Mildew-proof antibacterial composite packaging bag and preparation method thereof

Abstract

The invention relates to the field of packaging bags, in particular to a mildewproof and bacteriostatic composite packaging bag and a preparation method thereof, and aims to solve the problem that an existing packaging bag is lack of effective inhibition capability on breeding and reproduction of bacteria and molds. According to the composite packaging bag, the polypropylene resin serves as the main raw material, so that the composite packaging bag has high mechanical performance, the packaging requirements of different products can be met, reliable physical protection is provided for the products, and the products are prevented from being subjected to external physical damage and leakage; the fluorine-containing bis-imidazolium ionic compound and the modified nano-copper oxide are added into the composite packaging bag, growth of various common bacteria and molds can be effectively inhibited and killed under the synergistic effect of the fluorine-containing bis-imidazolium ionic compound and the modified nano-copper oxide, commodities in the packaging bag can be prevented from being damaged by microorganisms, the quality and the use value of the commodities are guaranteed, the shelf life of the commodities is prolonged, and moreover, the product quality is improved. The preparation method has the advantages of simple operation, easy industrial production, low cost and good market application prospect.

Description

Technical Field

[0001] The present invention relates to the field of packaging bags, and particularly to a mildew-proof and bacteriostatic composite packaging bag and a preparation method thereof. Background Art

[0002] During the storage and circulation of various products, the packaging bag is one of the key factors to ensure product quality. However, traditional packaging bags often only have basic physical protection functions, such as preventing products from being collided, squeezed, and invaded by external dust and moisture, but lack effective inhibitory ability against the growth and reproduction of bacteria and molds.

[0003] Products such as food, medicine, and cosmetics are rich in nutrients and are extremely likely to become a hotbed for the growth of bacteria and molds under suitable temperature and humidity conditions. The growth of bacteria and molds will not only cause the appearance of the product to deteriorate, such as the appearance of mildew spots, discoloration, peculiar smell, etc., but also reduce the quality and performance of the product, and even produce toxic and harmful substances, posing a serious threat to human health.

[0004] Therefore, developing a mildew-proof and bacteriostatic composite packaging bag and a preparation method thereof has important practical significance and market demand. Summary of the Invention

[0005] In order to overcome the above technical problems, the purpose of the present invention is to provide a mildew-proof and bacteriostatic composite packaging bag and a preparation method thereof, which solves the problem that the existing packaging bags lack effective inhibitory ability against the growth and reproduction of bacteria and molds, which will not only cause the appearance of the packaged products to deteriorate, but also reduce the quality and performance of the packaged products, and even produce toxic and harmful substances, posing a serious threat to human health.

[0006] The purpose of the present invention can be achieved by the following technical solutions:

[0007] A mildew-proof and bacteriostatic composite packaging bag, comprising the following components in parts by weight:

[0008] 90 - 100 parts of polypropylene resin, 0.5 - 3.5 parts of fluorinated bisimidazolium ionic compound, 2 - 6 parts of modified nano-copper oxide, 3 - 9 parts of light calcium carbonate, 10 - 12 parts of plasticizer, 2 - 6 parts of lubricant, and 1 - 3 parts of antioxidant;

[0009] Among them, the fluorinated bisimidazolium ionic compound is prepared by the following steps:

[0010] Step a1: Add 1-octylimidazole, 2,2-bis(bromomethyl)-1,3-propanediol, and dimethyl sulfoxide into a three-necked flask equipped with a stirrer, a thermometer, and a gas pipe. Introduce nitrogen for protection. Stir and react for 20 - 30 min under the conditions of a temperature of 20 - 25°C and a stirring rate of 200 - 300 r / min. Then raise the temperature to 120 - 125°C and continue to stir and react for 10 - 15 h. After the reaction is completed, cool the reaction product to room temperature, then rotary evaporate to remove the solvent. Then add it into anhydrous tetrahydrofuran, then let it stand to precipitate, then vacuum filter. Place the filter cake in a vacuum drying oven and dry it for 2 - 3 h under the condition of a temperature of 60 - 65°C to obtain bis(imidazolium) diol;

[0011] Step a2: Add bis(imidazolium) diol, perfluorobutyric acid, p-toluenesulfonic acid, and toluene into a three-necked flask equipped with a stirrer, a thermometer, and a gas pipe. Introduce nitrogen for protection. Stir and react for 20 - 30 min under the conditions of a temperature of 20 - 25°C and a stirring rate of 200 - 300 r / min. Then raise the temperature to 90 - 100°C and continue to stir and react for 6 - 8 h. After the reaction is completed, cool the reaction product to room temperature, then rotary evaporate to remove the solvent. Then wash it with anhydrous tetrahydrofuran 3 - 5 times, then place it in a vacuum drying oven and dry it for 3 - 5 h under the condition of a temperature of 70 - 75°C to obtain a fluorinated bis(imidazolium) ionic compound.

[0012] As a further scheme of the present invention: The dosage ratio of the 1-octylimidazole, 2,2-bis(bromomethyl)-1,3-propanediol, and dimethyl sulfoxide in step a1 is 22 - 25 mmol: 10 mmol: 30 - 40 mL.

[0013] As a further scheme of the present invention: The dosage ratio of the bis(imidazolium) diol, perfluorobutyric acid, p-toluenesulfonic acid, and toluene in step a2 is 10 mmol: 22 - 25 mmol: 0.09 - 0.13 g: 50 - 60 mL.

[0014] As a further scheme of the present invention: The modified nano-copper oxide is prepared by the following steps:

[0015] Step b1: Add copper chloride dihydrate and deionized water into a three-necked flask equipped with a stirrer, a thermometer, a gas pipe, and a constant-pressure dropping funnel. Introduce nitrogen for protection. Stir and react for 10 - 20 min under the conditions of a temperature of 25 - 30 °C and a stirring rate of 200 - 300 r / min. Then, while stirring, gradually add sodium hydroxide solution dropwise, controlling the dropping rate at 1 - 2 drops / s. After the addition is complete, continue to stir and react for 10 - 20 min. Then, raise the temperature to 100 - 110 °C and continue to stir and react for 10 - 15 h. After the reaction is completed, cool the reaction product to room temperature, then centrifuge. Wash the precipitate with distilled water and absolute ethanol 3 - 5 times successively, and then place it in a vacuum drying oven and dry it at a temperature of 90 - 95 °C for 3 - 5 h to obtain nano-copper oxide;

[0016] Step b2: Add nano-copper oxide, sodium dodecyl sulfate, and deionized water into a three-necked flask equipped with a stirrer and a thermometer. Stir and react for 20 - 30 min under the conditions of a temperature of 20 - 25 °C and a stirring rate of 200 - 300 r / min. Then, raise the temperature to 40 - 45 °C and continue to stir and react for 10 - 15 h. After the reaction is completed, cool the reaction product to room temperature, then centrifuge. Wash the precipitate with distilled water and absolute ethanol 3 - 5 times successively, and then place it in a vacuum drying oven and dry it at a temperature of 60 - 65 °C for 3 - 5 h to obtain modified nano-copper oxide.

[0017] As a further scheme of the present invention: The dosage ratio of the copper chloride dihydrate, deionized water, and sodium hydroxide solution in step b1 is 10 mmol: 40 - 50 mL: 10 - 15 mL.

[0018] As a further scheme of the present invention: The mass fraction of the sodium hydroxide solution in step b1 is 30 - 35%.

[0019] As a further scheme of the present invention: The dosage ratio of the nano-copper oxide, sodium dodecyl sulfate, and deionized water in step b2 is 5 g: 1.8 - 5.4 g: 80 - 100 mL.

[0020] As a further scheme of the present invention: A preparation method of a mildew-proof and bacteriostatic composite packaging bag includes the following steps:

[0021] Step 1: Weigh 90 - 100 parts of polypropylene resin, 0.5 - 3.5 parts of fluorine-containing bisimidazolium ionic compound, 2 - 6 parts of modified nano-copper oxide, 3 - 9 parts of light calcium carbonate, 10 - 12 parts of plasticizer, 2 - 6 parts of lubricant, and 1 - 3 parts of antioxidant by weight, and set aside;

[0022] Step 2: Add polypropylene resin, fluorinated bisimidazolium ionic compound, modified nano-copper oxide, light calcium carbonate, plasticizer, lubricant, and antioxidant into a mixer and stir to mix evenly to obtain a mold and mildew inhibiting mixture;

[0023] Step 3: Add the mold and mildew inhibiting mixture into a twin-screw extruder and melt-blend and extrude under the conditions of a temperature of 170 - 180 °C and a screw speed of 100 - 150 r / min, and then pelletize to obtain mold and mildew inhibiting pellets;

[0024] Step 4: Add the mold and mildew inhibiting pellets into a blown film machine, melt them under the condition of a temperature of 165 - 175 °C, then extrude and blow the film, and wind it up to obtain a mold and mildew inhibiting composite packaging bag.

[0025] As a further scheme of the present invention: The polypropylene resin is pp-t300.

[0026] As a further scheme of the present invention: The plasticizer is a mixture of dioctyl adipate and dicyclohexyl phthalate in a mass ratio of 2:3.

[0027] As a further scheme of the present invention: The lubricant is vinyl bisstearamide.

[0028] As a further scheme of the present invention: The antioxidant is a mixture of antioxidant 1076 and antioxidant 1010 in a mass ratio of 3:1.

[0029] Beneficial effects of the present invention:

[0030] A mold and mildew inhibiting composite packaging bag and a preparation method thereof of the present invention, by adding polypropylene resin, fluorinated bisimidazolium ionic compound, modified nano-copper oxide, light calcium carbonate, plasticizer, lubricant, and antioxidant into a mixer and stirring to mix evenly to obtain a mold and mildew inhibiting mixture, adding the mold and mildew inhibiting mixture into a twin-screw extruder for melt-blending and extrusion, then pelletizing to obtain mold and mildew inhibiting pellets, adding the mold and mildew inhibiting pellets into a blown film machine to melt, extrude and blow the film, and wind it up to obtain a mold and mildew inhibiting composite packaging bag; the composite packaging bag uses polypropylene resin as the main raw material, so that the composite packaging bag has high mechanical properties, can meet the packaging requirements of different products, provides reliable physical protection for products, prevents products from being physically damaged and leaking by the outside world, by adding fluorinated bisimidazolium ionic compound and modified nano-copper oxide to the composite packaging bag, the growth of a variety of common bacteria and molds can be effectively inhibited and killed under the synergistic effect of the two, can prevent the goods in the package from being invaded by microorganisms, ensure the quality and use value of the goods, extend the shelf life of the goods, and moreover, the preparation method is simple in operation, easy for industrial production, low in cost, and has good market application prospects.

[0031] In the process of preparing the mildew-proof and bacteriostatic composite packaging bag, a fluorinated bis-imidazolium ion compound was first prepared. 1-Octylimidazole and 2,2-bis(bromomethyl)-1,3-propanediol reacted, and the bromine atoms on 1-octylimidazole and 2,2-bis(bromomethyl)-1,3-propanediol reacted to form an imidazolium cation, obtaining bis-imidazolium ion diol. Then, bis-imidazolium ion diol and perfluorobutyric acid reacted, and the hydroxyl group on bis-imidazolium ion diol reacted with the carboxyl group on perfluorobutyric acid to introduce a large number of fluorine atoms, obtaining the fluorinated bis-imidazolium ion compound. The molecular structure of the fluorinated bis-imidazolium ion compound contains an imidazolium cation and a fluorine-containing group. The imidazolium cation can undergo electrostatic interaction with negatively charged phospholipid molecules, proteins and other biological macromolecules on the surface of the cell membranes of bacteria and molds, thereby destroying the integrity of the cell membrane and finally inhibiting the growth and reproduction of bacteria and molds. At the same time, the presence of the fluorine-containing group endows the composite packaging bag with excellent anti-adhesion performance, making it difficult for bacteria and molds to adhere and grow and reproduce, further enhancing the ability of the fluorinated bis-imidazolium ion compound to inhibit the growth and reproduction of bacteria and molds. Therefore, after adding it to the composite packaging bag, the mildew-proof and bacteriostatic performance of the composite packaging bag can be significantly improved.

[0032] In the process of preparing the mildew-proof and bacteriostatic composite packaging bag, a modified nano-copper oxide was also prepared. First, nano-copper oxide was prepared using copper chloride dihydrate as a raw material by hydrothermal synthesis technology. Then, nano-copper oxide was modified with sodium dodecyl sulfate to obtain modified nano-copper oxide. Under the action of water and oxygen, the copper atoms on the surface of nano-copper oxide will gradually oxidize and release copper ions. Copper ions have strong oxidizing properties and can react with biological macromolecules such as proteins and nucleic acids in the cells of bacteria and molds, thereby affecting the normal metabolism of the cells of bacteria and molds and achieving the inhibition of the growth and reproduction of bacteria and molds. When the nano-copper oxide is modified, the dispersibility of nano-copper oxide in the composite packaging bag can be improved, enabling it to be more evenly distributed in the composite packaging bag, increasing the contact opportunity with bacteria and molds, and further enhancing its mildew-proof and bacteriostatic performance. Moreover, the modified nano-copper oxide can continuously release copper ions. After adding it to the composite packaging bag, the mildew-proof and bacteriostatic performance and durability of the composite packaging bag can be significantly improved. Specific embodiments

[0033] The following will combine the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative efforts belong to the scope of protection of the present invention.

[0034] Example 1:

[0035] This embodiment is a preparation method of a mildew-proof and bacteriostatic composite packaging bag, including the following steps:

[0036] Step S1: Add 22 mmol of 1-octylimidazole, 10 mmol of dibromoneopentyl glycol, and 30 mL of dimethyl sulfoxide into a three-necked flask equipped with a stirrer, a thermometer, and a gas guide tube. Introduce nitrogen for protection. Stir and react for 20 min under the conditions of a temperature of 20 °C and a stirring rate of 200 r / min. Then, continue to stir and react for 10 h under the condition of heating to 120 °C. After the reaction is completed, cool the reaction product to room temperature, then remove the solvent by rotary evaporation. Then add it to anhydrous tetrahydrofuran, then let it stand to precipitate, then filter by vacuum filtration. Place the filter cake in a vacuum drying oven and dry it for 2 h at a temperature of 60 °C to obtain bis-imidazolium ion diol.

[0037] Step S2: Add 10 mmol of bis-imidazolium ion diol, 22 mmol of perfluorobutyric acid, 0.09 g of p-toluenesulfonic acid, and 50 mL of toluene into a three-necked flask equipped with a stirrer, a thermometer, and a gas guide tube. Introduce nitrogen for protection. Stir and react for 20 min under the conditions of a temperature of 20 °C and a stirring rate of 200 r / min. Then, continue to stir and react for 6 h under the condition of heating to 90 °C. After the reaction is completed, cool the reaction product to room temperature, then remove the solvent by rotary evaporation. Then wash it 3 times with anhydrous tetrahydrofuran, and then place it in a vacuum drying oven and dry it for 3 h at a temperature of 70 °C to obtain a fluorine-containing bis-imidazolium ion compound.

[0038] Step S3: Add 10 mmol of copper chloride dihydrate and 40 mL of deionized water into a three-necked flask equipped with a stirrer, a thermometer, a gas guide tube, and a constant pressure dropping funnel. Introduce nitrogen for protection. Stir and react for 10 min under the conditions of a temperature of 25 °C and a stirring rate of 200 r / min. Then, dropwise add 10 mL of a 30% sodium hydroxide solution drop by drop while stirring, control the dropping rate at 1 drop / s. After the dropping is completed, continue to stir and react for 10 min. Then, continue to stir and react for 10 h under the condition of heating to 100 °C. After the reaction is completed, cool the reaction product to room temperature, then centrifuge. Wash the precipitate 3 times with distilled water and anhydrous ethanol in sequence, and then place it in a vacuum drying oven and dry it for 3 h at a temperature of 90 °C to obtain nano-copper oxide.

[0039] Step S4: Add 5 g of nano-copper oxide, 1.8 g of sodium dodecyl sulfate, and 80 mL of deionized water into a three-necked flask equipped with a stirrer and a thermometer. Stir and react at a temperature of 20 °C and a stirring rate of 200 r / min for 20 min, then raise the temperature to 40 °C and continue to stir and react for 10 h. After the reaction is completed, cool the reaction product to room temperature, then centrifuge. Wash the precipitate with distilled water and absolute ethanol three times each, and then place it in a vacuum drying oven and dry at a temperature of 60 °C for 3 h to obtain modified nano-copper oxide;

[0040] Step S5: Weigh 90 parts of polypropylene resin, 0.5 part of fluorinated bis-imidazolium ionic compound, 2 parts of modified nano-copper oxide, 3 parts of light calcium carbonate, 10 parts of plasticizer, 2 parts of lubricant, and 1 part of antioxidant by weight, and set aside; the polypropylene resin is pp-t300; the plasticizer is a mixture of dioctyl adipate and dicyclohexyl phthalate in a mass ratio of 2:3; the lubricant is vinyl bis-stearamide; the antioxidant is a mixture of antioxidant 1076 and antioxidant 1010 in a mass ratio of 3:1;

[0041] Step S6: Add the polypropylene resin, fluorinated bis-imidazolium ionic compound, modified nano-copper oxide, light calcium carbonate, plasticizer, lubricant, and antioxidant into a mixer and stir and mix them evenly to obtain a mold and mildew inhibitor mixture;

[0042] Step S7: Add the mold and mildew inhibitor mixture into a twin-screw extruder and melt-blend and extrude it at a temperature of 170 °C and a screw speed of 100 r / min, and then pelletize to obtain a mold and mildew inhibitor pellet;

[0043] Step S8: Add the mold and mildew inhibitor pellet into a blown film machine, melt it at a temperature of 165 °C, then extrude and blow the film and wind it up to obtain a mold and mildew inhibitor composite packaging bag.

[0044] Example 2:

[0045] The preparation method of a mold and mildew inhibitor composite packaging bag in this example includes the following steps:

[0046] Step S1: Add 24 mmol of 1-octylimidazole, 10 mmol of 2,2-bis(bromomethyl)-1,3-propanediol, and 35 mL of dimethyl sulfoxide into a three-necked flask equipped with a stirrer, a thermometer, and a gas guide tube. Introduce nitrogen for protection. Stir and react for 25 min under the conditions of a temperature of 22 °C and a stirring rate of 250 r / min. Then, continue to stir and react for 12 h under the condition of heating to 122 °C. After the reaction is completed, cool the reaction product to room temperature, then rotary evaporate to remove the solvent. Then, add it into anhydrous tetrahydrofuran, and then let it stand to precipitate. Then, perform vacuum filtration. Place the filter cake in a vacuum drying oven and dry it for 2.5 h under the condition of a temperature of 62 °C to obtain bis(imidazolium) diol;

[0047] Step S2: Add 10 mmol of bis(imidazolium) diol, 24 mmol of perfluorobutyric acid, 0.11 g of p-toluenesulfonic acid, and 55 mL of toluene into a three-necked flask equipped with a stirrer, a thermometer, and a gas guide tube. Introduce nitrogen for protection. Stir and react for 25 min under the conditions of a temperature of 22 °C and a stirring rate of 250 r / min. Then, continue to stir and react for 7 h under the condition of heating to 95 °C. After the reaction is completed, cool the reaction product to room temperature, then rotary evaporate to remove the solvent. Then, wash it 4 times with anhydrous tetrahydrofuran. Then, place it in a vacuum drying oven and dry it for 4 h under the condition of a temperature of 72 °C to obtain a fluorinated bis(imidazolium) ionic compound;

[0048] Step S3: Add 10 mmol of copper(II) chloride dihydrate and 45 mL of deionized water into a three-necked flask equipped with a stirrer, a thermometer, a gas guide tube, and a constant pressure dropping funnel. Introduce nitrogen for protection. Stir and react for 15 min under the conditions of a temperature of 28 °C and a stirring rate of 250 r / min. Then, while stirring, gradually add 12 mL of a 32% sodium hydroxide solution dropwise, control the dropping rate at 1 drop / s. After the dropping is completed, continue to stir and react for 15 min. Then, continue to stir and react for 12 h under the condition of heating to 105 °C. After the reaction is completed, cool the reaction product to room temperature, then centrifuge. Wash the precipitate 4 times with distilled water and anhydrous ethanol in sequence. Then, place it in a vacuum drying oven and dry it for 4 h under the condition of a temperature of 92 °C to obtain nano-copper oxide;

[0049] Step S4: Add 5 g of nano-copper oxide, 3.6 g of sodium dodecyl sulfate, and 90 mL of deionized water into a three-necked flask equipped with a stirrer and a thermometer. Stir and react for 25 min under the conditions of a temperature of 22 °C and a stirring rate of 250 r / min. Then, continue to stir and react for 12 h under the condition of heating to 42 °C. After the reaction is completed, cool the reaction product to room temperature, then centrifuge. Wash the precipitate 4 times with distilled water and anhydrous ethanol in sequence. Then, place it in a vacuum drying oven and dry it for 4 h under the condition of a temperature of 62 °C to obtain modified nano-copper oxide;

[0050] Step S5: Weigh 95 parts by weight of polypropylene resin, 2 parts of fluorinated bisimidazolium ionic compound, 4 parts of modified nano-copper oxide, 6 parts of light calcium carbonate, 11 parts of plasticizer, 4 parts of lubricant and 2 parts of antioxidant, and set aside; the polypropylene resin is pp-t300; the plasticizer is a mixture of dioctyl adipate and dicyclohexyl phthalate in a mass ratio of 2:3; the lubricant is vinyl bisstearamide; the antioxidant is a mixture of antioxidant 1076 and antioxidant 1010 in a mass ratio of 3:1;

[0051] Step S6: Add the polypropylene resin, fluorinated bisimidazolium ionic compound, modified nano-copper oxide, light calcium carbonate, plasticizer, lubricant and antioxidant into a mixer and stir and mix them evenly to obtain a mold and mildew inhibiting mixture;

[0052] Step S7: Add the mold and mildew inhibiting mixture into a twin-screw extruder, and carry out melt blending and extrusion under the conditions of a temperature of 175°C and a screw speed of 125 r / min, and then pelletize to obtain mold and mildew inhibiting pellets;

[0053] Step S8: Add the mold and mildew inhibiting pellets into a blown film machine, melt them at a temperature of 170°C, then extrude and blow the film, and wind it up to obtain a mold and mildew inhibiting composite packaging bag.

[0054] Example 3:

[0055] The present embodiment is a preparation method of a mold and mildew inhibiting composite packaging bag, including the following steps:

[0056] Step S1: Add 25 mmol of 1-octylimidazole, 10 mmol of dibromoneopentyl glycol and 40 mL of dimethyl sulfoxide into a three-necked flask equipped with a stirrer, a thermometer and a gas guide tube, introduce nitrogen protection, and stir and react for 30 min under the conditions of a temperature of 25°C and a stirring rate of 300 r / min, then raise the temperature to 125°C and continue to stir and react for 15 h. After the reaction is completed, cool the reaction product to room temperature, then rotate and evaporate to remove the solvent, then add it into anhydrous tetrahydrofuran, then let it stand to precipitate, then carry out vacuum filtration, and place the filter cake in a vacuum drying oven and dry it at a temperature of 65°C for 3 h to obtain bisimidazolium ionic diol;

[0057] Step S2: Add 10 mmol of bis(imidazolium) diol, 25 mmol of perfluorobutyric acid, 0.13 g of p-toluenesulfonic acid, and 60 mL of toluene into a three-necked flask equipped with a stirrer, a thermometer, and a gas pipe. Introduce nitrogen for protection. Stir and react for 30 min under the conditions of a temperature of 25 °C and a stirring rate of 300 r / min. Then, raise the temperature to 100 °C and continue to stir and react for 8 h. After the reaction is completed, cool the reaction product to room temperature, then remove the solvent by rotary evaporation. Then, wash it 5 times with anhydrous tetrahydrofuran. Then, place it in a vacuum drying oven and dry it for 5 h at a temperature of 75 °C to obtain a fluorinated bis(imidazolium) ionic compound;

[0058] Step S3: Add 10 mmol of copper(II) chloride dihydrate and 50 mL of deionized water into a three-necked flask equipped with a stirrer, a thermometer, a gas pipe, and a constant-pressure dropping funnel. Introduce nitrogen for protection. Stir and react for 20 min under the conditions of a temperature of 30 °C and a stirring rate of 300 r / min. Then, gradually add 15 mL of a 35% sodium hydroxide solution drop by drop while stirring, controlling the dropping rate at 2 drops / s. After the dropping is completed, continue to stir and react for 20 min. Then, raise the temperature to 110 °C and continue to stir and react for 15 h. After the reaction is completed, cool the reaction product to room temperature, then centrifuge. Wash the precipitate 5 times with distilled water and anhydrous ethanol in sequence. Then, place it in a vacuum drying oven and dry it for 5 h at a temperature of 95 °C to obtain nano-copper oxide;

[0059] Step S4: Add 5 g of nano-copper oxide, 5.4 g of sodium dodecyl sulfate, and 100 mL of deionized water into a three-necked flask equipped with a stirrer and a thermometer. Stir and react for 30 min under the conditions of a temperature of 25 °C and a stirring rate of 300 r / min. Then, raise the temperature to 45 °C and continue to stir and react for 15 h. After the reaction is completed, cool the reaction product to room temperature, then centrifuge. Wash the precipitate 5 times with distilled water and anhydrous ethanol in sequence. Then, place it in a vacuum drying oven and dry it for 5 h at a temperature of 65 °C to obtain modified nano-copper oxide;

[0060] Step S5: Weigh 100 parts of polypropylene resin, 3.5 parts of fluorinated bis(imidazolium) ionic compound, 6 parts of modified nano-copper oxide, 9 parts of light calcium carbonate, 12 parts of plasticizer, 6 parts of lubricant, and 3 parts of antioxidant by weight for standby; the polypropylene resin is pp-t300; the plasticizer is a mixture of dioctyl adipate and dicyclohexyl phthalate in a mass ratio of 2:3; the lubricant is vinyl bisstearamide; the antioxidant is a mixture of antioxidant 1076 and antioxidant 1010 in a mass ratio of 3:1;

[0061] Step S6: Add polypropylene resin, fluorinated bisimidazolium ionic compound, modified nano-copper oxide, light calcium carbonate, plasticizer, lubricant and antioxidant into a mixer and stir to mix evenly to obtain a mold and mildew inhibiting mixture;

[0062] Step S7: Add the mold and mildew inhibiting mixture into a twin-screw extruder and melt-blend and extrude it under the conditions of a temperature of 180 °C and a screw rotation speed of 150 r / min, and then pelletize to obtain mold and mildew inhibiting pellets;

[0063] Step S8: Add the mold and mildew inhibiting pellets into a blown film machine, melt them at a temperature of 175 °C, then extrude and blow the film and wind it up to obtain a mold and mildew inhibiting composite packaging bag.

[0064] Comparative Example 1:

[0065] This comparative example is a preparation method of a mold and mildew inhibiting composite packaging bag, including the following steps:

[0066] Step S1: Weigh 100 parts of polypropylene resin, 9 parts of light calcium carbonate, 12 parts of plasticizer, 6 parts of lubricant and 3 parts of antioxidant by weight for standby; the polypropylene resin is pp-t300; the plasticizer is a mixture of dioctyl adipate and dicyclohexyl phthalate in a mass ratio of 2:3; the lubricant is vinyl bisstearamide; the antioxidant is a mixture of antioxidant 1076 and antioxidant 1010 in a mass ratio of 3:1;

[0067] Step S2: Add polypropylene resin, light calcium carbonate, plasticizer, lubricant and antioxidant into a mixer and stir to mix evenly to obtain a mold and mildew inhibiting mixture;

[0068] Step S3: Add the mold and mildew inhibiting mixture into a twin-screw extruder and melt-blend and extrude it under the conditions of a temperature of 180 °C and a screw rotation speed of 150 r / min, and then pelletize to obtain mold and mildew inhibiting pellets;

[0069] Step S4: Add the mold and mildew inhibiting pellets into a blown film machine, melt them at a temperature of 175 °C, then extrude and blow the film and wind it up to obtain a mold and mildew inhibiting composite packaging bag.

[0070] Comparative Example 2:

[0071] This comparative example is a preparation method of a mold and mildew inhibiting composite packaging bag, including the following steps:

[0072] Step S1: Add 10 mmol of copper chloride dihydrate and 50 mL of deionized water into a three-necked flask equipped with a stirrer, a thermometer, a gas pipe, and a constant-pressure dropping funnel. Introduce nitrogen for protection. Stir and react for 20 min at a temperature of 30 °C and a stirring rate of 300 r / min. Then, while stirring, gradually add 15 mL of a 35% sodium hydroxide solution drop by drop, controlling the dropping rate at 2 drops / s. After the addition is complete, continue to stir and react for 20 min. Then, raise the temperature to 110 °C and continue to stir and react for 15 h. After the reaction is completed, cool the reaction product to room temperature, then centrifuge. Wash the precipitate with distilled water and absolute ethanol 5 times in sequence. Then, place it in a vacuum drying oven and dry it at a temperature of 95 °C for 5 h to obtain nano-copper oxide;

[0073] Step S2: Add 5 g of nano-copper oxide, 5.4 g of sodium dodecyl sulfate, and 100 mL of deionized water into a three-necked flask equipped with a stirrer and a thermometer. Stir and react for 30 min at a temperature of 25 °C and a stirring rate of 300 r / min. Then, raise the temperature to 45 °C and continue to stir and react for 15 h. After the reaction is completed, cool the reaction product to room temperature, then centrifuge. Wash the precipitate with distilled water and absolute ethanol 5 times in sequence. Then, place it in a vacuum drying oven and dry it at a temperature of 65 °C for 5 h to obtain modified nano-copper oxide;

[0074] Step S3: Weigh 100 parts of polypropylene resin, 6 parts of modified nano-copper oxide, 9 parts of light calcium carbonate, 12 parts of plasticizer, 6 parts of lubricant, and 3 parts of antioxidant by weight for standby; the polypropylene resin is pp-t300; the plasticizer is a mixture of dioctyl adipate and dicyclohexyl phthalate in a mass ratio of 2:3; the lubricant is vinyl bisstearamide; the antioxidant is a mixture of antioxidant 1076 and antioxidant 1010 in a mass ratio of 3:1;

[0075] Step S4: Add the polypropylene resin, modified nano-copper oxide, light calcium carbonate, plasticizer, lubricant, and antioxidant into a mixer and stir and mix them evenly to obtain a mildew-proof and bacteriostatic mixture;

[0076] Step S5: Add the mildew-proof and bacteriostatic mixture into a twin-screw extruder and melt-blend and extrude it at a temperature of 180 °C and a screw speed of 150 r / min. Then, pelletize to obtain mildew-proof and bacteriostatic pellets;

[0077] Step S6: Add the mildew-proof and bacteriostatic pellets into a blown film machine, melt them at a temperature of 175 °C, then extrude and blow the film and wind it up to obtain a mildew-proof and bacteriostatic composite packaging bag.

[0078] Comparative Example 3:

[0079] This comparative example is a preparation method of a mildew-proof and bacteriostatic composite packaging bag, including the following steps:

[0080] Step S1: Add 25 mmol of 1-octylimidazole, 10 mmol of dibromoneopentyl glycol, and 40 mL of dimethyl sulfoxide into a three-necked flask equipped with a stirrer, a thermometer, and a gas guide tube. Introduce nitrogen for protection. Stir and react for 30 min under the conditions of a temperature of 25 °C and a stirring rate of 300 r / min. Then, continue to stir and react for 15 h under the condition of raising the temperature to 125 °C. After the reaction is completed, cool the reaction product to room temperature, then rotate and evaporate to remove the solvent. Then, add it to anhydrous tetrahydrofuran, then let it stand to precipitate, and then perform vacuum filtration. Place the filter cake in a vacuum drying oven and dry it for 3 h under the condition of a temperature of 65 °C to obtain bis-imidazolium ion diol;

[0081] Step S2: Add 10 mmol of bis-imidazolium ion diol, 25 mmol of perfluorobutyric acid, 0.13 g of p-toluenesulfonic acid, and 60 mL of toluene into a three-necked flask equipped with a stirrer, a thermometer, and a gas guide tube. Introduce nitrogen for protection. Stir and react for 30 min under the conditions of a temperature of 25 °C and a stirring rate of 300 r / min. Then, continue to stir and react for 8 h under the condition of raising the temperature to 100 °C. After the reaction is completed, cool the reaction product to room temperature, then rotate and evaporate to remove the solvent. Then, wash it 5 times with anhydrous tetrahydrofuran, and then place it in a vacuum drying oven and dry it for 5 h under the condition of a temperature of 75 °C to obtain a fluorine-containing bis-imidazolium ion compound;

[0082] Step S3: Weigh 100 parts of polypropylene resin, 3.5 parts of fluorine-containing bis-imidazolium ion compound, 9 parts of light calcium carbonate, 12 parts of plasticizer, 6 parts of lubricant, and 3 parts of antioxidant by weight, and set aside; the polypropylene resin is pp-t300; the plasticizer is a mixture of dioctyl adipate and dicyclohexyl phthalate in a mass ratio of 2:3; the lubricant is vinyl bis-stearamide; the antioxidant is a mixture of antioxidant 1076 and antioxidant 1010 in a mass ratio of 3:1;

[0083] Step S4: Add the polypropylene resin, fluorine-containing bis-imidazolium ion compound, light calcium carbonate, plasticizer, lubricant, and antioxidant into a mixer and stir and mix them evenly to obtain a mildew-proof and bacteriostatic mixing material;

[0084] Step S5: Add the mildew-proof and bacteriostatic mixing material into a twin-screw extruder and melt-blend and extrude it under the conditions of a temperature of 180 °C and a screw speed of 150 r / min, and then pelletize it to obtain mildew-proof and bacteriostatic pellets;

[0085] Step S6: Add the mildew and bacteria inhibiting pellets into a blown film machine, melt them at a temperature of 175 °C, then extrude, blow film and wind up to obtain a mildew and bacteria inhibiting composite packaging bag.

[0086] Comparative Example 4:

[0087] The preparation method of a mildew and bacteria inhibiting composite packaging bag in this comparative example includes the following steps:

[0088] Step S1: Add 25 mmol of 1-octylimidazole, 10 mmol of dibromoneopentyl glycol and 40 mL of dimethyl sulfoxide into a three-necked flask equipped with a stirrer, a thermometer and a gas guide tube, introduce nitrogen protection, stir and react for 30 min under the conditions of a temperature of 25 °C and a stirring rate of 300 r / min, then raise the temperature to 125 °C and continue to stir and react for 15 h. After the reaction is completed, cool the reaction product to room temperature, then rotate and evaporate to remove the solvent, then add it into anhydrous tetrahydrofuran, then let it stand to precipitate, then carry out vacuum filtration, place the filter cake in a vacuum drying oven, and dry it at a temperature of 65 °C for 3 h to obtain bis-imidazolium ion diol;

[0089] Step S2: Add 10 mmol of copper chloride dihydrate and 50 mL of deionized water into a three-necked flask equipped with a stirrer, a thermometer, a gas guide tube and a constant pressure dropping funnel, introduce nitrogen protection, stir and react for 20 min under the conditions of a temperature of 30 °C and a stirring rate of 300 r / min, then gradually dropwise add 15 mL of a sodium hydroxide solution with a mass fraction of 35% while stirring, control the dropping rate at 2 drops / s, continue to stir and react for 20 min after the dropping is completed, then raise the temperature to 110 °C and continue to stir and react for 15 h. After the reaction is completed, cool the reaction product to room temperature, then centrifuge, wash the precipitate with distilled water and absolute ethanol 5 times in sequence, then place it in a vacuum drying oven, and dry it at a temperature of 95 °C for 5 h to obtain nano-copper oxide;

[0090] Step S3: Weigh 100 parts of polypropylene resin, 3.5 parts of bis-imidazolium ion diol, 6 parts of nano-copper oxide, 9 parts of light calcium carbonate, 12 parts of plasticizer, 6 parts of lubricant and 3 parts of antioxidant according to parts by weight for standby; the polypropylene resin is pp-t300; the plasticizer is a mixture of dioctyl adipate and dicyclohexyl phthalate in a mass ratio of 2:3; the lubricant is vinyl bis-stearamide; the antioxidant is a mixture of antioxidant 1076 and antioxidant 1010 in a mass ratio of 3:1;

[0091] Step S4: Add the polypropylene resin, bis-imidazolium ion diol, nano-copper oxide, light calcium carbonate, plasticizer, lubricant and antioxidant into a mixer, stir and mix them evenly to obtain a mildew and bacteria inhibiting mixture;

[0092] Step S5: Add the mold and mildew inhibitor mixture into a twin-screw extruder, and melt and blend and extrude it under the conditions of a temperature of 180°C and a screw speed of 150 r / min, and then granulate to obtain mold and mildew inhibitor pellets;

[0093] Step S6: Add the mold and mildew inhibitor pellets into a blown film machine, melt them under the condition of a temperature of 175°C, then extrude and blow the film, and wind it up to obtain a mold and mildew inhibitor composite packaging bag.

[0094] Perform performance tests on the mold and mildew inhibitor composite packaging bags of Examples 1-3 and Comparative Examples 1-4 in accordance with QBT 2591-2003 "Antibacterial Plastics - Test Methods for Antibacterial Properties and Antibacterial Effects". The test results are shown in the following table:

[0095]

[0096] Referring to the data in the above table, based on the comparison between Examples 1-3 and Comparative Examples 1-4, it can be known that the mold and mildew inhibitor composite packaging bag of the present application has excellent mold and mildew inhibition performance.

[0097] In the description of this specification, the description referring to terms such as "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in a suitable manner in any one or more embodiments or examples.

[0098] The above content is only an example and illustration of the present invention. Those skilled in the art of this technology can make various modifications or supplements to the described specific embodiments or use similar methods to replace them. As long as they do not deviate from the invention or exceed the scope defined by this application, they should all belong to the protection scope of the present invention.

Claims

1. A mildew-proof and antibacterial composite packaging bag, characterized in that: It comprises the following components in parts by weight: 90-100 parts of polypropylene resin, 0.5-3.5 parts of fluorine-containing bisimidazolium ion compound, 2-6 parts of modified nano copper oxide, 3-9 parts of light calcium carbonate, 10-12 parts of plasticizer, 2-6 parts of lubricant and 1-3 parts of antioxidant; Wherein, the fluorine-containing bisimidazolium ion compound is prepared by the following steps: Step a1: 1-octylimidazole, dibromoneopentyl glycol and dimethyl sulfoxide are stirred for reaction. After the reaction is completed, the reaction product is cooled, then rotary evaporated, then added to anhydrous tetrahydrofuran and allowed to stand for precipitation, then vacuum filtered, and the filter cake is dried to obtain a bisimidazolium ion diol; Step a2: stirring the diimidazolium ion diol, perfluorobutyric acid, p-toluenesulfonic acid and toluene to react, cooling the reaction product after the reaction is completed, then rotary evaporating, washing and drying to obtain a fluorine-containing diimidazolium ion compound.

2. The mildew-proof and antibacterial composite packaging bag according to claim 1, characterized in that: The usage ratio of the 1-octylimidazole, dibromoneopentyl glycol and dimethyl sulfoxide in step a1 is 22-25 mmol:10 mmol:30-40 mL.

3. The mildew-proof and antibacterial composite packaging bag according to claim 1, characterized in that: The bisimidazolium ion diol, perfluorobutyric acid, p-toluenesulfonic acid and toluene in step a2 are used in a ratio of 10 mmol: 22-25 mmol: 0.09-0.13 g: 50-60 mL.

4. The mildew-proof and antibacterial composite packaging bag according to claim 1, characterized in that: The modified nano copper oxide is prepared by the following steps: Step b1: stirring cupric chloride dihydrate and deionized water for reaction, then adding sodium hydroxide solution dropwise while stirring, and continuing to stir the reaction after the addition is complete. After the reaction is complete, the reaction product is cooled, then centrifuged, and the precipitate is washed and dried to obtain nano copper oxide; Step b2: stirring the nano copper oxide, sodium dodecyl sulfate and deionized water for reaction, cooling the reaction product after the reaction is completed, and then centrifuging it, washing and drying the precipitate to obtain modified nano copper oxide.

5. The mildew-proof and antibacterial composite packaging bag according to claim 4, characterized in that: The usage ratio of the cupric chloride dihydrate, deionized water and sodium hydroxide solution in step b1 is 10 mmol:40-50 mL:10-15 mL.

6. The mildew-proof and antibacterial composite packaging bag according to claim 4, characterized in that: The mass fraction of the sodium hydroxide solution in step b1 is 30-35%.

7. The mildew-proof and antibacterial composite packaging bag according to claim 4, characterized in that: The usage ratio of the nano copper oxide, sodium dodecyl sulfate and deionized water in step b2 is 5g:1.8-5.4g:80-100mL.

8. A method for preparing a mildew-proof and antibacterial composite packaging bag, characterized in that: The following steps are involved: Step 1: weigh 90-100 parts of polypropylene resin, 0.5-3.5 parts of fluorine-containing bisimidazolium ion compound, 2-6 parts of modified nano copper oxide, 3-9 parts of light calcium carbonate, 10-12 parts of plasticizer, 2-6 parts of lubricant and 1-3 parts of antioxidant according to weight parts, and set aside; Step 2: Add polypropylene resin, fluorine-containing bisimidazolium ion compound, modified nano copper oxide, light calcium carbonate, plasticizer, lubricant and antioxidant into a mixer, stir and mix, mix evenly, and obtain a mildew-proof and antibacterial mixture; Step 3: adding the mildew-proof and antibacterial mixture into a twin-screw extruder, melt-blending and extruding at a temperature of 170-180° C. and a screw speed of 100-150 r / min, and then granulating to obtain mildew-proof and antibacterial granules; Step 4: Add the mildew-proof and antibacterial granules into the film blowing machine, melt them at a temperature of 165-175°C, extrude them into a film, and roll them up to obtain a mildew-proof and antibacterial composite packaging bag.

9. The method for preparing a mildew-proof and antibacterial composite packaging bag according to claim 8, characterized in that: The polypropylene resin is pp-t300; The plasticizer is a mixture of dioctyl adipate and dicyclohexyl phthalate in a mass ratio of 2:3; The lubricant is vinyl bisstearamide; The antioxidant is a mixture of antioxidant 1076 and antioxidant 1010 in a mass ratio of 3:1.

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