CN113121904A - Preparation process of antibacterial film - Google Patents
Preparation process of antibacterial film Download PDFInfo
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- CN113121904A CN113121904A CN202110435923.XA CN202110435923A CN113121904A CN 113121904 A CN113121904 A CN 113121904A CN 202110435923 A CN202110435923 A CN 202110435923A CN 113121904 A CN113121904 A CN 113121904A
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
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- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
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- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
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- C08J2497/00—Characterised by the use of lignin-containing materials
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
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- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/387—Borates
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- C08K3/28—Nitrogen-containing compounds
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- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0058—Biocides
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- C08K9/00—Use of pretreated ingredients
- C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
Abstract
The invention belongs to the technical field of plastic films, and particularly relates to a preparation process of an antibacterial film, which comprises the steps of taking 1-2 parts by weight of nano-silver antibacterial agent, 120 parts by weight of polyethylene resin blend, 2-4 parts by weight of modified lignocellulose, 0.5-1 part by weight of silver-loaded nano-zinc oxide, 1-2 parts by weight of plasticizer, 0.05-0.1 part by weight of dispersant and 0.1-0.6 part by weight of antioxidant, mixing, granulating, drying and blowing to prepare the antibacterial film. The invention provides a film with good antibacterial performance, which has good tensile strength, and the preparation process of the antibacterial film is simple and is suitable for large-scale industrial production.
Description
Technical Field
The invention relates to the technical field of plastic films, in particular to a preparation process of an antibacterial film.
Background
Plastic films are films made of polyvinyl chloride, polyethylene, polypropylene, polystyrene, and other resins, and are used for packaging and as a film coating layer. Plastic packages and plastic package products have an increasing share in the market and have been widely used in numerous fields, in particular in the technical fields of food, medicine, chemical industry and the like. However, when the plastic film is applied to the preservation of food, medicine and other specific temperature and humidity conditions, microorganisms such as bacteria and fungi harmful to human health are easily bred on the surface of the plastic film, so that the plastic film pollutes the food or medicine, causes the food or medicine to deteriorate, go mouldy and even rot, and easily causes food-borne diseases. The film with antibacterial and bacteriostatic properties in the market is high in manufacturing cost, unobvious in bacteriostatic effect and poor in tensile strength, so that the plastic film is endowed with good antibacterial properties and good physical properties, meets the requirements of production and life safety of people, and has important practical significance.
Disclosure of Invention
The invention aims to provide a polyethylene plastic film with good antibacterial performance, and the polyethylene plastic film has good tensile strength, so that the invention provides the following technical scheme:
a preparation process of an antibacterial film comprises the following steps of taking 1-2 parts by weight of nano-silver antibacterial agent, 120 parts by weight of polyethylene resin blend, 2-4 parts by weight of modified lignocellulose, 0.5-1 part by weight of silver-loaded nano zinc oxide, 1-2 parts by weight of plasticizer, 0.05-0.1 part by weight of dispersant and 0.1-0.6 part by weight of antioxidant, mixing, granulating, drying and blowing to prepare the antibacterial film.
The nano-silver bacteriostatic agent is prepared according to the following steps:
step a: drying and crushing dandelion leaves and dandelion roots respectively, mixing the dandelion leaves and the dandelion roots according to the weight ratio of 1: 2-3, mixing the dandelion leaves and the dandelion roots with a 50% ethanol solution, carrying out heating reflux for 30-40min at 100 ℃, repeating for 3 times, combining the extracts for 3 times, carrying out reduced pressure evaporation at 35 ℃ to obtain dandelion extract, and diluting the dandelion extract to 100mg/mL by using 70% ethanol to obtain dandelion extract.
Step b: taking 7-8 parts of dandelion extract and 0.05mol/L AgNO by weight3Mixing 1-2 parts of the solution, adding 30 parts of deionized water, stirring uniformly, heating and refluxing at 100 ℃, stopping heating when the solution gradually becomes dark yellow, and identifying the absorption peak to be 458nm and the absorption peak range to be 400-500nm by adopting an ultraviolet-visible spectrum method, thus determining that the nano-silver composition is obtained.
Step c: and c, adding 0.05-0.1 part by weight of plant gum and 0.02-0.05 part by weight of borax into the nano-silver composition prepared in the step b, stirring for 1-2 hours, standing and precipitating to obtain a flocculation extract.
Step d: and drying the flocculated extract to obtain the nano-silver bacteriostatic agent.
The polyethylene resin blend comprises the following components in parts by weight: 35-40 parts of low-density polyethylene, 20-25 parts of medium-density polyethylene and 5-8 parts of linear low-density polyethylene.
The modified lignocellulose is prepared by the following steps:
step A: adding 15-20 parts by weight of polyethylene glycol into 40 parts by weight of deionized water, and fully stirring until the polyethylene glycol is completely dissolved to obtain a polyethylene glycol aqueous solution.
And B: adding 5-8 parts by weight of lignocellulose into an alkaline solution for activation treatment, then adding 30 parts by weight of deionized water, and ultrasonically dispersing for 3 times in an ice water bath for 10min each time to obtain the lignocellulose aqueous solution.
And C: adding the lignocellulose aqueous solution into a polyethylene glycol aqueous solution, magnetically stirring for 2 hours at room temperature, stirring in a water bath at 90 ℃ to evaporate the water solvent, drying by distillation, placing in a vacuum drying oven, and drying into powder at 60 ℃ to obtain the modified lignocellulose.
Preferably, the alkaline solution is 3-5% of sodium hydroxide aqueous solution or 3-5% of potassium hydroxide aqueous solution in percentage by mass.
The silver-loaded nano zinc oxide is prepared by the following steps:
step I: adding 1 part of nano zinc oxide into 10 parts of deionized water by weight, and performing ultrasonic dispersion to obtain a nano zinc oxide aqueous solution.
Step II: slowly adding 1.2-1.5 parts by weight of AgNO into nano zinc oxide aqueous solution3Stirring for 3-5h at 70-80 ℃ and pH 4-5 to obtain the silver-loaded nano zinc oxide solution.
Step III: adding deionized water into the silver-loaded nano zinc oxide solution, filtering, drying filter residue, cooling and grinding into powder to obtain the silver-loaded nano zinc oxide.
The mixing method comprises the following steps: mixing materials by an internal mixer, wherein the working temperature of the internal mixer is set to be 160-180 ℃, the rotating speed is 60-80r/min, and the mixing time is 30-45 min.
The granulation method comprises the following steps: granulating by a double-screw extruder, wherein the heating temperature of each section of the double-screw extruder is respectively 145 ℃ plus or minus 5 ℃ in a first area, 150 ℃ plus or minus 5 ℃ in a second area, 160 ℃ plus or minus 5 ℃ in a third area, 170 ℃ plus or minus 5 ℃ in a fourth area, 170 ℃ plus or minus 5 ℃ in a fifth area, 160 ℃ plus or minus 5 ℃ in a sixth area, 150 ℃ plus or minus 5 ℃ in a seventh area, 145 ℃ plus or minus 5 ℃ in an eighth area, the rotating speed of a main machine is 25-30r/min, and the material pressure is 3-4.
The film blowing adopts a five-section heating film blowing machine, and the film blowing temperature is set to 140 +/-5 ℃ in a first area, 145 +/-5 ℃ in a second area, 150 +/-5 ℃ in a third area, 145 +/-5 ℃ in a fourth area and 140 +/-5 ℃ in a fifth area.
The dispersing agent is one or a mixture of several of ethylene bisstearamide, butyl stearate and microcrystalline paraffin in any proportion.
The antioxidant is prepared by mixing 2, 6-tertiary butyl-4-methylphenol and docosanol ester according to the weight ratio of 1: 0.3-0.5.
The invention has the following advantages:
(1) in the invention, the effective components of dandelion are extracted, and then the extracted dandelion extract and AgNO are mixed3The prepared nano-silver bacteriostatic agent has a far better bacteriostatic effect than the nano-silver bacteriostatic agent commonly used in the market at present.
(2) The dandelion is a common plant with low economic cost, and meanwhile, the dandelion extract has a high-efficiency bacteriostatic effect, so that the dandelion extract is suitable for industrial production.
(3) The nano silver has huge specific surface area, so that the antibacterial active ingredients in the dandelion extract can be effectively adsorbed.
(4) The nano silver adsorbed with the antibacterial active ingredients in the dandelion extract can be subjected to flocculation precipitation by adding the vegetable gum; therefore, the antibacterial active ingredients in the dandelion extract can be extracted, and the dandelion extract can be well purified. And borax is added as a cross-linking agent, so that the flocculation deposition process can be accelerated. The purification and purification process of the nano-silver bacteriostatic agent is simple and efficient to operate and is suitable for large-scale application in industrial production.
(5) The polyethylene resin blend adopts low-density polyethylene, medium-density polyethylene and linear low-density polyethylene which are mixed according to a certain proportion, and the added modified lignocellulose is combined, so that the prepared film has high strength, and the problem of low strength of the low-density polyethylene film in the market is effectively improved.
(6) The addition of the modified lignocellulose enhances the surface adhesion of the polyethylene resin blend, so that the polyethylene resin blend is better combined with a nano-silver bacteriostatic agent with bacteriostatic effect and silver-loaded nano-zinc oxide.
(7) The film produced by combining the nano-silver bacteriostatic agent, the polyethylene resin blend, the modified lignocellulose and the silver-loaded nano-zinc oxide has obvious bacteriostatic effect, is safe and has simple production and preparation process.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The first embodiment is as follows:
a preparation process of an antibacterial film comprises the following steps of taking 1 part of nano-silver antibacterial agent, 100 parts of polyethylene resin blend, 2 parts of modified lignocellulose, 0.5 part of silver-loaded nano zinc oxide, 1 part of plasticizer, 0.05 part of dispersant and 0.1 part of antioxidant by weight part, mixing, granulating, drying and blowing to obtain the antibacterial film.
The nano-silver bacteriostatic agent is prepared according to the following steps:
step a: drying and crushing dandelion leaves and dandelion roots respectively, mixing the dandelion leaves and the dandelion roots according to the weight ratio of 1:2, mixing the dandelion leaves and the dandelion roots with a 50% ethanol solution, heating and refluxing for 30min at 100 ℃, repeating for 3 times, combining the extracts for 3 times, evaporating under reduced pressure at 35 ℃ to obtain a dandelion extract, and diluting the dandelion extract to 100mg/mL by using 70% ethanol to obtain a dandelion extract.
Step b: taking 7 parts of dandelion extract and 0.05mol/L AgNO by weight3Mixing 1 part of the solution, adding 30 parts of deionized water, stirring uniformly, heating and refluxing at 100 ℃, stopping heating when the solution gradually becomes dark yellow, and identifying the absorption peak to be 458nm and the absorption peak range to be 400-500nm by adopting an ultraviolet-visible spectrum method, thus determining that the nano-silver composition is obtained.
Step c: and c, adding 0.05 part by weight of plant gum and 0.02 part by weight of borax into the nano-silver composition prepared in the step b, stirring for 1-2 hours, standing and precipitating to obtain a flocculation extract.
Step d: and drying the flocculated extract to obtain the nano-silver bacteriostatic agent.
The polyethylene resin blend comprises the following components in parts by weight: 35 parts of low-density polyethylene, 20 parts of medium-density polyethylene and 5 parts of linear low-density polyethylene.
The modified lignocellulose is prepared by the following steps:
step A: adding 15 parts by weight of polyethylene glycol into 40 parts by weight of deionized water, and fully stirring until the polyethylene glycol is completely dissolved to obtain a polyethylene glycol aqueous solution.
And B: adding 5 parts by weight of lignocellulose into an alkaline solution for activation treatment, then adding 30 parts by weight of deionized water, and ultrasonically dispersing for 3 times in an ice water bath, wherein the ultrasonic time is 10min each time, so as to obtain the lignocellulose aqueous solution.
And C: adding the lignocellulose aqueous solution into a polyethylene glycol aqueous solution, magnetically stirring for 2 hours at room temperature, stirring in a water bath at 90 ℃ to evaporate the water solvent, drying by distillation, placing in a vacuum drying oven, and drying into powder at 60 ℃ to obtain the modified lignocellulose.
Preferably, the alkaline solution is a 3% sodium hydroxide aqueous solution by mass fraction.
The silver-loaded nano zinc oxide is prepared by the following steps:
step I: adding 1 part of nano zinc oxide into 10 parts of deionized water by weight, and performing ultrasonic dispersion to obtain a nano zinc oxide aqueous solution.
Step II: slowly adding 1.2 weight parts of AgNO into nano zinc oxide aqueous solution3Stirring for 3 hours at the temperature of 70 ℃ and within the pH value range of 4-5 to prepare the silver-loaded nano zinc oxide solution.
Step III: adding deionized water into the silver-loaded nano zinc oxide solution, filtering, drying filter residue, cooling and grinding into powder to obtain the silver-loaded nano zinc oxide.
The mixing method comprises the following steps: mixing materials by an internal mixer, wherein the working temperature of the internal mixer is set to be 160 ℃, the rotating speed is 60r/min, and the mixing time is 30 min.
The granulation method comprises the following steps: granulating by a double-screw extruder, wherein the heating temperature of each section of the double-screw extruder is 140 ℃ in the first zone, 145 ℃ in the second zone, 155 ℃ in the third zone, 165 ℃ in the fourth zone, 165 ℃ in the fifth zone, 155 ℃ in the sixth zone, 145 ℃ in the seventh zone, 140 ℃ in the eighth zone, the rotating speed of a main machine is 25r/min, and the material pressure is 3 Mpa.
The film blowing adopts a five-section heating film blowing machine, and the film blowing temperature is set to be 135 ℃ in a first area, 140 ℃ in a second area, 145 ℃ in a third area, 140 ℃ in a fourth area and 135 ℃ in a fifth area.
The dispersant is ethylene distearamide.
The antioxidant is prepared by mixing 2, 6-tertiary butyl-4-methylphenol and docosanol ester according to the weight ratio of 1: 0.3.
Example two:
a preparation process of an antibacterial film comprises the steps of taking 2 parts by weight of nano-silver bacteriostat, 120 parts by weight of polyethylene resin blend, 4 parts by weight of modified lignocellulose, 1 part by weight of silver-loaded nano zinc oxide, 2 parts by weight of plasticizer, 0.1 part by weight of dispersant and 0.6 part by weight of antioxidant, mixing, granulating, drying and blowing to prepare the antibacterial film.
The nano-silver bacteriostatic agent is prepared according to the following steps:
step a: drying and crushing dandelion leaves and dandelion roots respectively, mixing the dandelion leaves and the dandelion roots according to the weight ratio of 1:3, mixing the dandelion leaves and the dandelion roots with a 50% ethanol solution, heating and refluxing for 40min at 100 ℃, repeating for 3 times, combining the extracts for 3 times, evaporating under reduced pressure at 35 ℃ to obtain a dandelion extract, and diluting the dandelion extract to 100mg/mL by using 70% ethanol to obtain a dandelion extract.
Step b: taking 8 parts of dandelion extract and 0.05mol/L AgNO by weight3Mixing 2 parts of the solution, adding 30 parts of deionized water, stirring uniformly, heating and refluxing at 100 ℃, stopping heating when the solution gradually becomes dark yellow, and identifying the absorption peak to be 458nm and the absorption peak range to be 400-500nm by adopting an ultraviolet-visible spectrum method, thus determining that the nano-silver compound is obtained.
Step c: and c, adding 0.1 part by weight of plant gum and 0.05 part by weight of borax into the nano-silver composition prepared in the step b, stirring for 2 hours, standing and precipitating to obtain a flocculation extract.
Step d: and drying the flocculated extract to obtain the nano-silver bacteriostatic agent.
The polyethylene resin blend comprises the following components in parts by weight: 40 parts of low-density polyethylene, 25 parts of medium-density polyethylene and 8 parts of linear low-density polyethylene.
The modified lignocellulose is prepared by the following steps:
step A: and adding 20 parts by weight of polyethylene glycol into 40 parts by weight of deionized water, and fully stirring until the polyethylene glycol is completely dissolved to obtain a polyethylene glycol aqueous solution.
And B: adding 8 parts by weight of lignocellulose into an alkaline solution for activation treatment, then adding 30 parts by weight of deionized water, and ultrasonically dispersing for 3 times in an ice water bath, wherein the ultrasonic time is 10min each time, so as to obtain the lignocellulose aqueous solution.
And C: adding the lignocellulose aqueous solution into a polyethylene glycol aqueous solution, magnetically stirring for 2 hours at room temperature, stirring in a water bath at 90 ℃ to evaporate the water solvent, drying by distillation, placing in a vacuum drying oven, and drying into powder at 60 ℃ to obtain the modified lignocellulose.
Preferably, the alkaline solution is a 5% potassium hydroxide aqueous solution by mass fraction.
The silver-loaded nano zinc oxide is prepared by the following steps:
step I: adding 1 part of nano zinc oxide into 10 parts of deionized water by weight, and performing ultrasonic dispersion to obtain a nano zinc oxide aqueous solution.
Step II: slowly adding 1.5 weight parts of AgNO into nano zinc oxide aqueous solution3Stirring for 5 hours at the temperature of 80 ℃ and within the pH value range of 4-5 to prepare the silver-loaded nano zinc oxide solution.
Step III: adding deionized water into the silver-loaded nano zinc oxide solution, filtering, drying filter residue, cooling and grinding into powder to obtain the silver-loaded nano zinc oxide.
The mixing method comprises the following steps: mixing materials by an internal mixer, wherein the working temperature of the internal mixer is set to 180 ℃, the rotating speed is 80r/min, and the mixing time is 45 min.
The granulation method comprises the following steps: granulating by a double-screw extruder, wherein the heating temperature of each section of the double-screw extruder is respectively 150 ℃ in a first zone, 155 ℃ in a second zone, 165 ℃ in a third zone, 175 ℃ in a fourth zone, 175 ℃ in a fifth zone, 165 ℃ in a sixth zone, 155 ℃ in a seventh zone, 150 ℃ in an eighth zone, the rotating speed of a main machine is 30r/min, and the material pressure is 4 Mpa.
The film blowing adopts a five-section heating film blowing machine, and the film blowing temperature is set to 145 ℃ in a first zone, 150 ℃ in a second zone, 155 ℃ in a third zone, 150 ℃ in a fourth zone and 145 ℃ in a fifth zone.
The dispersing agent is prepared by mixing ethylene distearamide, butyl stearate and microcrystalline paraffin in a weight ratio of 2:2: 3.
The antioxidant is prepared by mixing 2, 6-tertiary butyl-4-methylphenol and docosanol ester according to the weight ratio of 1: 0.5.
Example three:
a preparation process of an antibacterial film comprises the following steps of taking 1.5 parts by weight of nano-silver antibacterial agent, 110 parts by weight of polyethylene resin blend, 3 parts by weight of modified lignocellulose, 0.75 part by weight of silver-loaded nano zinc oxide, 1.5 parts by weight of plasticizer, 0.075 part by weight of dispersing agent and 0.35 part by weight of antioxidant, mixing, granulating, drying and blowing to obtain the antibacterial film.
The nano-silver bacteriostatic agent is prepared according to the following steps:
step a: drying and crushing dandelion leaves and dandelion roots respectively, mixing the dandelion leaves and the dandelion roots according to the weight ratio of 1:2.5, mixing the dandelion leaves and the dandelion roots with a 50% ethanol solution, heating and refluxing for 35min at 100 ℃, repeating for 3 times, combining the extracts for 3 times, evaporating under reduced pressure at 35 ℃ to obtain dandelion extract, and diluting the dandelion extract to 100mg/mL by using 70% ethanol to obtain dandelion extract.
Step b: taking 7.5 parts of dandelion extract and 0.05mol/L AgNO by weight3Mixing 1.5 parts of solution, adding 30 parts of deionized water, stirring uniformly, heating and refluxing at 100 ℃, stopping heating when the solution gradually becomes dark yellow, and identifying the absorption peak to be 458nm and the absorption peak range to be 400-500nm by adopting an ultraviolet-visible spectrum method, thus determining that the nano-silver composition is obtained.
Step c: and c, adding 0.075 part by weight of plant gum and 0.03 part by weight of borax into the nano-silver composition prepared in the step b, stirring for 1-2 hours, standing, and precipitating to obtain a flocculation extract.
Step d: and drying the flocculated extract to obtain the nano-silver bacteriostatic agent.
The polyethylene resin blend comprises the following components in parts by weight: 38 parts of low-density polyethylene, 22 parts of medium-density polyethylene and 6.5 parts of linear low-density polyethylene.
The modified lignocellulose is prepared by the following steps:
step A: adding 17.5 parts by weight of polyethylene glycol into 40 parts by weight of deionized water, and fully stirring until the polyethylene glycol is completely dissolved to obtain a polyethylene glycol aqueous solution.
And B: adding 6.5 parts by weight of lignocellulose into an alkaline solution for activation treatment, then adding 30 parts by weight of deionized water, and ultrasonically dispersing for 3 times in an ice water bath, wherein the ultrasonic time is 10min each time, so as to obtain the lignocellulose aqueous solution.
And C: adding the lignocellulose aqueous solution into a polyethylene glycol aqueous solution, magnetically stirring for 2 hours at room temperature, stirring in a water bath at 90 ℃ to evaporate the water solvent, drying by distillation, placing in a vacuum drying oven, and drying into powder at 60 ℃ to obtain the modified lignocellulose.
Preferably, the alkaline solution is a sodium hydroxide aqueous solution with the mass fraction of 4%.
The silver-loaded nano zinc oxide is prepared by the following steps:
step I: adding 1 part of nano zinc oxide into 10 parts of deionized water by weight, and performing ultrasonic dispersion to obtain a nano zinc oxide aqueous solution.
Step II: slowly adding 1.35 parts by weight of AgNO into nano zinc oxide aqueous solution3Stirring for 4 hours at the temperature of 75 ℃ and within the pH value range of 4-5 to prepare the silver-loaded nano zinc oxide solution.
Step III: adding deionized water into the silver-loaded nano zinc oxide solution, filtering, drying filter residue, cooling and grinding into powder to obtain the silver-loaded nano zinc oxide.
The mixing method comprises the following steps: mixing materials by an internal mixer, wherein the working temperature of the internal mixer is set to be 170 ℃, the rotating speed is 70r/min, and the mixing time is 38 min.
The granulation method comprises the following steps: granulating by a double-screw extruder, wherein the heating temperature of each section of the double-screw extruder is 145 ℃ in the first zone, 150 ℃ in the second zone, 160 ℃ in the third zone, 170 ℃ in the fourth zone, 170 ℃ in the fifth zone, +/-5 ℃ in the fifth zone, 160 ℃ in the sixth zone, 150 ℃ in the seventh zone, 145 ℃ in the eighth zone, the rotating speed of a main machine is 28r/min, and the material pressure is 3.5 MPa.
The film blowing adopts a five-section heating film blowing machine, and the film blowing temperature is set to be 140 ℃ in a first area, 145 ℃ in a second area, 150 ℃ in a third area, 145 ℃ in a fourth area and 140 ℃ in a fifth area.
The dispersing agent is prepared by mixing ethylene butyl stearate and microcrystalline wax in a weight ratio of 1:2.
The antioxidant is prepared by mixing 2, 6-tertiary butyl-4-methylphenol and docosanol ester according to the weight ratio of 1: 0.4.
Example four:
a preparation process of an antibacterial film comprises the following steps of taking 1.2 parts by weight of nano-silver antibacterial agent, 115 parts by weight of polyethylene resin blend, 2.8 parts by weight of modified lignocellulose, 0.7 part by weight of silver-loaded nano zinc oxide, 1.3 parts by weight of plasticizer, 0.05 part by weight of dispersant and 0.5 part by weight of antioxidant, mixing, granulating, drying and blowing to obtain the antibacterial film.
The nano-silver bacteriostatic agent is prepared according to the following steps:
step a: drying and crushing dandelion leaves and dandelion roots respectively, mixing the dandelion leaves and the dandelion roots according to the weight ratio of 1:2.8, mixing the dandelion leaves and the dandelion roots with a 50% ethanol solution, heating and refluxing for 33min at 100 ℃, repeating for 3 times, combining the extracts for 3 times, evaporating under reduced pressure at 35 ℃ to obtain dandelion extract, and diluting the dandelion extract to 100mg/mL by using 70% ethanol to obtain dandelion extract.
Step b: taking 7.2 parts of dandelion extract and 0.05mol/L AgNO by weight3Mixing 1.3 parts of solution, adding 30 parts of deionized water, stirring uniformly, heating and refluxing at 100 ℃, stopping heating when the solution gradually becomes dark yellow, and identifying the absorption peak to be 458nm and the absorption peak range to be 400-500nm by adopting an ultraviolet-visible spectrum method, thus determining that the nano-silver composition is obtained.
Step c: and c, adding 0.08 part by weight of plant gum and 0.03 part by weight of borax into the nano-silver composition prepared in the step b, stirring for 1.6 hours, standing and precipitating to obtain a flocculation extract.
Step d: and drying the flocculated extract to obtain the nano-silver bacteriostatic agent.
The polyethylene resin blend comprises the following components in parts by weight: 37 parts of low-density polyethylene, 22 parts of medium-density polyethylene and 6 parts of linear low-density polyethylene.
The modified lignocellulose is prepared by the following steps:
step A: adding 19 parts by weight of polyethylene glycol into 40 parts by weight of deionized water, and fully stirring until the polyethylene glycol is completely dissolved to obtain a polyethylene glycol aqueous solution.
And B: adding 7 parts by weight of lignocellulose into an alkaline solution for activation treatment, then adding 30 parts by weight of deionized water, and ultrasonically dispersing for 3 times in an ice water bath, wherein the ultrasonic time is 10min each time, so as to obtain the lignocellulose aqueous solution.
And C: adding the lignocellulose aqueous solution into a polyethylene glycol aqueous solution, magnetically stirring for 2 hours at room temperature, stirring in a water bath at 90 ℃ to evaporate the water solvent, drying by distillation, placing in a vacuum drying oven, and drying into powder at 60 ℃ to obtain the modified lignocellulose.
Preferably, the alkaline solution is a potassium hydroxide aqueous solution with the mass fraction of 4.5%.
The silver-loaded nano zinc oxide is prepared by the following steps:
step I: adding 1 part of nano zinc oxide into 10 parts of deionized water by weight, and performing ultrasonic dispersion to obtain a nano zinc oxide aqueous solution.
Step II: slowly adding 1.2 weight parts of AgNO into nano zinc oxide aqueous solution3Stirring for 4.5h at 77 ℃ and pH 4-5 to obtain the silver-loaded nano zinc oxide solution.
Step III: adding deionized water into the silver-loaded nano zinc oxide solution, filtering, drying filter residue, cooling and grinding into powder to obtain the silver-loaded nano zinc oxide.
The mixing method comprises the following steps: mixing the materials by an internal mixer, wherein the working temperature of the internal mixer is set to 165 ℃, the rotating speed is 75r/min, and the mixing time is 40 min.
The granulation method comprises the following steps: granulating by a double-screw extruder, wherein the heating temperature of each section of the double-screw extruder is 145 ℃ in the first zone, 155 ℃ in the second zone, 165 ℃ in the third zone, 175 ℃ in the fourth zone, 165 ℃ in the fifth zone, 160 ℃ in the sixth zone, 150 ℃ in the seventh zone, 145 ℃ in the eighth zone, the rotating speed of a main engine is 30r/min, and the material pressure is 4 Mpa.
The film blowing adopts a five-section heating film blowing machine, and the film blowing temperature is set to 140 ℃ in a first zone, 150 ℃ in a second zone, 155 ℃ in a third zone, 145 ℃ in a fourth zone and 135 ℃ in a fifth zone.
The dispersing agent is microcrystalline paraffin.
The antioxidant is prepared by mixing 2, 6-tertiary butyl-4-methylphenol and docosanol ester according to the weight ratio of 1: 0.35.
Comparative example one:
plastic films are commercially available.
Comparative example two:
the nano-silver bacteriostatic agent in the first embodiment is changed into nano-silver powder with the same weight part, the preparation step of the nano-silver bacteriostatic agent is omitted, and the rest raw materials and the preparation process are unchanged.
Comparative example three:
the nano-silver bacteriostat in the raw materials in the first embodiment is removed, the preparation step of the nano-silver bacteriostat is cancelled, and the other raw materials and the preparation process are not changed.
Comparative example four:
the silver-loaded nano zinc oxide in the first embodiment is changed into nano zinc oxide with the same weight part, the preparation step of the silver-loaded nano zinc oxide is cancelled, and other raw materials and the preparation process are unchanged.
Comparative example five:
the silver-loaded nano zinc oxide in the raw materials in the first embodiment is removed, the preparation step of the silver-loaded nano zinc oxide is cancelled, and the rest raw materials and the preparation process are unchanged.
Comparative example six:
the modified lignocellulose obtained in the first embodiment is changed into the lignocellulose with the same weight part, the preparation step of the modified lignocellulose is omitted, and the rest raw materials and the preparation process are unchanged.
Comparative example seven:
modified lignocellulose in the raw materials in the first embodiment is removed, the preparation step of the silver-loaded nano zinc oxide is cancelled, and the rest raw materials and the preparation process are unchanged.
Comparative example eight:
the polyethylene resin blend in the first embodiment is changed into the low-density polyethylene with the same weight part, and the rest raw materials and the preparation process are not changed.
The mechanical properties of the films prepared in the first to fourth examples and the first to eighth comparative examples were respectively tested; the bacteriostatic rate of the test film to escherichia coli and staphylococcus aureus is shown in the following table:
the data show that the film prepared by the nano-silver bacteriostatic agent added with the dandelion extract has obvious improvement on bacteriostatic efficiency; although the nano-silver also has a certain bacteriostatic action, when the nano-silver is used in combination with the dandelion extract, the bacteriostatic effect is better; the bacteriostatic efficiency of the film prepared after the silver-loaded nano zinc oxide is added is higher than that of the film prepared without the silver-loaded nano zinc oxide; although the nano zinc oxide has certain bacteriostatic efficiency, the bacteriostatic efficiency of the film prepared by the nano zinc oxide loaded with silver is not as high; the mechanical property of the film can be changed by the lignocellulose, so that the mechanical property of the film is better; the mechanical property of the film prepared from the modified lignocellulose is superior to that of the film prepared from the unmodified lignocellulose, and the modified lignocellulose improves the bacteriostasis rate of the film to a certain extent; the performance of the film prepared by using the polyethylene resin blend as the main raw material is superior to that of the film prepared by only using the low-density polyethylene as the main raw material. As shown above, when the film produced by combining the nano-silver bacteriostatic agent, the polyethylene resin blend, the modified lignocellulose and the silver-loaded nano zinc oxide is high in bacteriostatic effect and bacteriostatic rate, the mechanical property of the film is good, and the bacteriostatic rate and the mechanical property are obviously superior to those of the existing plastic film in the market.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (10)
1. A preparation process of an antibacterial film is characterized by taking 1-2 parts of nano-silver antibacterial agent, 120 parts of polyethylene resin blend, 2-4 parts of modified lignocellulose, 0.5-1 part of silver-loaded nano zinc oxide, 1-2 parts of plasticizer, 0.05-0.1 part of dispersant and 0.1-0.6 part of antioxidant by weight part, mixing, granulating, drying and blowing to prepare the antibacterial film.
2. The preparation process of the bacteriostatic film according to claim 1, wherein the nano-silver bacteriostatic agent is prepared according to the following steps:
step a: drying and crushing dandelion leaves and dandelion roots respectively, mixing the dandelion leaves and the dandelion roots according to a weight ratio of 1: 2-3, mixing the dandelion leaves and the dandelion roots with a 50% ethanol solution, carrying out heating reflux for 30-40min at 100 ℃, repeating for 3 times, combining the extracts for 3 times, carrying out reduced pressure evaporation at 35 ℃ to obtain dandelion extract, and diluting the dandelion extract to 100mg/mL by using 70% ethanol to obtain dandelion extract;
step b: taking 7-8 parts of dandelion extract and 0.05mol/L AgNO by weight3Mixing 1-2 parts of the solution, adding 30 parts of deionized water, stirring uniformly, heating and refluxing at 100 ℃, stopping heating when the solution gradually becomes dark yellow, and identifying the absorption peak to be 458nm and the absorption peak range of the nano-silver surface to be 400-500nm by adopting an ultraviolet-visible spectrum method, thus determining that the nano-silver composition is obtained;
step c: b, adding 0.05-0.1 part by weight of plant gum and 0.02-0.05 part by weight of borax into the nano-silver composition prepared in the step b, stirring for 1-2 hours, standing and precipitating to obtain a flocculation extract;
step d: and drying the flocculated extract to obtain the nano-silver bacteriostatic agent.
3. The preparation process of the bacteriostatic film according to claim 1, wherein the polyethylene resin blend comprises the following components in parts by weight: 35-40 parts of low-density polyethylene, 20-25 parts of medium-density polyethylene and 5-8 parts of linear low-density polyethylene.
4. The process for preparing a bacteriostatic film according to claim 1, wherein the modified lignocellulose is prepared by the following steps:
step A: adding 15-20 parts by weight of polyethylene glycol into 40 parts by weight of deionized water, and fully stirring until the polyethylene glycol is completely dissolved to prepare a polyethylene glycol aqueous solution;
and B: adding 5-8 parts by weight of lignocellulose into an alkaline solution for activation treatment, then adding 30 parts by weight of deionized water, and ultrasonically dispersing for 3 times in an ice water bath, wherein the ultrasonic time is 10min each time to obtain a lignocellulose aqueous solution;
and C: adding the lignocellulose aqueous solution into a polyethylene glycol aqueous solution, magnetically stirring for 2 hours at room temperature, stirring in a water bath at 90 ℃ to evaporate a water solvent, drying by distillation, placing in a vacuum drying oven, and drying into powder at 60 ℃ to obtain modified lignocellulose;
the alkaline solution is 3-5% of sodium hydroxide aqueous solution or 3-5% of potassium hydroxide aqueous solution by mass fraction.
5. The preparation process of the bacteriostatic film according to claim 1, wherein the silver-loaded nano zinc oxide is prepared according to the following steps:
step I: adding 1 part of nano zinc oxide into 10 parts of deionized water by weight, and performing ultrasonic dispersion to prepare a nano zinc oxide aqueous solution;
step II: into nano zinc oxide aqueous solutionSlowly adding 1.2-1.5 parts by weight of AgNO3Stirring for 3-5h at 70-80 ℃ and pH 4-5 to obtain silver-loaded nano zinc oxide solution;
step III: adding deionized water into the silver-loaded nano zinc oxide solution, filtering, drying filter residue, cooling and grinding into powder to obtain the silver-loaded nano zinc oxide.
6. The preparation process of the bacteriostatic film according to claim 1, wherein the mixing method comprises the following steps: mixing materials by an internal mixer, wherein the working temperature of the internal mixer is set to be 160-180 ℃, the rotating speed is 60-80r/min, and the mixing time is 30-45 min.
7. The process for preparing a bacteriostatic film according to claim 1, wherein the granulating method comprises the following steps: granulating by a double-screw extruder, wherein the heating temperature of each section of the double-screw extruder is respectively 145 ℃ plus or minus 5 ℃ in a first area, 150 ℃ plus or minus 5 ℃ in a second area, 160 ℃ plus or minus 5 ℃ in a third area, 170 ℃ plus or minus 5 ℃ in a fourth area, 170 ℃ plus or minus 5 ℃ in a fifth area, 160 ℃ plus or minus 5 ℃ in a sixth area, 150 ℃ plus or minus 5 ℃ in a seventh area, 145 ℃ plus or minus 5 ℃ in an eighth area, the rotating speed of a main machine is 25-30r/min, and the material pressure is 3-4.
8. The process for preparing a bacteriostatic film according to claim 1, wherein the film blowing adopts a five-section heating film blowing machine, and the film blowing temperature is set to 140 ℃ plus or minus 5 ℃ in the first zone, 145 ℃ plus or minus 5 ℃ in the second zone, 150 ℃ plus or minus 5 ℃ in the third zone, 145 ℃ plus or minus 5 ℃ in the fourth zone and 140 ℃ plus or minus 5 ℃ in the fifth zone.
9. The process for preparing a bacteriostatic film according to claim 1, wherein the dispersing agent is one or more of ethylene bis stearamide, butyl stearate and microcrystalline wax which are mixed in any proportion.
10. The preparation process of the antibacterial film according to claim 1, wherein the antioxidant is prepared by mixing 2, 6-tertiary butyl-4-methylphenol and didodecyl alcohol ester according to a weight ratio of 1: 0.3-0.5.
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