Mildew-proof antibacterial polyolefin material as well as processing technology and application thereof

Abstract

The invention relates to the technical field of polyolefin materials, in particular to a mildewproof and antibacterial polyolefin material and a processing technology and application thereof. The mildew-proof antibacterial polyolefin material comprises the following components in parts by weight: 60-80 parts of polypropylene, 5-15 parts of an elastomer, 2-5 parts of maleic anhydride grafted polypropylene, 15-25 parts of white oil, 10-30 parts of talcum powder, 1-5 parts of a mildew-proof antibacterial agent, 0.5-1.0 part of an antioxidant and 1-3 parts of a lubricant. The mildew-proof antibacterial agent is a mixture prepared from 0.5 to 2.0 parts of modified nano zinc oxide, 0.3 to 1.5 parts of methylisothiazolinone and 0.2 to 1.5 parts of epsilon-polylysine hydrochloride. The mildew-proof and antibacterial polyolefin material prepared by the invention has excellent mechanical properties and mildew-proof and antibacterial properties.

Description

Technical Field

[0001] The present invention relates to the technical field of polyolefin materials, in particular to a mildew-proof and antibacterial polyolefin material and a processing technology and application thereof. Background Art

[0002] As people's living standards improve and their health awareness grows, their requirements for living environments and product quality are becoming increasingly stringent, leading to a growing demand for polyolefin materials with mildew and antibacterial properties. This is particularly true in fields with strict hygiene requirements, such as healthcare, food, and sanitation, as well as in environments susceptible to microbial contamination, such as humid bathrooms and kitchens. These materials hold broad application prospects.

[0003] Polyolefin materials, such as polyethylene and polypropylene, have low production costs, excellent comprehensive mechanical properties, are non-toxic, lightweight, corrosion-resistant, and easy to process and recycle. They are widely used in the manufacture of pipes, daily necessities, films, home appliance housings, automotive interiors, and other fields. However, polyolefin materials are prone to breeding bacteria and mold in damp and dark environments, especially in areas with high hygiene requirements such as hospitals, food processing, and sanitary ware. Their use can lead to health problems such as cross-infection. Many existing antimicrobial agents are prone to failure during use, especially in high temperature and high humidity environments, where the antimicrobial effect is significantly reduced, resulting in the material being unable to maintain its antimicrobial properties for a long time.

[0004] Therefore, we propose a mildew-proof and antibacterial polyolefin material and its processing technology and application. Summary of the Invention

[0005] The purpose of the present invention is to provide a mildew-proof and antibacterial polyolefin material and its processing technology and application, so as to solve the problems raised in the prior art.

[0006] To achieve the above object, the present invention provides the following technical solutions: A processing technology for mildew-proof and antibacterial polyolefin materials comprises the following steps: After polypropylene, elastomer and white oil are evenly mixed, maleic anhydride grafted polypropylene, talcum powder, mildew and antibacterial agent, antioxidant and lubricant are added and mixed evenly, and melt-extruded and granulated through a twin-screw extruder at an extrusion temperature of 180-220° C. to obtain mildew and antibacterial polyolefin material.

[0007] Furthermore, the mildew-proof and antibacterial polyolefin material includes the following components by weight: 60-80 parts of polypropylene, 5-15 parts of elastomer, 2-5 parts of maleic anhydride grafted polypropylene, 15-25 parts of white oil, 10-30 parts of talc, 1-5 parts of mildew-proof and antibacterial agent, 0.5-1.0 part of antioxidant, and 1-3 parts of lubricant.

[0008] Furthermore, the elastomer is a mixture of one or more of ethylene-hexene copolymer, ethylene-butene copolymer, and ethylene-octene copolymer.

[0009] Furthermore, the mildew and antibacterial agent is a mixture of 0.5-2.0 parts of modified nano zinc oxide, 0.3-1.5 parts of methylisothiazolinone and 0.2-1.5 parts of ε-polylysine hydrochloride.

[0010] Furthermore, the preparation method of the modified nano zinc oxide is as follows: Step 1: Add nano zinc oxide to a mixed solution of anhydrous ethanol and deionized water, ultrasonically disperse for 10-30 minutes, add vinyl triethoxysilane and mix, adjust the pH of the system to 4-5, react at 60-70°C for 4-6 hours, centrifuge, wash, and dry to obtain vinyl nano zinc oxide; Step 2: Dissolve polyhexamethyleneguanidine hydrochloride in dimethyl sulfoxide, add 4-epoxyisoeugenol, react at 50-60°C for 22-24 hours, filter, wash, and dry to obtain a double-bond guanidine compound; Step 3: Evenly mix vinyl nano zinc oxide and deionized water, add methyl methacrylate, double-bond guanidine compound and modified chitosan, introduce nitrogen, add potassium persulfate, react at 70-80°C for 10-12h, centrifuge, wash and dry to obtain modified nano zinc oxide.

[0011] Furthermore, in the step 1, the mass ratio of nano zinc oxide, anhydrous ethanol, deionized water and vinyltrimethoxysilane is 1: (15-20): (3-5): (1-3).

[0012] Furthermore, in the step 2, the molar ratio of polyhexamethyleneguanidine hydrochloride to 4-epoxyisoeugenol is 1:1.

[0013] Furthermore, in the step three, the mass ratio of vinyl nano zinc oxide, deionized water, methyl methacrylate, double-bond guanidine compound and modified chitosan is 1: (15-20): (1-2): (2-4): (0.5-1.5).

[0014] Furthermore, the amount of potassium persulfate used is 1-3% of the total mass of the vinyl nano zinc oxide, methyl methacrylate, the double-bond guanidine compound and the modified chitosan.

[0015] Furthermore, the preparation method of the modified chitosan is as follows: Sorbic acid and ethanol are mixed evenly, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide, MES buffer and N-hydroxysuccinimide are added, and the mixture is reacted under ice bath conditions for 1-2 hours. Chitosan solution is then added, and the mixture is reacted at room temperature for 10-12 hours. After dialysis and drying, a chitosan-sorbic acid graft copolymer is obtained. The chitosan-sorbic acid graft copolymer and ethanol are mixed evenly, sodium hydroxide solution is added to adjust the pH to 9-10, 2,3-epoxypropyltrimethylammonium chloride is added, the mixture is reacted at 60-70° C. for 5-7 hours, and modified chitosan is obtained after precipitation, filtration, washing and drying.

[0016] Furthermore, the mass ratio of sorbic acid, ethanol, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide, MES buffer and N-hydroxysuccinimide is 1:(5-10):(0.1-0.2):(1-2):(0.08-1.0), and the pH of the MES buffer is 5.5.

[0017] Furthermore, the amount of the chitosan solution is 50-75 times the mass of sorbic acid, the concentration of the chitosan solution is 2-4wt%, and the solvent is 2wt% acetic acid solution.

[0018] Furthermore, the mass ratio of the chitosan-sorbic acid graft copolymer, ethanol and 2,3-epoxypropyltrimethylammonium chloride is 1:(15-30):(3-5), and the concentration of the sodium hydroxide solution is 40wt%.

[0019] Furthermore, the lubricant is a mixture of one or more of polypropylene wax, polyethylene wax, silicone masterbatch, polytetrafluoroethylene, and paraffin wax powder.

[0020] Furthermore, the antioxidant is antioxidant 1010.

[0021] Compared with the prior art, the present invention has the following beneficial effects: 1. The present invention discloses a mildew-proof and antibacterial polyolefin material, a processing technology and an application thereof. Chitosan has excellent antibacterial properties such as biodegradability, broad-spectrum antibacterial properties, and biocompatibility. Sorbic acid is grafted onto chitosan using a 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide (EDC) / N-hydroxysuccinimide (NHS) chemical cross-linking method to form a chitosan-sorbic acid graft copolymer, introducing an unsaturated double bond. Finally, 2,3-epoxypropyltrimethylammonium chloride (GTA) quaternary ammonium salt is grafted onto the C6 hydroxyl group of chitosan to obtain a modified chitosan, which further improves the antibacterial properties and biocompatibility of the material and extends the service life of the material.

[0022] 2. The present invention discloses a mildew-proof and antibacterial polyolefin material, its processing technology, and application. Functionalized polyhexamethyleneguanidine hydrochloride containing carbon-carbon double bond groups is prepared by reacting the terminal amino group in polyhexamethyleneguanidine hydrochloride with the epoxy group in 4-epoxyisoeugenol. This double-bonded guanidine compound can be used as a macromonomer and copolymerized with other monomers to significantly enhance its long-lasting antibacterial properties. Vinyltrimethoxysilane (VTES) was used to modify the surface of nano-zinc oxide to obtain vinyl nano-zinc oxide. Finally, methyl methacrylate, double-bond guanidine compounds and modified chitosan were copolymerized and coated on the surface of modified chitosan through free radical copolymerization to form a high-density layer, which significantly improved the antibacterial effect. It is beneficial to improve its compatibility and dispersibility in the polypropylene matrix (PP), reduce phase separation, and solve the problem that traditional small molecule antibacterial agents are easy to migrate and dissolve, resulting in a short-term antibacterial effect. In this scheme, the guanidine compound itself has broad-spectrum antibacterial properties, and forms a synergistic effect with modified chitosan and nano-zinc oxide, enhancing the anti-mildew and antibacterial effect through multiple mechanisms such as contact sterilization and inhibition of microbial metabolism.

[0023] 2. The present invention discloses a mildew-proof and antibacterial polyolefin material, a processing technology and an application thereof. The mildew-proof and antibacterial agent is obtained by compounding modified nano zinc oxide, methylisothiazolinone and ε-polylysine hydrochloride. The prepared polyolefin material not only has excellent mildew-proof and antibacterial properties, but also can extend the service life of the material. DETAILED DESCRIPTION

[0024] The following is a clear and complete description of the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts are within the scope of protection of the present invention.

[0025] In this embodiment, polypropylene: model PP K8303, purchased from Yanshan Petrochemical; elastomer: ethylene-octene copolymer, brand VERSIFY POE 2300, Dow, USA; talc: particle size 5000 mesh, purchased from Jiangyin Guangyuan Superfine Powder Co., Ltd.; maleic anhydride grafted polypropylene: brand Exxelor PO 1020, Exxon; white oil: No. 3, purchased from Dongguan Kangjin New Materials Technology Co., Ltd.; nano zinc oxide: particle size 20 nm, purchased from Shanghai Yaotian New Materials Technology Co., Ltd.; methylisothiazolinone:; ε-polylysine hydrochloride: model P2658, purchased from Merck; polyhexamethylene guanidine hydrochloride: PGHC, purchased from Hubei Kemaidi Chemical Co., Ltd.; lubricant: polyethylene wax, model Honeywell AC-6A; antioxidant: model antioxidant 1010.

[0026] The following parts are by mass unless otherwise specified.

[0027] Example 1: A process for processing mildew-proof and antibacterial polyolefin materials, comprising the following processes: 60 parts of polypropylene, 5 parts of elastomer and 15 parts of white oil are uniformly mixed, and then 2 parts of maleic anhydride grafted polypropylene, 10 parts of talc, 1 part of mildew and antibacterial agent, 0.5 part of antioxidant and 1 part of lubricant are added and mixed evenly, and then melt-extruded and granulated by a twin-screw extruder at an extrusion temperature of 180° C. to obtain a mildew and antibacterial polyolefin material; the mildew and antibacterial agent is a mixture of 0.5 parts of modified nano zinc oxide, 0.3 parts of methylisothiazolinone and 0.2 parts of ε-polylysine hydrochloride; The preparation method of modified nano zinc oxide is as follows: Step 1: Add 0.5 parts of nano zinc oxide to a mixed solution of 7.5 parts of anhydrous ethanol and 1.5 parts of deionized water, ultrasonically disperse for 10 minutes, add 0.5 parts of vinyl triethoxysilane and mix, adjust the pH of the system to 4, react at 60°C for 4 hours, centrifuge, wash, and dry to obtain vinyl nano zinc oxide; Step 2: Dissolve 1 part of polyhexamethyleneguanidine hydrochloride in dimethyl sulfoxide, add 4-epoxyisoeugenol, react at 50°C for 22 hours, filter, wash, and dry to obtain a double-bond guanidine compound; the molar ratio of polyhexamethyleneguanidine hydrochloride to 4-epoxyisoeugenol is 1:1; Step 3: 0.5 parts of vinyl nano zinc oxide and 7.5 parts of deionized water were mixed evenly, 0.5 parts of methyl methacrylate, 1 part of a double-bond guanidine compound and 0.25 parts of modified chitosan were added, nitrogen was introduced, 0.023 parts of potassium persulfate were added, and the mixture was reacted at 70°C for 10 hours. After centrifugation, washing and drying, modified nano zinc oxide was obtained; The preparation method of modified chitosan is as follows: 0.25 parts of sorbic acid and 1.25 parts of ethanol were mixed evenly, 0.025 parts of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide, 0.25 parts of MES buffer and 0.02 parts of N-hydroxysuccinimide were added, and the mixture was reacted in an ice bath for 1 hour. Then, 12.5 parts of 2wt% chitosan solution were added, and the mixture was reacted at room temperature for 10 hours. After dialysis and drying, a chitosan-sorbic acid graft copolymer was obtained. 0.25 parts of chitosan-sorbic acid graft copolymer and 3.75 parts of ethanol were mixed evenly, 40wt% sodium hydroxide solution was added to adjust the pH to 9, 0.75 parts of 2,3-epoxypropyltrimethylammonium chloride was added, and the mixture was reacted at 60°C for 5 hours. After precipitation, filtration, washing and drying, a modified chitosan was obtained.

[0028] Example 2: A processing technology for mildew-proof and antibacterial polyolefin material, comprising the following processes: 70 parts of polypropylene, 10 parts of elastomer and 20 parts of white oil are uniformly mixed, and then 4 parts of maleic anhydride grafted polypropylene, 20 parts of talc, 3 parts of mildew and antibacterial agent, 0.8 parts of antioxidant and 2 parts of lubricant are added and mixed evenly. The mixture is melt-extruded and granulated through a twin-screw extruder at an extrusion temperature of 200° C. to obtain a mildew and antibacterial polyolefin material; the mildew and antibacterial agent is a mixture of 1 part of modified nano zinc oxide, 1 part of methylisothiazolinone and 1 part of ε-polylysine hydrochloride; The preparation method of modified nano zinc oxide is as follows: Step 1: Add 1 part of nano zinc oxide to a mixed solution of 18 parts of anhydrous ethanol and 4 parts of deionized water, ultrasonically disperse for 20 minutes, add 2 parts of vinyl triethoxysilane and mix, adjust the pH of the system to 4.5, react at 65°C for 5 hours, centrifuge, wash, and dry to obtain vinyl nano zinc oxide; Step 2: Dissolve 3 parts of polyhexamethyleneguanidine hydrochloride in dimethyl sulfoxide, add 4-epoxyisoeugenol, react at 55°C for 23 hours, filter, wash, and dry to obtain a double-bond guanidine compound; the molar ratio of polyhexamethyleneguanidine hydrochloride to 4-epoxyisoeugenol is 1:1; Step 3: Mix 1 part of vinyl nano zinc oxide and 18 parts of deionized water, add 1.5 parts of methyl methacrylate, 3 parts of a double-bond guanidine compound and 1 part of modified chitosan, introduce nitrogen, add 0.13 parts of potassium persulfate, react at 75°C for 11 hours, centrifuge, wash and dry to obtain modified nano zinc oxide; The preparation method of modified chitosan is as follows: 0.6 parts of sorbic acid and 4.8 parts of ethanol were mixed evenly, 0.09 parts of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide, 0.9 parts of MES buffer and 0.5 parts of N-hydroxysuccinimide were added, and the mixture was reacted in an ice bath for 1.5 hours. Then, 40 parts of 3wt% chitosan solution were added, and the mixture was reacted at room temperature for 11 hours. After dialysis and drying, a chitosan-sorbic acid graft copolymer was obtained. 1 part of chitosan-sorbic acid graft copolymer and 18 parts of ethanol were mixed evenly, 40wt% sodium hydroxide solution was added to adjust the pH to 9.5, 4 parts of 2,3-epoxypropyltrimethylammonium chloride were added, and the mixture was reacted at 65°C for 6 hours. After precipitation, filtration, washing and drying, a modified chitosan was obtained.

[0029] Example 3: A process for processing mildew-proof and antibacterial polyolefin materials, comprising the following processes: 80 parts of polypropylene, 15 parts of elastomer and 25 parts of white oil were uniformly mixed, and then 5 parts of maleic anhydride grafted polypropylene, 30 parts of talc, 5 parts of mildew and antibacterial agent, 1 part of antioxidant and 3 parts of lubricant were added and mixed uniformly. The mixture was melt-extruded and granulated through a twin-screw extruder at an extrusion temperature of 220° C. to obtain a mildew and antibacterial polyolefin material; the mildew and antibacterial agent was a mixture of 2.0 parts of modified nano zinc oxide, 1.5 parts of methylisothiazolinone and 1.5 parts of ε-polylysine hydrochloride; The preparation method of modified nano zinc oxide is as follows: Step 1: Add 2 parts of nano zinc oxide to a mixed solution of 40 parts of anhydrous ethanol and 10 parts of deionized water, ultrasonically disperse for 30 minutes, add 6 parts of vinyl triethoxysilane and mix, adjust the pH of the system to 5, react at 70°C for 6 hours, centrifuge, wash, and dry to obtain vinyl nano zinc oxide; Step 2: dissolving 8 parts of polyhexamethyleneguanidine hydrochloride in dimethyl sulfoxide, adding 4-epoxyisoeugenol, reacting at 60°C for 24 hours, filtering, washing, and drying to obtain a double-bond guanidine compound; the molar ratio of polyhexamethyleneguanidine hydrochloride to 4-epoxyisoeugenol is 1:1; Step 3: Mix 2 parts of vinyl nano zinc oxide and 40 parts of deionized water, add 4 parts of methyl methacrylate, 8 parts of a double-bond guanidine compound and 3 parts of modified chitosan, introduce nitrogen, add 0.51 parts of potassium persulfate, react at 80°C for 12 hours, centrifuge, wash and dry to obtain modified nano zinc oxide; The preparation method of modified chitosan is as follows: 1 part of sorbic acid and 10 parts of ethanol were mixed evenly, 0.2 parts of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide, 2 parts of MES buffer and 1 part of N-hydroxysuccinimide were added, and the mixture was reacted in an ice bath for 2 hours. Then, 75 parts of 4wt% chitosan solution were added, and the mixture was reacted at room temperature for 12 hours. After dialysis and drying, a chitosan-sorbic acid graft copolymer was obtained. 3 parts of chitosan-sorbic acid graft copolymer and 90 parts of ethanol were mixed evenly, 40wt% sodium hydroxide solution was added to adjust the pH to 10, 15 parts of 2,3-epoxypropyltrimethylammonium chloride were added, and the mixture was reacted at 70°C for 7 hours. After precipitation, filtration, washing and drying, a modified chitosan was obtained.

[0030] Comparative Example 1: A processing technology for mildew-proof and antibacterial polyolefin material, comprising the following processes: Compared with Example 2, the mildew-proof and antibacterial agent of Comparative Example 1 is a mixture of 1 part of nano zinc oxide, 1 part of methylisothiazolinone and 1 part of ε-polylysine hydrochloride; Comparative Example 1 replaces the modified nano zinc oxide with nano zinc oxide of the same mass, and the other steps are the same as Example 2.

[0031] Comparative Example 2: A processing technology for mildew-proof and antibacterial polyolefin materials, comprising the following processes: The preparation method of modified nano zinc oxide is as follows: Step 1: Add 1 part of nano zinc oxide to a mixed solution of 18 parts of anhydrous ethanol and 4 parts of deionized water, ultrasonically disperse for 20 minutes, add 2 parts of vinyl triethoxysilane and mix, adjust the pH of the system to 4.5, react at 65°C for 5 hours, centrifuge, wash, and dry to obtain vinyl nano zinc oxide; Step 2: Dissolve 3 parts of polyhexamethyleneguanidine hydrochloride in dimethyl sulfoxide, add 4-epoxyisoeugenol, react at 55°C for 23 hours, filter, wash, and dry to obtain a double-bond guanidine compound; the molar ratio of polyhexamethyleneguanidine hydrochloride to 4-epoxyisoeugenol is 1:1; Step 3: Mix 1 part of vinyl nano zinc oxide and 18 parts of deionized water, add 1.5 parts of methyl methacrylate and 3 parts of a double-bond guanidine compound, introduce nitrogen, add 0.13 parts of potassium persulfate, react at 75°C for 11 hours, centrifuge, wash, and dry to obtain modified nano zinc oxide; Compared with Example 2, modified chitosan was not added in step 3 of Comparative Example 2, and the other steps were the same as those in Example 2.

[0032] Comparative Example 3: A processing technology for mildew-proof and antibacterial polyolefin materials, comprising the following processes: The preparation method of modified nano zinc oxide is as follows: Step 1: Add 1 part of nano zinc oxide to a mixed solution of 18 parts of anhydrous ethanol and 4 parts of deionized water, ultrasonically disperse for 20 minutes, add 2 parts of vinyl triethoxysilane and mix, adjust the pH of the system to 4.5, react at 65°C for 5 hours, centrifuge, wash, and dry to obtain vinyl nano zinc oxide; Step 3: Mix 1 part of vinyl nano zinc oxide and 18 parts of deionized water, add 1.5 parts of methyl methacrylate and 1 part of modified chitosan, introduce nitrogen, add 0.13 parts of potassium persulfate, react at 75°C for 11 hours, centrifuge, wash, and dry to obtain modified nano zinc oxide; The preparation method of modified chitosan is as follows: 0.6 parts of sorbic acid and 4.8 parts of ethanol were mixed evenly, 0.09 parts of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide, 0.9 parts of MES buffer and 0.5 parts of N-hydroxysuccinimide were added, and the mixture was reacted in an ice bath for 1.5 hours. Then, 40 parts of 3wt% chitosan solution were added, and the mixture was reacted at room temperature for 11 hours. After dialysis and drying, a chitosan-sorbic acid graft copolymer was obtained. 1 part of chitosan-sorbic acid graft copolymer and 18 parts of ethanol were mixed evenly, 40wt% sodium hydroxide solution was added to adjust the pH to 9.5, 4 parts of 2,3-epoxypropyltrimethylammonium chloride were added, and the mixture was reacted at 65°C for 6 hours. After precipitation, filtration, washing and drying, a modified chitosan was obtained. Compared with Example 2, in step 3 of Comparative Example 3, no double-bond guanidine compound is added, and the other steps are the same as those in Example 2.

[0033] Comparative Example 4: A processing technology for mildew-proof and antibacterial polyolefin material, comprising the following processes: Compared with Example 2, the mildew and antibacterial agent of Comparative Example 4 is a mixture of 1 part of nano zinc oxide and 1 part of ε-polylysine hydrochloride, and the other steps are the same as those of Example 2.

[0034] Experiment: The mildew-proof and antibacterial polyolefin materials obtained in Examples 1-3 and Comparative Examples 1-4 were injection molded into standard specimens at an injection temperature of 240°C. The properties of the specimens were tested and the test results were recorded: Tensile strength test: Tested in accordance with GB / T 1040.2-2022, with a test speed of 50 mm / min.

[0035] Antibacterial performance test: tested in accordance with JIS Z2801-2012, the test bacteria are Escherichia coli ATCC 25922 and Staphylococcus aureus ATCC 6538P, and the sample size is 50mm×50mm×2mm.

[0036] Anti-mildew performance test: According to JIS Z2911-2018 test, the tested bacterial species include Aspergillus niger ATCC 6275, Penicillium pinophilum ATCC 36839, Paecilomyces variotii ATCC 18502, Trichoderma viride ATCC 9645 and Chaetomium globosum ATCC6205. Level 0 means no mold growth, level 1 means initial growth, and level 2 means general anti-mildew performance. Mildew can be clearly seen with the naked eye. The surface coverage area of the sample is 10%-30%.

[0037] The test results are shown in Table 1.

[0038] Table 1 Test results of mildew-proof and antibacterial polyolefin material properties

[0039] According to the data in the above table, we can clearly draw the following conclusions: 1. Compared with Examples 1-3, the tensile strength, antibacterial rate and mildew resistance grade of the products obtained in Comparative Examples 1 and 4 are all reduced, indicating that the present invention significantly improves the mechanical properties and mildew resistance and antibacterial properties of the material by preparing modified nano zinc oxide; and further improves the mildew resistance and antibacterial properties of the material by introducing methylisothiazolinone and compounding with nano zinc oxide and ε-polylysine hydrochloride.

[0040] 2. Compared with Examples 1-3, the antibacterial rate and mildew resistance grade of the products obtained in Comparative Examples 2 and 3 decreased after 30 days, which shows that the present invention significantly improves the antiseptic and antibacterial properties of the material by introducing modified chitosan and double-bond guanidine compound to exert synergistic effects, and also enhances the compatibility and stability of the material, ensuring its effectiveness in long-term use.

[0041] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above and that the invention can be embodied in other specific forms without departing from the spirit or essential characteristics of the invention. Therefore, the embodiments should be considered in all respects as illustrative and non-restrictive, and the scope of the invention is defined by the appended claims rather than the foregoing description, and it is intended that all variations that come within the meaning and range of equivalents of the claims be embraced therein.

Claims

1. A processing technology for mildew-proof and antibacterial polyolefin materials, characterized by: The steps include: After polypropylene, elastomer and white oil are evenly mixed, maleic anhydride grafted polypropylene, talcum powder, mildew and antibacterial agent, antioxidant and lubricant are added and mixed evenly, and melt-extruded and granulated through a twin-screw extruder at an extrusion temperature of 180-220° C. to obtain mildew and antibacterial polyolefin material.

2. The processing technology of a mildew-proof and antibacterial polyolefin material according to claim 1, characterized in that: The mildew-proof and antibacterial polyolefin material comprises the following components by weight: 60-80 parts of polypropylene, 5-15 parts of elastomer, 2-5 parts of maleic anhydride grafted polypropylene, 15-25 parts of white oil, 10-30 parts of talc, 1-5 parts of mildew-proof and antibacterial agent, 0.5-1.0 parts of antioxidant, and 1-3 parts of lubricant.

3. The processing technology of the mildew-proof and antibacterial polyolefin material according to claim 2, characterized in that: The mildew and antibacterial agent is a mixture of 0.5-2.0 parts of modified nano zinc oxide, 0.3-1.5 parts of methylisothiazolinone and 0.2-1.5 parts of epsilon-polylysine hydrochloride.

4. The processing technology of the mildew-proof and antibacterial polyolefin material according to claim 3, characterized in that: The preparation method of the modified nano zinc oxide is as follows: Step 1: Add nano zinc oxide to a mixed solution of anhydrous ethanol and deionized water, ultrasonically disperse for 10-30 minutes, add vinyl triethoxysilane and mix, adjust the pH of the system to 4-5, react at 60-70°C for 4-6 hours, centrifuge, wash, and dry to obtain vinyl nano zinc oxide; Step 2: Mix polyhexamethyleneguanidine hydrochloride and dimethyl sulfoxide evenly, add 4-epoxyisoeugenol, react at 50-60°C for 22-25h, filter, wash, and dry to obtain a double-bond guanidine compound; Step 3: Evenly mix vinyl nano zinc oxide and deionized water, add methyl methacrylate, double-bond guanidine compound and modified chitosan, introduce nitrogen, add potassium persulfate, react at 70-80°C for 10-12h, centrifuge, wash and dry to obtain modified nano zinc oxide.

5. The processing technology of the mildew-proof and antibacterial polyolefin material according to claim 4, characterized in that: In the step three, the mass ratio of vinyl nano zinc oxide, methyl methacrylate, double-bond guanidine compound and modified chitosan is 1: (1-2): (2-4): (0.5-1.5).

6. The processing technology of the mildew-proof and antibacterial polyolefin material according to claim 5, characterized in that: The preparation method of the modified chitosan is as follows: Sorbic acid and ethanol are mixed evenly, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide, MES buffer and N-hydroxysuccinimide are added, and the mixture is reacted under ice bath conditions for 1-2 hours. Chitosan solution is then added, and the mixture is reacted at room temperature for 10-12 hours. After dialysis and drying, a chitosan-sorbic acid graft copolymer is obtained. The chitosan-sorbic acid graft copolymer and ethanol are mixed evenly, sodium hydroxide solution is added to adjust the pH to 9-10, 2,3-epoxypropyltrimethylammonium chloride is added, the mixture is reacted at 60-70° C. for 5-7 hours, and after precipitation, filtration, washing and drying, a modified chitosan is obtained.

7. The processing technology of the mildew-proof and antibacterial polyolefin material according to claim 2, characterized in that: The elastomer is a mixture of one or more of ethylene-hexene copolymer, ethylene-butene copolymer and ethylene-octene copolymer.

8. The processing technology of the mildew-proof and antibacterial polyolefin material according to claim 2, characterized in that: The lubricant is a mixture of one or more of polypropylene wax, polyethylene wax, silicone masterbatch, polytetrafluoroethylene, and paraffin wax powder.

9. A mildew-proof and antibacterial polyolefin material obtained according to the processing technology according to any one of claims 1 to 8.

10. Use of the mildew-proof and antibacterial polyolefin material according to claim 9 in a toothbrush handle.

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