impact polystyrene, inorganic composite guanidine salt polymer anti-harmful microbial material, composite antioxidant, dispersant, and FAU molecular sieve raw powder are mixed evenly according to a proportion, placed in a hot air dryer at 70°C to 80°C for 3 to 5 hours, and then added to a twin-screw extruder; S3: nitrogen protection, the temperature of the twin-screw extruder is set to 180°C to 220°C, the speed is set to 200 to 350rpm, 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 high-impact polystyrene antibacterial and mildew-proof masterbatch.

5. The method for preparing the high-impact polystyrene antibacterial and mildew-proof masterbatch 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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