High-temperature-resistant sterilization packaging bag and preparation method thereof

Abstract

The invention relates to the technical field of packaging bags, and discloses a high-temperature-resistant sterilization packaging bag and a preparation method thereof. The high-temperature-resistant sterilization packaging bag comprises a surface layer and a filling layer, the surface layer is composed of an upper surface layer and a lower surface layer, the filling layer is arranged between the upper surface layer and the lower surface layer, and the surface layer is prepared from, by mass, 45-55 parts of modified polyethylene, 15-25 parts of linear low-density polyethylene, 10-15 parts of low-density polyethylene and 2-4 parts of macromolecular stabilizer; the filling layer is prepared from the following raw materials in parts by mass: 45 to 55 parts of modified polyethylene, 15 to 25 parts of linear low-density polyethylene, 10 to 15 parts of low-density polyethylene, 2 to 4 parts of macromolecular stabilizer, 3 to 7 parts of nano CaCO3, 8 to 12 parts of micron CaCO3 and 2 to 4 parts of polypropylene resin. According to the prepared high-temperature-resistant sterilization packaging bag, the high-temperature-resistant performance and the mechanical performance of the packaging bag are synergistically enhanced by modifying polyethylene, adding a macromolecular stabilizer and controlling the proportion of micron calcium carbonate and nano calcium carbonate.

Description

Technical Field

[0001] The invention belongs to the technical field of packaging bags, and in particular relates to a high temperature resistant sterilization packaging bag and a preparation method thereof. Background Art

[0002] With the continuous development of disinfection and sterilization technology, the types of sterilization packaging are becoming more and more abundant, and the packaging bags need to be sterilized before or after use. In this process, the sterilization bags need good high temperature resistance; polyethylene is a widely used general plastic. Due to its unique crystal structure and chemical and thermal stability, it is widely used in various packaging materials. The thermal degradation and / or photo-oxidative degradation of polyolefin materials during processing, storage and use will affect the impact and tensile strength of the packaging bags and the elongation capacity, limiting their use and affecting the performance of the packaging bags. Summary of the invention

[0003] The object of the present invention is to provide a high temperature resistant sterilization packaging bag and a preparation method thereof, so as to solve the technical problem of improving the high temperature resistance of the packaging bag in the prior art.

[0004] In order to achieve the above object, the present invention adopts the following technical solutions: The technical solution provided by the present invention is as follows: In a first aspect, the present invention provides a high-temperature sterilization packaging bag, the high-temperature sterilization packaging bag comprises a surface layer composed of an upper surface layer and a lower surface layer and a filling layer, the filling layer is arranged between the upper surface layer and the lower surface layer, the surface layer is composed of the following raw materials by weight: 45-55 parts of modified polyethylene, 15-25 parts of linear low-density polyethylene, 10-15 parts of low-density polyethylene, and 2-4 parts of macromolecular stabilizer; the filling layer is composed of the following raw materials by weight: 45-55 parts of modified polyethylene, 15-25 parts of linear low-density polyethylene, 10-15 parts of low-density polyethylene, 2-4 parts of macromolecular stabilizer, nano-CaCO 3 3-7 parts, micron CaCO 3 8-12 parts, polypropylene resin 2-4 parts.

[0005] Preferably, the linear low-density polyethylene has a density of 0.92 g / cm 3 , its melt index is 2g / 10min, and the density of the low-density polyethylene is 0.93g / cm 3 , the melt index is 1.9g / 10min.

[0006] Preferably, the linear low-density polyethylene is any one of ethylene butene copolymer and ethylene hexene copolymer.

[0007] Preferably, the method for preparing the modified polyethylene comprises the following steps: S1: 40-80 g of o-carborane was added to 2.7-5.4 L of ether, 0.38-0.76 L of n-butyl lithium was added at -78 °C in a nitrogen atmosphere, and then stirred at room temperature for 1.5-2.5 h, and then 0.14-0.28 g of 6-bromo-1-hexene was added at -78 °C, heated to 40-50 °C and refluxed overnight, and then 0.44-0.88 L of saturated NH 4 The reaction was quenched with Cl solution, and then 20-40 L of ethyl acetate was added for extraction. The organic layer was washed with water and saturated sodium chloride solution for 3-5 times, and then anhydrous Na 2 SO 4 Dry for 12-16 hours, evaporate and concentrate, purify by silica flash chromatography with petroleum ether as eluent to obtain grafted o-carborane; S2: 11.8-20 g of grafted o-carborane is added to 12.5-25 L of dichloromethane, and then 1.6-3.2 g of Grubbs second-generation catalyst is added, and the mixture is refluxed at 40-50° C. overnight, and then 3-6 mL of vinyl ethyl ether is added to cool the reaction, and then stirred for 20-40 min, evaporated and concentrated, and then purified by silica flash chromatography using petroleum ether as eluent to obtain cyclized o-carborane; The structural formula of cyclized o-carborane is as follows: S3: 4-8 g of cyclized o-carborane and 4-8 g of cycloolefin were mixed, nitrogen purged for 8-12 min, 40-80 mL of dichloromethane was added, and then 0.04-0.08 g of Grubbs second-generation catalyst was added. After reacting for 2-4 h, 1-2 mL of vinyl ethyl ether was added to quench the copolymerization, and the mixture was precipitated in methanol for 2-4 times and filtered. The filter residue was vacuum dried for 12-18 h to obtain an intermediate product; S4: Add 4-8 g of the intermediate product to 0.4-0.8 L of toluene, purge with nitrogen for 18-22 min, add 35-39 g of toluenesulfonyl hydrazide and 26-30 g of tripropylamine, heat to 115-125 ° C, reflux overnight and then cool to room temperature, precipitate in methanol 2-4 times, filter, and vacuum dry the filter residue for 12-18 h to obtain modified polyethylene.

[0008] The structural formula of modified polyethylene is as follows: Preferably, the method for preparing the macromolecular stabilizer comprises the following steps: P1: 2.4-4.8g LiAlH 4Add 50-100 mL of tetrahydrofuran to obtain a suspension, then slowly add 41-82 g of antioxidant 1010 to the suspension at 0°C, stir at room temperature for 36-54 h, add 0.1 mol / L hydrochloric acid dropwise until there are no bubbles, dilute with 50-100 mL of water, extract with 100-200 mL of ethyl acetate, and add Na 2 SO 4 Dry for 12-18h, filter, evaporate and concentrate, purify by flash chromatography on silica gel with petroleum ether-ethyl acetate (4:1) as eluent to obtain product 1; P2: Add 20-40 g of product 1 to 50-100 mL of pyridine, place at 0 ° C for 10-20 min, stir at room temperature for 2-4 h, then dilute with 0.1 mol / L hydrochloric acid to pH 4, extract with 800-1600 mL of ethyl acetate, wash the organic layer with water 3-5 times, and then use Na 2 SO 4 Dry for 12-18 h, filter, and evaporate the solvent to obtain product 2; P3: 5.2-10.4 g of product 2 was added to 400-800 mL of anhydrous ethanol, and then 400-800 mL of 33% (V / V) NH 4 OH solution, the reaction was refluxed and stirred at 65-75°C for 16-20h, then diluted with 1-2L of water, extracted with 0.8-1.6L of ethyl acetate, and the organic layer was washed 3-5 times with 1-2mL of saturated NaCl solution, and then anhydrous Na 2 SO 4 Dry for 12-18 hours, filter, and evaporate the solvent to obtain an amino antioxidant; The structural formula of the amino antioxidant is as follows: P4: 2-4 g of polyethylene grafted maleic anhydride and 1-2 g of amino antioxidant were mixed in a stainless steel grinding jar, and 6 stainless steel grinding balls with a diameter of 5 mm were used for ball milling at a speed of 1600-2000 rpm for 1-3 h. After separating the grinding balls, the mixture was washed with ethyl acetate for 3-5 times, filtered, and vacuum dried for 20-28 h to obtain a macromolecular stabilizer.

[0009] The structural formula of the macromolecular stabilizer is as follows: In a second aspect, the present invention further provides a method for preparing a high temperature sterilization resistant packaging bag, comprising the following steps: Step (1) adding 45-55 parts of modified polyethylene, 15-25 parts of linear low-density polyethylene, 10-15 parts of low-density polyethylene, and 2-4 parts of macromolecular stabilizer into a blender, stirring evenly, and blending and extruding to form a surface molten material; Step (2) 45-55 parts of modified polyethylene, 15-25 parts of linear low-density polyethylene, 10-15 parts of low-density polyethylene, 2-4 parts of macromolecular stabilizer, 3-7 parts of nano-CaCO 3 , 8-12 microns CaCO 3 , add 2-4 parts of polypropylene resin into a mixer, stir evenly, and extrude the mixture to form a molten material for the filling layer; Step (3) extruding the molten materials in step (1) and step (2) from a co-extrusion die head, so that the filling layer and the surface layer are sequentially superimposed in a molten state from the outside to the inside to form a molten film, and then inflating the molten film and quenching it to obtain a film; Step (4) is to roll up the film obtained in step (3), and to seal and cut the rolled film by a bag making machine to obtain a high temperature sterilization resistant packaging bag.

[0010] Preferably, in step (1), the rotation speed of the stirrer is 1500-2000 rpm; and the melting temperature of the co-extrusion is 175-185°C.

[0011] Preferably, in step (2), the rotation speed of the mixer is 1500-2000 rpm; and the melting temperature of the co-extrusion is 165-180°C.

[0012] Preferably, in step (3), the mixing ratio of the molten materials in step (1) and step (2) is 2:1; and the extrusion temperature is 170-185°C.

[0013] In summary, due to the adoption of the above technical solution, the beneficial effects of the present invention are: 1. In the present invention, o-carborane is a rigid icosahedral boron cluster compound with excellent thermal stability and chemical stability. At 600°C, o-carborane will only isomerize to p-carborane without decomposing. o-carborane is added to the main chain of polyethylene to obtain modified polyethylene with large pieces of o-carborane as pendants. By maintaining its inherent all-hydrocarbon main chain properties and improving the rigidity of the hydrocarbon skeleton, the thermal stability, oxidation resistance and mechanical properties of the polyethylene are improved.

[0014] 2. In the present invention, a macromolecular stabilizer with an antioxidant part is prepared by reactive blending of polyethylene grafted maleic anhydride and butylated hydroxytoluene derivatives promoted by solvent-free mechanochemical reaction. The macromolecular stabilizer has a polymerization property in which about 1% mol of stabilizing groups are covalently connected to the polymer main chain, which ensures their good dispersion in polyethylene, and due to their inherent non-release characteristics, their migration loss is zero, and they have very good antioxidant protection; the macromolecular stabilizer eliminates the release of small molecular weight stabilizers, reduces the total amount of additives added to the polymer material, and maintains the stabilizing ability of the additives, which is healthy, safe and environmentally friendly when in contact with drugs; the macromolecular stabilizer is added to the polymer, and the amide group is cyclized and converted into cyclic imide when heated. The imide group is chemically more stable than amide, which can improve the macromolecular free radical scavenging ability of the stabilizer. At the same time, the macromolecular stabilizer also acts as a compatibilizer to improve the thermal stability and mechanical properties of the packaging material.

[0015] 3. Nano-CaCO in the present invention 3 In plastic processing, it can improve the rheological properties and plasticity of plastic masterbatch, and can play a dual role of toughening and strengthening in plastic performance, thereby improving the flexural strength, elastic modulus, heat deflection temperature and dimensional stability of plastics. However, nano-CaCO 3 The specific surface area is large, the surface energy is high, and it is easy to agglomerate. 3 The particle surface is in a thermodynamically stable state and is not easy to agglomerate. By mixing nano and micro calcium carbonate in a specific ratio, calcium carbonate enables linear low-density polyethylene and low-density polyethylene to crystallize at a higher temperature, thereby improving the thermal stability of the mixed system and synergistically improving the high temperature resistance of the packaging bag. The connection between the nano and micro calcium carbonate and the matrix ensures that the external force is transmitted to the dispersed filler, thereby improving the mechanical properties of the packaging bag. Therefore, controlling the ratio of nano and micro calcium carbonate achieves a synergistic enhancement effect on the packaging bag. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0017] Figure 1 It is a process flow chart of the preparation of the high temperature resistant sterilization packaging bag of the present invention; Figure 2 is a histogram of the thermal stability of the high temperature sterilization packaging bag of the present invention; Figure 3 It is a bar graph of the mechanical properties of the high temperature sterilization packaging bag of the present invention. DETAILED DESCRIPTION

[0018] The following will be combined with the drawings in 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 part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0019] Example 1 This embodiment discloses a method for preparing modified polyethylene, comprising the following steps: S1: 60 g of o-carborane was added to 4.1 L of ether, 0.57 L of n-butyl lithium was added at -78 °C in a nitrogen atmosphere, and then stirred at room temperature for 2 h, and then 0.21 g of 6-bromo-1-hexene was added at -78 °C, heated to 45 °C and refluxed overnight, and then 0.66 L of saturated NH 4 The reaction was quenched with Cl solution, and then 30 L of ethyl acetate was added for extraction. The organic layer was washed with water and saturated sodium chloride solution four times in sequence, and then anhydrous Na 2 SO 4 The mixture was dried for 14 h, concentrated by evaporation, and purified by silica flash chromatography using petroleum ether as eluent to obtain grafted o-carborane; S2: 16 g of grafted o-carborane was added to 18.8 L of dichloromethane, and then 2.4 g of Grubbs second-generation catalyst was added, and the mixture was refluxed at 45° C. overnight, and then 4.5 mL of vinyl ethyl ether was added to cool the reaction, stirred for 30 min, evaporated and concentrated, and then purified by silica flash chromatography using petroleum ether as eluent to obtain cyclized o-carborane; S3: 6 g of cyclized o-carborane and 6 g of cycloolefin were mixed, purged with nitrogen for 10 min, 60 mL of dichloromethane was added, and then 0.06 g of Grubbs second-generation catalyst was added. After reacting for 3 h, 1.5 mL of vinyl ethyl ether was added to quench the copolymerization, and the mixture was precipitated in methanol for 3 times and filtered. The filter residue was vacuum dried for 16 h to obtain an intermediate product; S4: 6 g of the intermediate product was added to 0.6 L of toluene, and after nitrogen purging for 20 min, 37 g of toluenesulfonyl hydrazide and 28 g of tripropylamine were added, and the mixture was heated to 120 ° C. After reflux overnight, it was cooled to room temperature, precipitated in methanol for 3 times and filtered, and the filter residue was vacuum dried for 15 h to obtain modified polyethylene.

[0020] Example 2 This embodiment discloses a method for preparing a macromolecular stabilizer, comprising the following steps: P1: 3.6 g LiAlH 4Add 75 mL of tetrahydrofuran to obtain a suspension, then slowly add 61.5 g of antioxidant 1010 to the suspension at 0 ° C, stir at room temperature for 48 hours, add 0.1 mol / L hydrochloric acid dropwise until there are no bubbles, dilute with 75 mL of water, extract with 150 mL of ethyl acetate, and add Na 2 SO 4 The mixture was dried for 15 h, filtered, evaporated and concentrated, and purified by flash chromatography on silica gel with petroleum ether-ethyl acetate (4:1) as eluent to obtain product 1; P2: 30 g of product 1 was added to 75 mL of pyridine, placed at 0 °C for 15 min, stirred at room temperature for 3 h, then diluted with 0.1 mol / L hydrochloric acid to pH 4, extracted with 1200 mL of ethyl acetate, washed the organic layer with water 4 times, and then washed with Na 2 SO 4 Dry for 15 h, filter, and evaporate the solvent to obtain product 2; P3: 7.8 g of product 2 was added to 600 mL of anhydrous ethanol, and then 600 mL of 33% (V / V) NH 4 OH solution, the reaction was refluxed and stirred at 70 ° C for 18 h, then diluted with 1.5 L of water, extracted with 1.2 L of ethyl acetate, and the organic layer was washed 4 times with 1.5 mL of saturated NaCl solution, and then anhydrous Na 2 SO 4 Dry for 15 h, filter, and evaporate the solvent to obtain an amino antioxidant; P4: 3 g of polyethylene grafted maleic anhydride and 1.5 g of amino antioxidant were mixed in a stainless steel grinding jar, and ball-milled at a speed of 1800 rpm for 2 h using 6 stainless steel grinding balls with a diameter of 5 mm. After separating the grinding balls, the mixture was washed with ethyl acetate for 4 times, filtered, and vacuum dried for 24 h to obtain a macromolecular stabilizer.

[0021] Example 3 See also Figure 1 As shown, this embodiment discloses a method for preparing a high temperature resistant sterilization packaging bag, comprising the following steps: Step (1) adding 50 parts of the modified polyethylene prepared in Example 1, 20 parts of the linear low-density polyethylene, 12 parts of the low-density polyethylene, and 3 parts of the macromolecular stabilizer prepared in Example 2 into a stirrer and stirring them uniformly at a speed of 1700 rpm, and then blending and extruding them at a melting temperature of 180° C. to form a surface layer molten material; Step (2) 50 parts of the modified polyethylene prepared in Example 1, 20 parts of linear low-density polyethylene, 12 parts of low-density polyethylene, 3 parts of the macromolecular stabilizer prepared in Example 2, 5 parts of nano-CaCO 3 , 10 microns CaCO 3, 3 parts of polypropylene resin were added into a mixer and stirred evenly at a rotation speed of 1700 rpm, and then blended and extruded at a melting temperature of 175° C. to form a filling layer molten material; Step (3) at 180° C., extruding the molten materials in step (1) and step (2) from a co-extrusion die head at a mixing ratio of 2:1, so that the filling layer and the surface layer are sequentially superimposed in a molten state from the outside to the inside to form a molten film, and then inflating the molten film and quenching it to obtain a film; Step (4) is to roll up the film obtained in step (3), and to seal and cut the rolled film by a bag making machine to obtain a high temperature sterilization resistant packaging bag.

[0022] Example 4 See also Figure 1 As shown, this embodiment discloses a method for preparing a high temperature resistant sterilization packaging bag, comprising the following steps: Step (1) 45 parts of the modified polyethylene prepared in Example 1, 25 parts of the linear low-density polyethylene, 10 parts of the low-density polyethylene, and 4 parts of the macromolecular stabilizer prepared in Example 2 were added to a stirrer and stirred evenly at a speed of 1500 rpm, and then blended and extruded at a melting temperature of 185° C. to form a surface molten material; Step (2) 45 parts of the modified polyethylene prepared in Example 1, 25 parts of linear low-density polyethylene, 10 parts of low-density polyethylene, 4 parts of the macromolecular stabilizer prepared in Example 2, and 3 parts of nano-CaCO 3 , 12 microns CaCO 3 , 2 parts of polypropylene resin are added into a mixer and stirred evenly at a rotation speed of 2000 rpm, and then blended and extruded at a melting temperature of 165° C. to form a filling layer molten material; Step (3) at 185° C., extruding the molten materials in step (1) and step (2) from a co-extrusion die head at a mixing ratio of 2:1, so that the filling layer and the surface layer are sequentially superimposed in a molten state from the outside to the inside to form a molten film, and then inflating the molten film and quenching it to obtain a film; Step (4) is to roll up the film obtained in step (3), and to seal and cut the rolled film by a bag making machine to obtain a high temperature sterilization resistant packaging bag.

[0023] Example 5 See also Figure 1 As shown, this embodiment discloses a method for preparing a high temperature resistant sterilization packaging bag, comprising the following steps: Step (1) 55 parts of the modified polyethylene prepared in Example 1, 15 parts of the linear low-density polyethylene, 15 parts of the low-density polyethylene, and 2 parts of the macromolecular stabilizer prepared in Example 2 were added to a stirrer and stirred evenly at a speed of 2000 rpm, and then blended and extruded at a melting temperature of 175° C. to form a surface molten material; Step (2) 55 parts of the modified polyethylene prepared in Example 1, 15 parts of linear low-density polyethylene, 15 parts of low-density polyethylene, 2 parts of the macromolecular stabilizer prepared in Example 2, 7 parts of nano-CaCO 3 , 8 microns CaCO 3 , 4 parts of polypropylene resin are added into a mixer and stirred evenly at a speed of 1500 rpm, and then blended and extruded at a melting temperature of 180° C. to form a filling layer molten material; Step (3) at 170° C., the molten materials in step (1) and step (2) are extruded from a co-extrusion die head at a mixing ratio of 2:1, so that the filling layer and the surface layer are sequentially superimposed in a molten state from the outside to the inside to form a molten film, and then the molten film is inflated and quenched to obtain a film; Step (4) is to roll up the film obtained in step (3), and to seal and cut the rolled film by a bag making machine to obtain a high temperature sterilization resistant packaging bag.

[0024] Example 6 See also Figure 1 As shown, this embodiment discloses a method for preparing a high temperature resistant sterilization packaging bag, comprising the following steps: Step (1) adding 48 parts of the modified polyethylene prepared in Example 1, 22 parts of the linear low-density polyethylene, 11 parts of the low-density polyethylene, and 3 parts of the macromolecular stabilizer prepared in Example 2 into a stirrer and stirring them uniformly at a speed of 1600 rpm, and blending and extruding them at a melting temperature of 182° C. to form a surface layer molten material; Step (2) 47 parts of the modified polyethylene prepared in Example 1, 22 parts of linear low-density polyethylene, 11 parts of low-density polyethylene, 3 parts of the macromolecular stabilizer prepared in Example 2, 4 parts of nano-CaCO 3 , 11 microns CaCO 3 , 3 parts of polypropylene resin were added into a mixer and stirred evenly at a speed of 1800 rpm, and then blended and extruded at a melting temperature of 168° C. to form a filling layer molten material; Step (3) at 182° C., the molten materials in step (1) and step (2) are extruded from a co-extrusion die head at a mixing ratio of 2:1, so that the filling layer and the surface layer are sequentially superimposed in a molten state from the outside to the inside to form a molten film, and then the molten film is inflated and quenched to obtain a film; Step (4) is to roll up the film obtained in step (3), and to seal and cut the rolled film by a bag making machine to obtain a high temperature sterilization resistant packaging bag.

[0025] Example 7 See also Figure 1 As shown, this embodiment discloses a method for preparing a high temperature resistant sterilization packaging bag, comprising the following steps: Step (1) 52 parts of the modified polyethylene prepared in Example 1, 16 parts of the linear low-density polyethylene, 14 parts of the low-density polyethylene, and 2 parts of the macromolecular stabilizer prepared in Example 2 were added to a stirrer and stirred evenly at a speed of 1900 rpm, and then blended and extruded at a melting temperature of 178° C. to form a surface molten material; Step (2) 53 parts of the modified polyethylene prepared in Example 1, 16 parts of linear low-density polyethylene, 14 parts of low-density polyethylene, 4 parts of the macromolecular stabilizer prepared in Example 2, 6 parts of nano-CaCO 3 , 9 microns CaCO 3 , 4 parts of polypropylene resin were added into a mixer and stirred evenly at a speed of 1600 rpm, and then blended and extruded at a melting temperature of 178° C. to form a filling layer molten material; Step (3) at 172° C., the molten materials in step (1) and step (2) are extruded from a co-extrusion die head at a mixing ratio of 2:1, so that the filling layer and the surface layer are sequentially superimposed in a molten state from the outside to the inside to form a molten film, and then the molten film is inflated and quenched to obtain a film; Step (4) is to roll up the film obtained in step (3), and to seal and cut the rolled film by a bag making machine to obtain a high temperature sterilization resistant packaging bag.

[0026] Comparative Example 1 Compared with Example 3, in Comparative Example 1, high-density polyethylene is used to replace modified polyethylene during the preparation of the high-temperature sterilization packaging bag, and other conditions remain unchanged.

[0027] Comparative Example 2 Compared with Example 3, in Comparative Example 2, no macromolecular stabilizer was added during the preparation of the high-temperature sterilization-resistant packaging bag, and other conditions remained unchanged.

[0028] Experimental example The performance of the high temperature sterilization packaging bags prepared in Examples 3-7 and Comparative Examples 1-2 was tested: 1. Heat resistance Table 1 It can be seen from Table 1 that the high temperature resistant sterilization packaging bags prepared in Examples 3-7 have good high temperature resistance; from the comparison between Comparative Example 1 and Example 3, it can be seen that in the process of preparing the high temperature resistant sterilization packaging bags, the modified polyethylene is used to improve the high temperature resistance of the high temperature resistant sterilization packaging bags; from the comparison between Comparative Example 2 and Example 3, it can be seen that in the process of preparing the high temperature resistant sterilization packaging bags, the macromolecular stabilizer is added to improve the high temperature resistance of the high temperature resistant sterilization packaging bags.

[0029] 2. Mechanical properties The tensile strength was tested according to GB / T1040-1992, and the tear strength was tested according to QB / T1130-1991. The test results are shown in Table 2: Table 2 It can be seen from Table 1 that the high temperature resistant sterilization packaging bags prepared in Examples 3-7 have good mechanical properties. From the comparison between Comparative Example 1 and Example 3, it can be seen that in the process of preparing the high temperature resistant sterilization packaging bags, the modified polyethylene is used to improve the mechanical properties of the high temperature resistant sterilization packaging bags. From the comparison between Comparative Example 2 and Example 3, it can be seen that in the process of preparing the high temperature resistant sterilization packaging bags, the macromolecular stabilizer is added to improve the mechanical properties of the high temperature resistant sterilization packaging bags.

[0030] The above description is only a preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any technician familiar with the technical field can make equivalent replacements or changes according to the technical scheme and inventive concept of the present invention within the technical scope disclosed by the present invention, which should be covered by the protection scope of the present invention.

[0031] The preferred embodiments of the present invention disclosed above are only used to help explain the present invention. The preferred embodiments do not describe all the details in detail, nor do they limit the invention to only specific implementation methods. Obviously, many modifications and changes can be made according to the content of this specification. This specification selects and specifically describes these embodiments in order to better explain the principles and practical applications of the present invention, so that those skilled in the art can understand and use the present invention well. The present invention is limited only by the claims and their full scope and equivalents.

Claims

1. A high temperature sterilization packaging bag, characterized in that: The high-temperature sterilization packaging bag comprises a surface layer consisting of an upper surface layer and a lower surface layer and a filling layer, wherein the filling layer is arranged between the upper surface layer and the lower surface layer, and the surface layer is composed of the following raw materials in parts by mass: 45-55 parts of modified polyethylene, 15-25 parts of linear low-density polyethylene, 10-15 parts of low-density polyethylene, and 2-4 parts of macromolecular stabilizer; the filling layer is composed of the following raw materials in parts by mass: 45-55 parts of modified polyethylene, 15-25 parts of linear low-density polyethylene, 10-15 parts of low-density polyethylene, 2-4 parts of macromolecular stabilizer, 3-7 parts of nano-CaCO3, 8-12 parts of micron-CaCO3, and 2-4 parts of polypropylene resin.

2. The high temperature sterilization packaging bag according to claim 1, characterized in that: The linear low-density polyethylene has a density of 0.92 g / cm 3 , its melt index is 2g / 10min, and the density of the low-density polyethylene is 0.93g / cm 3 , the melt index is 1.9g / 10min.

3. The high temperature sterilization packaging bag according to claim 1, characterized in that: The linear low-density polyethylene is any one of ethylene-butene copolymer and ethylene-hexene copolymer.

4. The high temperature sterilization packaging bag according to claim 1, characterized in that: The preparation method of the modified polyethylene comprises the following steps: S1: 40-80 g of o-carborane is added to 2.7-5.4 L of ether, 0.38-0.76 L of n-butyl lithium is added at -78 ° C in a nitrogen atmosphere, and then stirred at room temperature for 1.5-2.5 h, and then 0.14-0.28 g of 6-bromo-1-hexene is added at -78 ° C, heated to 40-50 ° C and refluxed overnight, and then 0.44-0.88 L of saturated NH4Cl solution is added to quench the reaction, and then 20-40 L of ethyl acetate is added for extraction, and the organic layer is washed with water and saturated sodium chloride solution for 3-5 times in sequence, and then anhydrous Na2SO4 is added to dry for 12-16 h, evaporated and concentrated, and purified by silica flash chromatography with petroleum ether as eluent to obtain grafted o-carborane; S2: 11.8-20 g of grafted o-carborane is added to 12.5-25 L of dichloromethane, and then 1.6-3.2 g of Grubbs second-generation catalyst is added, and the mixture is refluxed at 40-50° C. overnight, and then 3-6 mL of vinyl ethyl ether is added to cool the reaction, and then stirred for 20-40 min, evaporated and concentrated, and then purified by silica flash chromatography using petroleum ether as eluent to obtain cyclized o-carborane; S3: 4-8 g of cyclized o-carborane and 4-8 g of cycloolefin were mixed, nitrogen purged for 8-12 min, 40-80 mL of dichloromethane was added, and then 0.04-0.08 g of Grubbs second-generation catalyst was added. After reacting for 2-4 h, 1-2 mL of vinyl ethyl ether was added to quench the copolymerization, and the mixture was precipitated in methanol for 2-4 times and filtered. The filter residue was vacuum dried for 12-18 h to obtain an intermediate product; S4: Add 4-8 g of the intermediate product to 0.4-0.8 L of toluene, purge with nitrogen for 18-22 min, add 35-39 g of toluenesulfonyl hydrazide and 26-30 g of tripropylamine, heat to 115-125 ° C, reflux overnight and then cool to room temperature, precipitate in methanol 2-4 times, filter, and vacuum dry the filter residue for 12-18 h to obtain modified polyethylene.

5. The high temperature sterilization packaging bag according to claim 1, characterized in that: The preparation method of the macromolecular stabilizer comprises the following steps: P1: 2.4-4.8 g of LiAlH4 was added to 50-100 mL of tetrahydrofuran to obtain a suspension, and then 41-82 g of antioxidant 1010 was slowly added to the suspension at 0°C, and stirred at room temperature for 36-54 h, and then 0.1 mol / L hydrochloric acid was added dropwise until there were no bubbles, and then 50-100 mL of water was added to dilute it, and then extracted with 100-200 mL of ethyl acetate, and Na2SO4 was added to the organic layer to dry it for 12-18 h, filtered, evaporated and concentrated, and purified by flash chromatography on silica gel with petroleum ether-ethyl acetate as eluent to obtain product 1; P2: Add 20-40 g of product 1 to 50-100 mL of pyridine, place at 0°C for 10-20 min, stir at room temperature for 2-4 h, then dilute with 0.1 mol / L hydrochloric acid to pH 4, extract with 800-1600 mL of ethyl acetate, wash the organic layer with water 3-5 times, dry with Na2SO4 for 12-18 h, filter, and evaporate the solvent to obtain product 2; P3: 5.2-10.4 g of product 2 was added to 400-800 mL of anhydrous ethanol, and then 400-800 mL of 33% (V / V) NH4OH solution was added. The reaction was refluxed and stirred at 65-75°C for 16-20 h, and then 1-2 L of water was added for dilution. After extraction with 0.8-1.6 L of ethyl acetate, the organic layer was washed 3-5 times with 1-2 mL of saturated NaCl solution, and then anhydrous Na2SO4 was added for drying for 12-18 h, filtered, and the solvent was evaporated to obtain an amino antioxidant; P4: 2-4 g of polyethylene grafted maleic anhydride and 1-2 g of amino antioxidant were mixed in a stainless steel grinding jar, and 6 stainless steel grinding balls with a diameter of 5 mm were used for ball milling at a speed of 1600-2000 rpm for 1-3 h. After separating the grinding balls, the mixture was washed with ethyl acetate for 3-5 times, filtered, and vacuum dried for 20-28 h to obtain a macromolecular stabilizer.

6. A method for preparing a high temperature sterilization packaging bag according to any one of claims 1 to 5, characterized in that: The steps include: Step (1) adding 45-55 parts of modified polyethylene, 15-25 parts of linear low-density polyethylene, 10-15 parts of low-density polyethylene, and 2-4 parts of macromolecular stabilizer into a blender, stirring evenly, and blending and extruding to form a surface molten material; Step (2) adding 45-55 parts of modified polyethylene, 15-25 parts of linear low-density polyethylene, 10-15 parts of low-density polyethylene, 2-4 parts of macromolecular stabilizer, 3-7 parts of nano-CaCO3, 8-12 parts of micron-CaCO3, and 2-4 parts of polypropylene resin into a blender, stirring evenly, and blending and extruding to form a filling layer molten material; Step (3) extruding the molten materials in step (1) and step (2) from a co-extrusion die head, so that the filling layer and the surface layer are sequentially superimposed in a molten state from the outside to the inside to form a molten film, and then inflating the molten film and quenching it to obtain a film; Step (4) is to roll up the film obtained in step (3), and to seal and cut the rolled film by a bag making machine to obtain a high temperature sterilization resistant packaging bag.

7. The method for preparing a high temperature sterilization packaging bag according to claim 6, characterized in that: In the step (1), the rotation speed of the stirrer is 1500-2000 rpm; and the melting temperature of the blending extrusion is 175-185°C.

8. The method for preparing a high temperature sterilization packaging bag according to claim 6, characterized in that: In the step (2), the rotation speed of the mixer is 1500-2000 rpm; and the melting temperature of the blending extrusion is 165-180°C.

9. The method for preparing a high temperature sterilization packaging bag according to claim 6, characterized in that: In the step (3), the mixing ratio of the molten materials in step (1) and step (2) is 2:1; and the extrusion temperature is 170-185°C.

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