Mildew-proof and bacteriostatic composite packaging bag and preparation method thereof

Abstract

The present application relates to the field of packaging bags, in particular to a mildew-proof and antibacterial composite packaging bag and a preparation method thereof, which is used to solve the problem that the existing packaging bags lack effective inhibitory capacity for the breeding and propagation of bacteria and mold; the composite packaging bag takes 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, and provides reliable physical protection for the products to prevent the products from being physically damaged and leaking by the outside world; by adding fluorine-containing bis-imidazolium ion compound and modified nano copper oxide to the composite packaging bag, the growth of various common bacteria and mold can be effectively inhibited and killed under the synergistic action of the two, the goods in the package can be prevented from being damaged by microorganisms, the quality and use value of the goods are ensured, and the shelf life of the goods is prolonged; moreover, the preparation method is simple to operate, easy to industrialize, low in cost, and has good market application prospect.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of packaging bags, in particular to a mildew and bacteria inhibiting type composite packaging bag and a preparation method thereof. BACKGROUND

[0002] In the storage and flow process of various products, packaging bags are one of the key factors to protect product quality. However, traditional packaging bags often only have basic physical protection functions, such as preventing products from being impacted, squeezed, and invaded by external dust and moisture, but lack effective inhibition ability for the growth and reproduction of bacteria and mold.

[0003] Food, medicine, cosmetics and other products are rich in nutrients, and under suitable temperature and humidity conditions, they are easy to become a breeding ground for bacteria and mold. The growth of bacteria and mold not only causes the appearance of the product to deteriorate, such as the appearance of mold spots, discoloration, and odor, but also reduces the quality and performance of the product, and even produces toxic and harmful substances, which poses a serious threat to human health.

[0004] Therefore, it is of great practical significance and market demand to develop a mildew and bacteria inhibiting type composite packaging bag and a preparation method thereof. SUMMARY

[0005] In order to overcome the above technical problems, the purpose of the present application is to provide a mildew and bacteria inhibiting type composite packaging bag and a preparation method thereof, which solves the problem that the existing packaging bags lack effective inhibition ability for the growth and reproduction of bacteria and mold, which not only causes the appearance of the packaged product to deteriorate, but also reduces the quality and performance of the packaged product, and even produces toxic and harmful substances, which poses a serious threat to human health.

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

[0007] A mildew and bacteria inhibiting type composite packaging bag comprises the following components by weight:

[0008] polypropylene resin 90-100 parts, fluorine-containing bis-imidazolium ion compound 0.5-3.5 parts, modified nano copper oxide 2-6 parts, light calcium carbonate 3-9 parts, plasticizer 10-12 parts, lubricant 2-6 parts, and antioxidant 1-3 parts;

[0009] The fluorine-containing bis-imidazolium ion compound is prepared by the following steps:

[0010] Step a1: 1-octyl imidazole, dibromoneopentyl glycol and dimethyl sulfoxide are added to a three-necked flask equipped with a stirrer, a thermometer and a gas inlet tube, and protected by nitrogen, stirred at a temperature of 20-25℃ and a stirring rate of 200-300r / min for 20-30min, then heated to 120-125℃ and stirred for 10-15h, after the reaction is completed, the reaction product is cooled to room temperature, then solvent is removed by rotary evaporation, then added to anhydrous tetrahydrofuran, then precipitate is separated by standing, then vacuum filtered, and the filter cake is placed in a vacuum drying oven and dried at a temperature of 60-65℃ for 2-3h to obtain a bisimidazolium ion diol;

[0011] Step a2: the bisimidazolium ion diol, perfluorobutyric acid, p-toluenesulfonic acid and toluene are added to a three-necked flask equipped with a stirrer, a thermometer and a gas inlet tube, and protected by nitrogen, stirred at a temperature of 20-25℃ and a stirring rate of 200-300r / min for 20-30min, then heated to 90-100℃ and stirred for 6-8h, after the reaction is completed, the reaction product is cooled to room temperature, then solvent is removed by rotary evaporation, then washed with anhydrous tetrahydrofuran for 3-5 times, then placed in a vacuum drying oven and dried at a temperature of 70-75℃ for 3-5h to obtain a fluorine-containing bisimidazolium ion compound.

[0012] As a further scheme of the application: the amount ratio of the 1-octyl imidazole, dibromoneopentyl glycol and dimethyl sulfoxide in step a1 is 22-25mmol:10mmol:30-40mL.

[0013] As a further scheme of the application: the amount ratio of the bisimidazolium ion diol, perfluorobutyric acid, p-toluenesulfonic acid and toluene in step a2 is 10mmol:22-25mmol:0.09-0.13g:50-60mL.

[0014] As a further scheme of the application: the modified nano copper oxide is prepared by the following steps:

[0015] Step b1: copper chloride dihydrate, deionized water were added into a three-necked flask equipped with a stirrer, a thermometer, a gas inlet tube and a constant pressure dropping funnel, and nitrogen was introduced for protection, and then the mixture was stirred at a temperature of 25-30 DEG C and a stirring speed of 200-300 r / min for 10-20 min, and then sodium hydroxide solution was added dropwise while stirring, and the dropping speed was controlled at 1-2 drops / s, and after the addition was completed, the mixture was continuously stirred for 10-20 min, and then the temperature was raised to 100-110 DEG C, and the mixture was continuously stirred for 10-15 h, and after the reaction was completed, the reaction product was cooled to room temperature, and then centrifuged, and the precipitate was washed with distilled water and anhydrous ethanol for 3-5 times, and then placed in a vacuum drying oven, and dried at a temperature of 90-95 DEG C for 3-5 h to obtain nano copper oxide;

[0016] Step b2: the nano copper oxide, sodium dodecyl sulfate and deionized water were added into a three-necked flask equipped with a stirrer and a thermometer, and stirred at a temperature of 20-25 DEG C and a stirring speed of 200-300 r / min for 20-30 min, and then the temperature was raised to 40-45 DEG C, and the mixture was continuously stirred for 10-15 h, and after the reaction was completed, the reaction product was cooled to room temperature, and then centrifuged, and the precipitate was washed with distilled water and anhydrous ethanol for 3-5 times, and then placed in a vacuum drying oven, and dried at a temperature of 60-65 DEG C for 3-5 h to obtain modified nano copper oxide.

[0017] As a further scheme of the application: the amount 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 application: the mass fraction of the sodium hydroxide solution in step b1 is 30-35%.

[0019] As a further scheme of the application: the amount 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 application: a preparation method of a mildew-resistant and antibacterial composite packaging bag, comprising the following steps:

[0021] Step one: polypropylene resin 90-100 parts, fluorine-containing bis-imidazole onium ion compound 0.5-3.5 parts, modified nano copper oxide 2-6 parts, light calcium carbonate 3-9 parts, plasticizer 10-12 parts, lubricant 2-6 parts and antioxidant 1-3 parts were weighed according to weight parts, and prepared for use;

[0022] Step two: the polypropylene resin, fluorine-containing bis-imidazolium ionic compound, modified nano copper oxide, light calcium carbonate, plasticizer, lubricant and antioxidant are added into a mixer and stirred and mixed until uniform to obtain a mildew-resistant and antibacterial mixture;

[0023] Step three: the mildew-resistant and antibacterial mixture is added into a twin-screw extruder and melt blended and extruded under the conditions of a temperature of 170-180 DEG C and a screw rotation speed of 100-150 r / min, and then pelletized to obtain mildew-resistant and antibacterial granules;

[0024] Step four: the mildew-resistant and antibacterial granules are added into a film blowing machine and extruded and blown into a film after melting under the condition of a temperature of 165-175 DEG C, and then wound to obtain a mildew-resistant and antibacterial composite packaging bag.

[0025] As a further scheme of the application, the polypropylene resin is pp-t300.

[0026] As a further scheme of the application, 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 application, the lubricant is vinyl bis-stearamide.

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

[0029] The application has the following beneficial effects:

[0030] The application discloses a mildew-resistant and antibacterial composite packaging bag and a preparation method thereof.

[0031] In the process of preparing the mildew-proof and antibacterial composite packaging bag, a fluorine-containing bis-imidazolium ion compound is first prepared. The fluorine-containing bis-imidazolium ion compound is prepared by the reaction of 1-octyl imidazole and dibromoneopentyl glycol, the reaction of 1-octyl imidazole and bromine atoms on the dibromoneopentyl glycol to form imidazolium cation, the reaction of bis-imidazolium ion diol and perfluorobutyric acid, and the introduction of a large number of fluorine atoms. The molecular structure of the fluorine-containing bis-imidazolium ion compound contains imidazolium cation and fluorine-containing groups. The imidazolium cation can interact with the negatively charged phospholipid molecules, proteins and other biological macromolecules on the surface of the bacterial and mold cell membrane, thereby destroying the integrity of the cell membrane and ultimately inhibiting the growth and reproduction of bacteria and mold. At the same time, the presence of the fluorine-containing group endows the composite packaging bag with excellent anti-adhesion performance, so that bacteria and mold are not easy to adhere and grow and reproduce, further enhancing the ability of the fluorine-containing bis-imidazolium ion compound to inhibit the growth and reproduction of bacteria and mold. Therefore, after the fluorine-containing bis-imidazolium ion compound is added to the composite packaging bag, the mildew-proof and antibacterial performance of the composite packaging bag can be significantly improved.

[0032] In the process of preparing the mildew-proof and antibacterial composite packaging bag, a modified nano copper oxide is also prepared. The modified nano copper oxide is prepared by using copper chloride dihydrate as raw material and hydrothermal synthesis technology to prepare nano copper oxide, and then modifying the nano copper oxide with sodium dodecyl sulfate. Under the action of water and oxygen, the copper atoms on the surface of the nano copper oxide are gradually oxidized and release copper ions. The copper ions have strong oxidizing properties and can react with biological macromolecules such as proteins and nucleic acids in the cells of bacteria and mold, thereby affecting the normal metabolism of the bacterial and mold cells and achieving the inhibition of the growth and reproduction of bacteria and mold. After the modification of the nano copper oxide, the dispersibility of the nano copper oxide in the composite packaging bag is improved, so that it can be more uniformly distributed in the composite packaging bag, increasing the contact opportunity with bacteria and mold, thereby further improving the mildew-proof and antibacterial performance. In addition, the modified nano copper oxide can continuously release copper ions, so that after it is added to the composite packaging bag, the mildew-proof and antibacterial performance and durability of the composite packaging bag can be significantly improved. DETAILED DESCRIPTION

[0033] The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, not all. Based on the embodiments in the present application, all other embodiments obtained by those of ordinary skill in the art without creative labor fall within the scope of the present application.

[0034] Example 1:

[0035] The embodiment is a preparation method of a mildew-proof and antibacterial composite packaging bag, comprising the following steps:

[0036] Step S1: 22 mmol of 1-octyl imidazole, 10 mmol of dibromoneopentyl glycol and 30 mL of dimethyl sulfoxide were added into a three-neck flask provided with a stirrer, a thermometer and a gas inlet pipe, nitrogen protection was performed, stirring was performed at a temperature of 20 DEG C and a stirring speed of 200 r / min for 20 min, then the temperature was increased to 120 DEG C, and stirring was continuously performed for 10 h, after the reaction was completed, the reaction product was cooled to room temperature, then the solvent was removed by rotary evaporation, then it was added into anhydrous tetrahydrofuran, then precipitation was separated by standing, then vacuum filtration was performed, the filter cake was placed in a vacuum drying box, and drying was performed at a temperature of 60 DEG C for 2 h, thereby obtaining a bisimidazolium ion glycol;

[0037] Step S2: 10 mmol of bisimidazolium ion glycol, 22 mmol of perfluorobutyric acid, 0.09 g of p-toluenesulfonic acid and 50 mL of toluene were added into a three-neck flask provided with a stirrer, a thermometer and a gas inlet pipe, nitrogen protection was performed, stirring was performed at a temperature of 20 DEG C and a stirring speed of 200 r / min for 20 min, then the temperature was increased to 90 DEG C, and stirring was continuously performed for 6 h, after the reaction was completed, the reaction product was cooled to room temperature, then the solvent was removed by rotary evaporation, then washing was performed with anhydrous tetrahydrofuran for 3 times, then it was placed in a vacuum drying box, and drying was performed at a temperature of 70 DEG C for 3 h, thereby obtaining a fluorine-containing bisimidazolium ion compound;

[0038] Step S3: 10 mmol of copper chloride dihydrate and 40 mL of deionized water were added into a three-neck flask provided with a stirrer, a thermometer, a gas inlet pipe and a constant-pressure dropping funnel, nitrogen protection was performed, stirring was performed at a temperature of 25 DEG C and a stirring speed of 200 r / min for 10 min, then 10 mL of a 30% sodium hydroxide solution was added drop by drop in a stirring manner, the dropping speed was controlled to be 1 drop / s, after the addition was completed, stirring was continuously performed for 10 min, then the temperature was increased to 100 DEG C, and stirring was continuously performed for 10 h, after the reaction was completed, the reaction product was cooled to room temperature, then centrifugal separation was performed, the precipitate was washed with distilled water and anhydrous ethanol for 3 times, then it was placed in a vacuum drying box, and drying was performed at a temperature of 90 DEG C for 3 h, thereby obtaining nano copper oxide;

[0039] Step S4: 5 g of nano copper oxide, 1.8 g of sodium dodecyl sulfate and 80 mL of deionized water were added to a three-necked flask equipped with a stirrer and a thermometer, and stirred at a temperature of 20℃ and a stirring rate of 200 r / min for 20 min, then the temperature was raised to 40℃ and the stirring was continued for 10 h. After the reaction was completed, the reaction product was cooled to room temperature, then centrifuged, and the precipitate was washed with distilled water and anhydrous ethanol three times, then placed in a vacuum drying oven and dried at a temperature of 60℃ for 3 h to obtain modified nano copper oxide;

[0040] Step S5: polypropylene resin 90 parts, fluorine-containing bis-imidazolium ionic compound 0.5 parts, modified nano copper oxide 2 parts, light calcium carbonate 3 parts, plasticizer 10 parts, lubricant 2 parts and antioxidant 1 part were weighed according to weight parts, and were ready for use; the polypropylene resin was pp-t300; the plasticizer was a mixture of dioctyl adipate and dicyclohexyl phthalate in a mass ratio of 2:3; the lubricant was vinyl bis-stearamide; the antioxidant was a mixture of antioxidant 1076 and antioxidant 1010 in a mass ratio of 3:1;

[0041] Step S6: polypropylene resin, fluorine-containing bis-imidazolium ionic compound, modified nano copper oxide, light calcium carbonate, plasticizer, lubricant and antioxidant were added to a mixer and stirred and mixed until uniform to obtain a mildew-resistant and antibacterial mixture;

[0042] Step S7: the mildew-resistant and antibacterial mixture was added to a twin-screw extruder and melt blended and extruded at a temperature of 170℃ and a screw speed of 100 r / min, then pelletized to obtain mildew-resistant and antibacterial granules;

[0043] Step S8: the mildew-resistant and antibacterial granules were added to a film blowing machine and extruded and blown into a film after melting at a temperature of 165℃, then wound to obtain a mildew-resistant and antibacterial composite packaging bag.

[0044] Example 2:

[0045] The present embodiment is a preparation method of a mildew-resistant and antibacterial composite packaging bag, comprising the following steps:

[0046] Step S1: 24 mmol of 1-octyl imidazole, 10 mmol of dibromoneopentyl glycol, and 35 mL of dimethyl sulfoxide were added to a three-neck flask equipped with a stirrer, a thermometer, and a gas inlet tube, and protected by nitrogen, stirred at a temperature of 22°C and a stirring rate of 250 r / min for 25 min, then heated to 122°C and continued to stir for 12 h, after the reaction was completed, the reaction product was cooled to room temperature, then rotary evaporation was used to remove the solvent, then added to anhydrous tetrahydrofuran, then precipitated, then vacuum filtration, the filter cake was placed in a vacuum drying oven, dried at a temperature of 62°C for 2.5 h, to obtain a bisimidazolium ion glycol;

[0047] Step S2: 10 mmol of bisimidazolium ion glycol, 24 mmol of perfluorobutyric acid, 0.11 g of p-toluenesulfonic acid, and 55 mL of toluene were added to a three-neck flask equipped with a stirrer, a thermometer, and a gas inlet tube, and protected by nitrogen, stirred at a temperature of 22°C and a stirring rate of 250 r / min for 25 min, then heated to 95°C and continued to stir for 7 h, after the reaction was completed, the reaction product was cooled to room temperature, then rotary evaporation was used to remove the solvent, then washed with anhydrous tetrahydrofuran 4 times, then placed in a vacuum drying oven, dried at a temperature of 72°C for 4 h, to obtain a fluorine-containing bisimidazolium ion compound;

[0048] Step S3: 10 mmol of copper chloride dihydrate, 45 mL of deionized water were added to a three-neck flask equipped with a stirrer, a thermometer, a gas inlet tube, and a constant pressure dropping funnel, and protected by nitrogen, stirred at a temperature of 28°C and a stirring rate of 250 r / min for 15 min, then 12 mL of 32% sodium hydroxide solution was added dropwise while stirring, the dropping rate was controlled at 1 drop / s, after the addition was completed, the reaction was continued to stir for 15 min, then heated to 105°C and continued to stir for 12 h, after the reaction was completed, the reaction product was cooled to room temperature, then centrifuged, the precipitate was washed with distilled water and anhydrous ethanol 4 times in turn, then placed in a vacuum drying oven, dried at a temperature of 92°C for 4 h, to obtain nano copper oxide;

[0049] Step S4: 5 g of nano copper oxide, 3.6 g of sodium dodecyl sulfate, and 90 mL of deionized water were added to a three-neck flask equipped with a stirrer and a thermometer, and stirred at a temperature of 22°C and a stirring rate of 250 r / min for 25 min, then heated to 42°C and continued to stir for 12 h, after the reaction was completed, the reaction product was cooled to room temperature, then centrifuged, the precipitate was washed with distilled water and anhydrous ethanol 4 times in turn, then placed in a vacuum drying oven, dried at a temperature of 62°C for 4 h, to obtain modified nano copper oxide;

[0050] Step S5: 95 parts by weight of polypropylene resin, 2 parts by weight of fluorine-containing bis-imidazolium ionic compound, 4 parts by weight of modified nano copper oxide, 6 parts by weight of light calcium carbonate, 11 parts by weight of plasticizer, 4 parts by weight of lubricant and 2 parts by weight of antioxidant were weighed and prepared; the polypropylene resin was pp-t300; the plasticizer was a mixture of dioctyl adipate and dicyclohexyl phthalate in a mass ratio of 2:3; the lubricant was vinyl bis-stearamide; the antioxidant was a mixture of antioxidant 1076 and antioxidant 1010 in a mass ratio of 3:1;

[0051] Step S6: The polypropylene resin, fluorine-containing bis-imidazolium ionic compound, modified nano copper oxide, light calcium carbonate, plasticizer, lubricant and antioxidant were added to the mixer and stirred and mixed until uniform to obtain a mildew-resistant and antibacterial mixture;

[0052] Step S7: The mildew-resistant and antibacterial mixture was added to the twin-screw extruder and melt blended and extruded under the conditions of a temperature of 175°C and a screw rotation speed of 125r / min, and then pelletized to obtain mildew-resistant and antibacterial granules;

[0053] Step S8: The mildew-resistant and antibacterial granules were added to the film blowing machine and extruded and blown into a film after melting under the condition of a temperature of 170°C, and then wound to obtain a mildew-resistant and antibacterial composite packaging bag.

[0054] Example 3:

[0055] The present embodiment is a preparation method of a mildew-resistant and antibacterial composite packaging bag, comprising the following steps:

[0056] Step S1: 25mmol of 1-octyl imidazole, 10mmol of dibromoneopentyl glycol and 40mL of dimethyl sulfoxide were added to a three-necked flask equipped with a stirrer, a thermometer and a gas inlet tube, protected by nitrogen, stirred at a temperature of 25°C and a stirring speed of 300r / min for 30min, then heated to 125°C and continued to stir for 15h, after the reaction was completed, the reaction product was cooled to room temperature, then rotary evaporated to remove the solvent, then added to anhydrous tetrahydrofuran, then placed to precipitate, then vacuum filtered, the filter cake was placed in a vacuum drying oven and dried at a temperature of 65°C for 3h to obtain bis-imidazolium ionic diol;

[0057] Step S2: 10 mmol of bisimidazolium ion diol, 25 mmol of perfluorobutyric acid, 0.13 g of p-toluenesulfonic acid, and 60 mL of toluene were added to a three-necked flask equipped with a stirrer, a thermometer, and a gas inlet tube, protected by nitrogen, stirred at a temperature of 25℃ and a stirring rate of 300 r / min for 30 min, then heated to 100℃ and continued to stir for 8 h. After the reaction was completed, the reaction product was cooled to room temperature, then rotary evaporation was used to remove the solvent, then washed with anhydrous tetrahydrofuran for 5 times, then placed in a vacuum drying oven, dried at a temperature of 75℃ for 5 h, to obtain a fluorine-containing bisimidazolium ion compound;

[0058] Step S3: 10 mmol of copper chloride dihydrate, 50 mL of deionized water were added to a three-necked flask equipped with a stirrer, a thermometer, a gas inlet tube, and a constant pressure dropping funnel, protected by nitrogen, stirred at a temperature of 30℃ and a stirring rate of 300 r / min for 20 min, then 15 mL of 35% sodium hydroxide solution was added dropwise while stirring, the dropping rate was controlled at 2 drops / s, after the addition was completed, the reaction was continued to stir for 20 min, then heated to 110℃ and continued to stir for 15 h. After the reaction was completed, the reaction product was cooled to room temperature, then centrifuged, the precipitate was washed with distilled water and anhydrous ethanol for 5 times, then placed in a vacuum drying oven, dried at a temperature of 95℃ for 5 h, to obtain nano copper oxide;

[0059] Step S4: 5 g of nano copper oxide, 5.4 g of sodium dodecyl sulfate, and 100 mL of deionized water were added to a three-necked flask equipped with a stirrer and a thermometer, stirred at a temperature of 25℃ and a stirring rate of 300 r / min for 30 min, then heated to 45℃ and continued to stir for 15 h. After the reaction was completed, the reaction product was cooled to room temperature, then centrifuged, the precipitate was washed with distilled water and anhydrous ethanol for 5 times, then placed in a vacuum drying oven, dried at a temperature of 65℃ for 5 h, to obtain modified nano copper oxide;

[0060] Step S5: polypropylene resin 100 parts, fluorine-containing bisimidazolium ion compound 3.5 parts, modified nano copper oxide 6 parts, light calcium carbonate 9 parts, plasticizer 12 parts, lubricant 6 parts, and antioxidant 3 parts were weighed according to the weight parts, and were ready for use. The polypropylene resin was pp-t300; the plasticizer was a mixture of dioctyl adipate and dicyclohexyl phthalate in a mass ratio of 2:3; the lubricant was vinyl bis-stearamide; the antioxidant was a mixture of antioxidant 1076 and antioxidant 1010 in a mass ratio of 3:1;

[0061] Step S6: The polypropylene resin, fluorine-containing bis-imidazolium ionic compound, modified nano copper oxide, light calcium carbonate, plasticizer, lubricant and antioxidant are added into a mixer and stirred and mixed until uniform to obtain a mildew-resistant and antibacterial mixture;

[0062] Step S7: The mildew-resistant and antibacterial mixture is added into a twin-screw extruder and melt blended and extruded at a temperature of 180°C and a screw speed of 150 r / min, and then pelletized to obtain mildew-resistant and antibacterial granules.

[0063] Step S8: The mildew-resistant and antibacterial granules are added into a film blowing machine and extruded and blown into a film after melting at a temperature of 175°C, and then wound to obtain a mildew-resistant and antibacterial composite packaging bag.

[0064] Comparative Example 1

[0065] The present comparative example is a preparation method of a mildew-resistant and antibacterial composite packaging bag, comprising the following steps:

[0066] Step S1: 100 parts of polypropylene resin, 9 parts of light calcium carbonate, 12 parts of plasticizer, 6 parts of lubricant and 3 parts of antioxidant are weighed according to weight parts 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;

[0067] Step S2: The polypropylene resin, light calcium carbonate, plasticizer, lubricant and antioxidant are added into a mixer and stirred and mixed until uniform to obtain a mildew-resistant and antibacterial mixture.

[0068] Step S3: The mildew-resistant and antibacterial mixture is added into a twin-screw extruder and melt blended and extruded at a temperature of 180°C and a screw speed of 150 r / min, and then pelletized to obtain mildew-resistant and antibacterial granules.

[0069] Step S4: The mildew-resistant and antibacterial granules are added into a film blowing machine and extruded and blown into a film after melting at a temperature of 175°C, and then wound to obtain a mildew-resistant and antibacterial composite packaging bag.

[0070] Comparative Example 2

[0071] The present comparative example is a preparation method of a mildew-resistant and antibacterial composite packaging bag, comprising the following steps:

[0072] Step S1: 10 mmol of copper chloride dihydrate, 50 mL of deionized water were added to a three-necked flask equipped with a stirrer, a thermometer, a gas inlet tube and a constant pressure dropping funnel, protected by nitrogen, stirred at a temperature of 30℃ and a stirring rate of 300 r / min for 20 min, then 15 mL of 35% sodium hydroxide solution was added dropwise while stirring, the dropping rate was controlled at 2 drops / s, after the addition was completed, the reaction was continued to stir for 20 min, then the temperature was raised to 110℃ and the reaction was continued to stir for 15 h, after the reaction was completed, the reaction product was cooled to room temperature, then centrifuged, the precipitate was washed with distilled water and anhydrous ethanol for 5 times, then placed in a vacuum drying oven, dried at a temperature of 95℃ for 5 h, to obtain nano copper oxide;

[0073] Step S2: 5 g of nano copper oxide, 5.4 g of sodium dodecyl sulfate and 100 mL of deionized water were added to a three-necked flask equipped with a stirrer and a thermometer, stirred at a temperature of 25℃ and a stirring rate of 300 r / min for 30 min, then the temperature was raised to 45℃ and the reaction was continued to stir for 15 h, after the reaction was completed, the reaction product was cooled to room temperature, then centrifuged, the precipitate was washed with distilled water and anhydrous ethanol for 5 times, then placed in a vacuum drying oven, dried at a temperature of 65℃ for 5 h, to obtain modified nano copper oxide;

[0074] Step S3: polypropylene resin 100 parts, modified nano copper oxide 6 parts, light calcium carbonate 9 parts, plasticizer 12 parts, lubricant 6 parts and antioxidant 3 parts were weighed according to weight parts, 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;

[0075] Step S4: polypropylene resin, modified nano copper oxide, light calcium carbonate, plasticizer, lubricant and antioxidant were added to a mixer and stirred and mixed to obtain a mildew-resistant and antibacterial mixture;

[0076] Step S5: the mildew-resistant and antibacterial mixture was added to a twin-screw extruder, melt blended and extruded at a temperature of 180℃ and a screw speed of 150 r / min, then pelletized to obtain mildew-resistant and antibacterial granules;

[0077] Step S6: the mildew-resistant and antibacterial granules were added to a film blowing machine, melted and extruded at a temperature of 175℃, then wound to obtain a mildew-resistant and antibacterial composite packaging bag.

[0078] Comparative Example 3:

[0079] The present comparative example is a preparation method of a mildew-proof and antibacterial composite packaging bag, comprising the following steps:

[0080] Step S1: 25 mmol of 1-octyl imidazole, 10 mmol of dibromo neopentyl glycol, and 40 mL of dimethyl sulfoxide were added to a three-necked flask equipped with a stirrer, a thermometer, and a gas inlet tube, and protected by nitrogen. The reaction was stirred at a temperature of 25°C and a stirring rate of 300 r / min for 30 min, and then continued to be stirred at a temperature of 125°C for 15 h. After the reaction was completed, the reaction product was cooled to room temperature, and then the solvent was removed by rotary evaporation. Then, the reaction product was added to anhydrous tetrahydrofuran, and then the precipitate was separated by standing. Then, the filter cake was placed in a vacuum drying oven and dried at a temperature of 65°C for 3 h to obtain a bisimidazolium ion glycol;

[0081] Step S2: 10 mmol of bisimidazolium ion glycol, 25 mmol of perfluorobutyric acid, 0.13 g of p-toluenesulfonic acid, and 60 mL of toluene were added to a three-necked flask equipped with a stirrer, a thermometer, and a gas inlet tube, and protected by nitrogen. The reaction was stirred at a temperature of 25°C and a stirring rate of 300 r / min for 30 min, and then continued to be stirred at a temperature of 100°C for 8 h. After the reaction was completed, the reaction product was cooled to room temperature, and then the solvent was removed by rotary evaporation. Then, the reaction product was washed with anhydrous tetrahydrofuran for 5 times, and then placed in a vacuum drying oven and dried at a temperature of 75°C for 5 h to obtain a fluorine-containing bisimidazolium ion compound;

[0082] Step S3: polypropylene resin 100 parts, fluorine-containing bisimidazolium ion compound 3.5 parts, light calcium carbonate 9 parts, plasticizer 12 parts, lubricant 6 parts, and antioxidant 3 parts were weighed according to weight parts, and were prepared for use. The polypropylene resin was pp-t300; the plasticizer was a mixture of dioctyl adipate and dicyclohexyl phthalate in a mass ratio of 2:3; the lubricant was vinyl bis-stearamide; and the antioxidant was a mixture of antioxidant 1076 and antioxidant 1010 in a mass ratio of 3:1;

[0083] Step S4: The polypropylene resin, the fluorine-containing bisimidazolium ion compound, the light calcium carbonate, the plasticizer, the lubricant, and the antioxidant were added to a mixer and stirred and mixed to obtain a mildew-proof and antibacterial mixture;

[0084] Step S5: The mildew-proof and antibacterial mixture was added to a twin-screw extruder, and melt blended and extruded at a temperature of 180°C and a screw rotation speed of 150 r / min. Then, the product was granulated to obtain mildew-proof and antibacterial granules;

[0085] Step S6: The mildew-proof and bacteriostatic granules are added to a film blowing machine, melted at a temperature of 175℃, and then extruded and rolled to obtain a mildew-proof and bacteriostatic composite packaging bag.

[0086] Comparative Example 4:

[0087] The present comparative example is a preparation method of a mildew-proof and bacteriostatic composite packaging bag, comprising the following steps:

[0088] Step S1: 25 mmol of 1-octyl imidazole, 10 mmol of dibromo neopentyl glycol, and 40 mL of dimethyl sulfoxide are added to a three-necked flask equipped with a stirrer, a thermometer, and a gas inlet tube, and protected by nitrogen, stirred at a temperature of 25℃ and a stirring speed of 300 r / min for 30 min, then heated to 125℃ and continued to stir for 15 h, after the reaction is completed, the reaction product is cooled to room temperature, then the solvent is removed by rotary evaporation, then added to anhydrous tetrahydrofuran, then placed to precipitate, then vacuum filtered, the filter cake is placed in a vacuum drying oven and dried at a temperature of 65℃ for 3 h to obtain a bisimidazolium ion diol;

[0089] Step S2: 10 mmol of copper chloride dihydrate, 50 mL of deionized water are added to a three-necked flask equipped with a stirrer, a thermometer, a gas inlet tube, and a constant pressure dropping funnel, and protected by nitrogen, stirred at a temperature of 30℃ and a stirring speed of 300 r / min for 20 min, then 15 mL of 35% sodium hydroxide solution is added dropwise while stirring, the dropping rate is controlled at 2 drops / s, after the addition is completed, the stirring is continued for 20 min, then heated to 110℃ and continued to stir for 15 h, after the reaction is completed, the reaction product is cooled to room temperature, then centrifuged, the precipitate is washed with distilled water and anhydrous ethanol for 5 times in turn, then placed in a vacuum drying oven and dried at a temperature of 95℃ for 5 h to obtain nano copper oxide;

[0090] Step S3: polypropylene resin 100 parts, bisimidazolium ion diol 3.5 parts, nano copper oxide 6 parts, light calcium carbonate 9 parts, plasticizer 12 parts, lubricant 6 parts, and antioxidant 3 parts are weighed according to weight parts, and reserved; 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: The polypropylene resin, bisimidazolium ion diol, nano copper oxide, light calcium carbonate, plasticizer, lubricant, and antioxidant are added to a mixer and stirred and mixed to obtain a mildew-proof and bacteriostatic mixture;

[0092] Step S5: The mildew-proof and bacteriostatic mixture was added into the twin-screw extruder, and melt blended and extruded at a temperature of 180°C and a screw rotation speed of 150 r / min, and then pelletized to obtain the mildew-proof and bacteriostatic granules;

[0093] Step S6: The mildew-proof and bacteriostatic granules were added into the film blowing machine, and melt extruded and blown into a film at a temperature of 175°C, and then wound to obtain the mildew-proof and bacteriostatic composite packaging bag.

[0094] The mildew-proof and bacteriostatic composite packaging bags of Examples 1-3 and Comparative Examples 1-4 were subjected to performance detection according to QBT 2591-2003 "Antibacterial plastics-antibacterial performance test method and antibacterial effect", and the detection results are shown in the following table:

[0095]

[0096] Referring to the data in the above table, according to the comparison between Examples 1-3 and Comparative Examples 1-4, it can be seen that the mildew-proof and bacteriostatic composite packaging bag of the present application has excellent mildew-proof and bacteriostatic performance.

[0097] In the description of the present specification, the description of the terms "one embodiment", "example", "specific example" and the like means that the specific features, structures, materials or characteristics described in connection with the embodiment or example are contained in at least one embodiment or example of the present application. In the present specification, the illustrative description of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.

[0098] The above is only an example and description of the present application, and those skilled in the art can make various modifications or supplements to the described specific embodiments or use similar ways to replace, as long as the modifications or supplements do not deviate from the invention or exceed the scope defined by the present application, and should belong to the protection scope of the present application.

Claims

1. A mildew-proof and bacteriostatic composite packaging bag, characterized in that, Comprise the following components by weight parts: Polypropylene resin 90-100 parts, fluorine-containing bis-imidazolium ionic compound 0.5-3.5 parts, modified nano copper oxide 2-6 parts, light calcium carbonate 3-9 parts, plasticizer 10-12 parts, lubricant 2-6 parts and antioxidant 1-3 parts; Wherein, the fluorine-containing bis-imidazolium ionic compound is prepared by the following steps: Step a1: 1-octyl imidazole, dibromoneopentyl glycol and dimethyl sulfoxide are stirred to react, the reaction product is cooled after the reaction is completed, then rotary evaporation is carried out, then the reaction product is added to anhydrous tetrahydrofuran and left to precipitate, then vacuum filtration is carried out, the filter cake is dried, and bis-imidazolium ionic diol is obtained; Step a2: bis-imidazolium ionic diol, perfluorobutyric acid, p-toluenesulfonic acid and toluene are stirred to react, the reaction product is cooled after the reaction is completed, then rotary evaporation is carried out, then washing and drying are carried out, and the fluorine-containing bis-imidazolium ionic compound is obtained.

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

3. The mildew-proof and bacteriostatic composite packaging bag according to claim 1, characterized in that, The amount ratio of bis-imidazolium ionic 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.

4. The mildew-proof and bacteriostatic composite packaging bag according to claim 1, characterized in that, The modified nano copper oxide is prepared by the following steps: Step b1: copper chloride dihydrate and deionized water are stirred to react, then sodium hydroxide solution is added dropwise while stirring, the reaction is continued after the dropwise addition is completed, the reaction product is cooled after the reaction is completed, then centrifugation is carried out, the precipitate is washed and dried, and nano copper oxide is obtained; Step b2: nano copper oxide, sodium dodecyl sulfate and deionized water are stirred to react, the reaction product is cooled after the reaction is completed, then centrifugation is carried out, the precipitate is washed and dried, and the modified nano copper oxide is obtained.

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

8. A method of producing the mold and bacteria inhibiting composite packaging bag according to any one of claims 1 to 7, characterized by, Comprise the following steps: Step one: polypropylene resin 90-100 parts, fluorine-containing bis-imidazolium ionic compound 0.5-3.5 parts, modified nano copper oxide 2-6 parts, light calcium carbonate 3-9 parts, plasticizer 10-12 parts, lubricant 2-6 parts and antioxidant 1-3 parts are weighed according to weight parts, and prepared for use; Step two: polypropylene resin, fluorine-containing bis-imidazolium ionic compound, modified nano copper oxide, light calcium carbonate, plasticizer, lubricant and antioxidant are added to a mixer and stirred and mixed, uniformly mixed, and a mildew-resistant and antibacterial mixture is obtained; Step three: the mildew-resistant and antibacterial mixture is added to a twin-screw extruder, melt blended and extruded under the conditions of a temperature of 170-180 DEG C and a screw rotation speed of 100-150 r / min, then pelletized, and a mildew-resistant and antibacterial pellet is obtained; Step four: the anti-mildew and bacteriostatic granules are added into a film blowing machine, and after melting at a temperature of 165-175 DEG C, the film blowing is extruded and rolled to obtain the anti-mildew and bacteriostatic composite packaging bag.

9. The method of claim 8, wherein the method further comprises the step of: 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.

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