CN114539697B - PVA film modified by one-step reaction extrusion method and preparation method and application thereof - Google Patents

PVA film modified by one-step reaction extrusion method and preparation method and application thereof Download PDF

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CN114539697B
CN114539697B CN202210069816.4A CN202210069816A CN114539697B CN 114539697 B CN114539697 B CN 114539697B CN 202210069816 A CN202210069816 A CN 202210069816A CN 114539697 B CN114539697 B CN 114539697B
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肖性龙
刘峰松
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South China University of Technology SCUT
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
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    • C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
    • C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
    • C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
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Abstract

The invention belongs to the technical field of polyvinyl alcohol (PVA) antibacterial films, and discloses a PVA film modified by a one-step reaction extrusion method, and a preparation method and application thereof, wherein the PVA film comprises the following raw materials in parts by mass: 10-30 parts of PVA, 5-15 parts of chitosan, 3-5 parts of alkyl compound, 5-15 parts of halogenated propylene oxide, 10-20 parts of isopropanol solution, 5-15 parts of sodium hydroxide solution, 3-5 parts of plasticizer and 20-60 parts of water. The method comprises the following steps: firstly, obtaining quaternary ammonium salt modified chitosan through nucleophilic substitution reaction by a double-screw reaction extruder, conveying the quaternary ammonium salt modified chitosan to a single-screw extruder for plasticizing and uniformly mixing, extruding the quaternary ammonium salt modified chitosan into a film by a machine head under high temperature and high pressure, and finally, drying the film in vacuum to obtain the modified PVA film. The film provided by the invention has the advantages of simple manufacture, low cost, stable antibacterial performance, biodegradability and excellent mechanical property, and can be applied to the field of food preservation to replace the traditional packaging film material.

Description

PVA film modified by one-step reaction extrusion method and preparation method and application thereof
Technical Field
The invention belongs to the technical field of PVA antibacterial films, and particularly relates to a PVA film modified by a one-step reaction extrusion method, and a preparation method and application thereof.
Background
The traditional food packaging plastic products such as plastic bags, plastic films, plastic trays and the like are mostly made of polyethylene, polypropylene and the like, so that the plastic products are difficult to degrade and pollute the environment, and bacteria are easy to grow on the plastic products to harm the health of human beings. And the polyvinyl alcohol (PVA) has excellent biodegradability, easy film formation, good biocompatibility and mechanical property, and is very beneficial to processing and preparing the film material. For this reason, the problem of how to improve the compatibility between the antibacterial agent and PVA and the stable release of the antibacterial ability of the antibacterial agent, which is a difficulty and breakthrough in the current research, is beginning to be introduced into the antibacterial function of the product by adding the antibacterial agent to the PVA film and applying the antibacterial coating.
The chitosan is a natural polysaccharide compound and has the advantages of wide sources, environmental protection, easy degradation, easy modification and the like, but the natural chitosan has poor compatibility with water-soluble PVA, which limits the application modification. The quaternary ammonium salt modified cationic chitosan derivative not only enhances the water solubility and the compatibility with PVA, but also has stronger antibacterial property, good film forming property and excellent degradation property. However, the conventional quaternary ammonium salt chitosan, such as hydroxypropyl trimethyl ammonium chloride chitosan, has poor hot workability and poor stability, and has unsatisfactory antibacterial effect, and the antibacterial agent is easily volatilized or decomposed in the film preparation process by the PVA film modified by hydroxypropyl trimethyl ammonium chloride chitosan, so that the antibacterial effect and the antibacterial stability of the antibacterial agent are affected. For example, patent CN103144280a provides films of different antimicrobial capabilities by controlling the mass ratio of PVA to chitosan. Further, as disclosed in patent CN104987635a, the PVA antibacterial packaging film uses PVA resin as a base material, uses glycerol, potassium sorbate and quaternary ammonium salt chitosan as a modifying auxiliary agent, and the biggest problem of the quaternary ammonium salt chitosan modified PVA film is how to solve the problems of release of antibacterial performance and insufficient antibacterial stability of the quaternary ammonium salt chitosan on the film, so that a new method is urgently needed to modify PVA by using quaternary ammonium salt chitosan, thereby preparing a modified PVA film material with excellent antibacterial performance and great application prospect and industrial value.
Aiming at the defects of easy decomposition at high temperature and insufficient antibacterial stability of the traditional quaternary ammonium salt chitosan, the invention adopts the high-temperature resistant quaternary ammonium salt modified chitosan such as polyalkyl ammonium chloride, omits the complicated repeated high-temperature processing technology to damage the modified quaternary ammonium salt chitosan by a one-step reaction extrusion method, and ensures the stable release of the antibacterial capability of the modified quaternary ammonium salt chitosan on the PVA film. For example, patent CN103144280a discloses a preparation method of degradable PVA blown film with antibacterial property, PVA and chitosan are used as main raw materials, and after granulation and film blowing are performed by a single screw extruder, the antibacterial stability of chitosan is obviously reduced after repeated extrusion processing. The PVA film modified by the one-step reaction extrusion method has the advantages of convenient preparation, low cost, high efficiency, strong antibacterial stability, complete biodegradation, environmental protection and no pollution, can completely replace products such as film materials which are not degradable in the market, and has great application prospect and value in the fields of food packaging and other film packaging, and is worthy of popularization.
Disclosure of Invention
Aiming at the defects of the prior art, the primary aim of the invention is to provide a PVA film modified by a one-step reaction extrusion method.
Another object of the present invention is to provide a method for preparing a PVA film modified by a one-step reactive extrusion method.
It is a further object of the present invention to provide the use of a PVA film modified by a one-step reactive extrusion process.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a PVA film modified by a one-step reaction extrusion method comprises the following components in parts by mass:
Figure BDA0003481630460000021
preferably, the PVA has an alcoholysis degree of 80-98%, a viscosity of 3-30 mPas and a molecular weight of 20,000-200,000.
Preferably, the deacetylation degree of the chitosan is more than or equal to 80%, the viscosity is 100-300 mPa.s, and the molecular weight is 30,000-500,000.
Preferably, the alkyl compound is one or more than two of hexadecyldimethylamine, tetradecyldimethylamine and dodecyl dimethylamine; the halogenated epoxypropane is one or more than two of epoxychloropropane, epoxybromopropane or epoxyiodopropane; the plasticizer is one or more than two of citric acid, glycerol, polyethylene glycol or water.
The preparation method of the film comprises the following steps:
(1) Twin-screw reactive extrusion modification: slowly adding halogenated epoxypropane and an alkyl compound into a double-screw extruder, then adding chitosan and isopropanol solution, uniformly stirring, adding sodium hydroxide solution to adjust the pH to 8-9, and reacting for 2-4 hours at the constant temperature of 65-75 ℃ to obtain the reaction extrusion modified quaternary ammonium salt chitosan;
(2) Single screw extrusion film forming: adding PVA, plasticizer and water into a single screw extruder, after the PVA is completely plasticized, conveying the modified quaternary ammonium salt chitosan obtained in the step (1) into the single screw extruder, stirring and mixing uniformly, extruding the mixture into a film through a machine head, and drying the film in vacuum to obtain the PVA film modified by the one-step reaction extrusion method.
Preferably, the screw speed of the twin-screw extruder in the step (1) is 20-100rpm, the heating temperature of the melting zone of the extruder is 60-70 ℃, the heating temperature of the reaction zone is 65-75 ℃, and the heating temperature of the conveying zone is 60-70 ℃.
Preferably, the screw speed of the single screw extruder in the step (2) is 20-100rpm, the heating temperature of the melting zone of the extruder is 75-90 ℃, the heating temperature of the conveying zone is 75-85 ℃, and the heating temperature of the pressure building zone is 80-90 ℃.
Preferably, the vacuum drying temperature in the step (2) is 50-60 ℃ and the drying time is 4-8h.
Preferably, the conditions for extrusion film formation by the handpiece in step (2) are as follows: the temperature of the die head is 90-100 ℃, and the internal pressure of the die head is 8-15MPa.
The film is applied to food preservation and film packaging.
Compared with the prior art, the invention has the advantages that:
(1) The modified PVA film material developed and prepared by the invention adopts a one-step reactive extrusion method preparation process, has the advantages of convenient preparation, high efficiency and low cost, omits the damage of complex processes of granulating and then film blowing of the traditional plastic preparation process to the modified quaternary ammonium salt chitosan, ensures the stable release of the antibacterial capability of the modified quaternary ammonium salt chitosan on the film, has strong process practicability, and can be applied and popularized industrially on a large scale.
(2) According to the PVA film modified by the one-step reaction extrusion method, the defects of poor processability, poor high-temperature stability and insufficient antibacterial effect of the traditional quaternary ammonium salt chitosan are overcome by introducing the polyalkyl ammonium chloride modified chitosan.
(3) The modified film has water absorption rate of 8% at the minimum, good hydrophobic property, mechanical property basically similar to that of common films such as polyethylene and polypropylene in the market, and can completely replace the nondegradable plastic film packaging material in the market.
(4) The invention provides a novel PVA film modified by a one-step reaction extrusion method, which has better effects on escherichia coli and staphylococcus aureusAntibacterial effect, 2.1 mug/ml and 3.l mug/ml modified long-chain alkyl quaternary ammonium salt chitosan solution can kill 10 respectively 6 The antibacterial capacity of the CFU/ml escherichia coli and staphylococcus aureus is improved by about 200 times compared with unmodified chitosan, and the antibacterial capacity of the CFU/ml escherichia coli and staphylococcus aureus is improved by about 150 times compared with hydroxypropyl trimethyl ammonium chloride chitosan. The PVA film modified by the invention can be widely applied to the film packaging fields of fruit and vegetable fresh-keeping, meat product refrigeration and the like, can greatly prolong the shelf life of foods and accelerate the popularization and application of the PVA film in the food fresh-keeping field.
Drawings
FIG. 1 is a simplified flow chart of the preparation of the present invention.
FIG. 2 is a graph of infrared spectroscopic measurements of Chitosan (CS), epoxypropyl dimethyl hexadecyl ammonium chloride (GDCA) and epoxypropyl dimethyl hexadecyl ammonium chloride modified chitosan (GDCA-CS) of example 1.
FIG. 3 is a graph showing the antibacterial property test of examples 1, 6 and 7 against E.coli and Staphylococcus aureus (S.aureus), wherein Control is the growth curve of E.coli or Staphylococcus aureus without modified quaternary chitosan; 3a) E.coli growth curves under different examples; 3b) Staphylococcus aureus growth curves for different examples.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by a person skilled in the art without making any inventive effort, are within the scope of the present invention based on the embodiments of the present invention.
In the embodiment of the invention, PVA (alcoholysis degree 80% -98%, guangzhou Minwei polyvinyl alcohol marketing Co., ltd.), chitosan (deacetylation degree not less than 80%, shanghai microphone Biochemical Co., ltd.), alkyl compound (cetyl dimethylamine, tetradecyl dimethylamine or dodecyl dimethylamine, purity not less than 97%, shanghai microphone Biochemical Co., ltd.), epichlorohydrin (molecular weight 92.52, tianjin Fuchen chemical reagent Co., ltd.), isopropanol (purity not less than 99.7%, tianjin Fuyu fine chemical Co., ltd.), plasticizer (glycerin, purity not less than 95%, tianjin Fuyu fine chemical Co., ltd.), deionized water.
Example 1
(1) Twin-screw reactive extrusion modification: setting the screw speed of a double-screw extruder to be 50rpm, heating the melting zone, the reaction zone and the conveying zone to be 60 ℃, 65 ℃ and 70 ℃ respectively, slowly adding 5 parts of epoxy chloropropane and 5 parts of cetyl dimethyl ammonium through a charging port, then adding 5 parts of chitosan and 10 parts of 50% isopropanol solution, slowly stirring and dispersing uniformly, adding 5 parts of 1mol/L sodium hydroxide solution, reacting at constant temperature for 2-4 hours, and obtaining the modified quaternary ammonium salt chitosan after nucleophilic substitution reaction is completed;
(2) Single screw extrusion film forming: the screw speed of a single screw extruder is regulated to 80rpm, the heating temperatures of each area of a banburying area, a conveying area and a pressure building area are respectively 80, 85 and 90 ℃, 10 parts of PVA, 3 parts of glycerol and 50 parts of water are added into a charging port, after PVA plasticization is complete, the quaternary ammonium salt chitosan after double screw reaction extrusion modification is conveyed into the single screw extruder, fully stirred and uniformly mixed, finally extruded into a film under the conditions that the die head temperature of a machine head is 90 ℃ and the internal pressure of the machine head is 9.8MPa, and immediately placed into a vacuum drying box and fully dried for 4 hours at 60 ℃, so that the PVA film modified by the one-step reaction extrusion method is finally obtained.
Example 2
(1) Twin-screw reactive extrusion modification: setting the screw speed of a double-screw extruder to be 50rpm, heating the melting zone, the reaction zone and the conveying zone to be 60 ℃, 65 ℃ and 70 ℃ respectively, slowly adding 5 parts of epoxy chloropropane and 5 parts of cetyl dimethyl ammonium through a charging port, then adding 10 parts of chitosan and 10 parts of 50% isopropanol solution, slowly stirring and dispersing uniformly, adding 5 parts of 1mol/L sodium hydroxide solution, reacting at constant temperature for 2-4 hours, and obtaining the modified quaternary ammonium salt chitosan after nucleophilic substitution reaction is completed;
(2) Single screw extrusion film forming: the screw speed of a single screw extruder is regulated to 80rpm, the heating temperatures of each area of a banburying area, a conveying area and a pressure building area are respectively 80, 85 and 90 ℃, 10 parts of PVA, 3 parts of glycerol and 50 parts of water are added into a charging port, after PVA plasticization is complete, the quaternary ammonium salt chitosan after double screw reaction extrusion modification is conveyed into the single screw extruder, fully stirred and uniformly mixed, finally extruded into a film under the conditions that the die head temperature of a machine head is 90 ℃ and the internal pressure of the machine head is 9.8MPa, and immediately placed into a vacuum drying box and fully dried for 4 hours at 60 ℃, so that the PVA film modified by the one-step reaction extrusion method is finally obtained.
Example 3
(1) Twin-screw reactive extrusion modification: setting the screw speed of a double-screw extruder to be 50rpm, heating the melting zone, the reaction zone and the conveying zone to be 60 ℃, 65 ℃ and 70 ℃ respectively, slowly adding 5 parts of epoxy chloropropane and 5 parts of cetyl dimethyl ammonium through a charging port, then adding 15 parts of chitosan and 10 parts of 50% isopropanol solution, slowly stirring and dispersing uniformly, adding 5 parts of 1mol/L sodium hydroxide solution, reacting at constant temperature for 2-4 hours, and obtaining the modified quaternary ammonium salt chitosan after nucleophilic substitution reaction is completed;
(2) Single screw extrusion film forming: the screw speed of a single screw extruder is regulated to 80rpm, the heating temperatures of each area of a banburying area, a conveying area and a pressure building area are respectively 80, 85 and 90 ℃, 10 parts of PVA, 3 parts of glycerol and 50 parts of water are added into a charging port, after PVA plasticization is complete, the quaternary ammonium salt chitosan after double screw reaction extrusion modification is conveyed into the single screw extruder, fully stirred and uniformly mixed, finally extruded into a film under the conditions that the die head temperature of a machine head is 90 ℃ and the internal pressure of the machine head is 9.8MPa, and immediately placed into a vacuum drying box and fully dried for 4 hours at 60 ℃, so that the PVA film modified by the one-step reaction extrusion method is finally obtained.
Example 4
(1) Twin-screw reactive extrusion modification: setting the screw speed of a double-screw extruder to be 50rpm, heating the melting zone, the reaction zone and the conveying zone to be 60 ℃, 65 ℃ and 70 ℃ respectively, slowly adding 10 parts of epoxy chloropropane and 5 parts of cetyl dimethyl ammonium through a charging port, then adding 5 parts of chitosan and 10 parts of 50% isopropanol solution, slowly stirring and dispersing uniformly, adding 5 parts of 1mol/L sodium hydroxide solution, reacting at constant temperature for 2-4 hours, and obtaining the modified quaternary ammonium salt chitosan after nucleophilic substitution reaction is completed;
(2) Single screw extrusion film forming: the screw speed of a single screw extruder is regulated to 80rpm, the heating temperatures of each area of a banburying area, a conveying area and a pressure building area are respectively 80, 85 and 90 ℃, 10 parts of PVA, 3 parts of glycerol and 50 parts of water are added into a charging port, after PVA plasticization is complete, the quaternary ammonium salt chitosan after double screw reaction extrusion modification is conveyed into the single screw extruder, fully stirred and uniformly mixed, finally extruded into a film under the conditions that the die head temperature of a machine head is 90 ℃ and the internal pressure of the machine head is 9.8MPa, and immediately placed into a vacuum drying box and fully dried for 4 hours at 60 ℃, so that the PVA film modified by the one-step reaction extrusion method is finally obtained.
Example 5
(1) Twin-screw reactive extrusion modification: setting the screw speed of a double-screw extruder to be 50rpm, heating the melting zone, the reaction zone and the conveying zone to be 60 ℃, 65 ℃ and 70 ℃ respectively, slowly adding 15 parts of epichlorohydrin and 5 parts of hexadecyl dimethyl ammonium through a charging port, then adding 5 parts of chitosan and 10 parts of 50% isopropanol solution, slowly stirring and dispersing uniformly, adding 5 parts of 1mol/L sodium hydroxide solution, reacting at constant temperature for 2-4 hours, and obtaining the modified quaternary ammonium salt chitosan after nucleophilic substitution reaction is completed;
(2) Single screw extrusion film forming: the screw speed of a single screw extruder is regulated to 80rpm, the heating temperatures of each area of a banburying area, a conveying area and a pressure building area are respectively 80, 85 and 90 ℃, 10 parts of PVA, 3 parts of glycerol and 50 parts of water are added into a charging port, after PVA plasticization is complete, the quaternary ammonium salt chitosan after double screw reaction extrusion modification is conveyed into the single screw extruder, fully stirred and uniformly mixed, finally extruded into a film under the conditions that the die head temperature of a machine head is 90 ℃ and the internal pressure of the machine head is 9.8MPa, and immediately placed into a vacuum drying box and fully dried for 4 hours at 60 ℃, so that the PVA film modified by the one-step reaction extrusion method is finally obtained.
Example 6
(1) Twin-screw reactive extrusion modification: setting the screw speed of a double-screw extruder to be 50rpm, heating the melting zone, the reaction zone and the conveying zone to be 60 ℃, 65 ℃ and 70 ℃ respectively, slowly adding 5 parts of epichlorohydrin and 5 parts of tetradecyl dimethyl ammonium through a charging port, then adding 5 parts of chitosan and 10 parts of 50% isopropanol solution, slowly stirring and dispersing uniformly, adding 5 parts of 1mol/L sodium hydroxide solution, reacting at constant temperature for 2-4 hours, and obtaining the modified quaternary ammonium salt chitosan after nucleophilic substitution reaction is completed;
(2) Single screw extrusion film forming: the screw speed of a single screw extruder is regulated to 80rpm, the heating temperatures of each area of a banburying area, a conveying area and a pressure building area are respectively 80, 85 and 90 ℃, 10 parts of PVA, 3 parts of glycerol and 50 parts of water are added into a charging port, after PVA plasticization is complete, the quaternary ammonium salt chitosan after double screw reaction extrusion modification is conveyed into the single screw extruder, fully stirred and uniformly mixed, finally extruded into a film under the conditions that the die head temperature of a machine head is 90 ℃ and the internal pressure of the machine head is 9.8MPa, and immediately placed into a vacuum drying box and fully dried for 4 hours at 60 ℃, so that the PVA film modified by the one-step reaction extrusion method is finally obtained.
Example 7
(1) Twin-screw reactive extrusion modification: setting the screw speed of a double-screw extruder to be 50rpm, heating the melting zone, the reaction zone and the conveying zone to be 60 ℃, 65 ℃ and 70 ℃ respectively, slowly adding 5 parts of epoxy chloropropane and 5 parts of dodecyl dimethyl ammonium through a charging port, then adding 5 parts of chitosan and 10 parts of 50% isopropanol solution, slowly stirring and dispersing uniformly, adding 5 parts of 1mol/L sodium hydroxide solution, reacting at constant temperature for 2-4 hours, and obtaining the modified quaternary ammonium salt chitosan after nucleophilic substitution reaction is completed;
(2) Single screw extrusion film forming: the screw speed of a single screw extruder is regulated to 80rpm, the heating temperatures of each area of a banburying area, a conveying area and a pressure building area are respectively 80, 85 and 90 ℃, 10 parts of PVA, 3 parts of glycerol and 50 parts of water are added into a charging port, after PVA plasticization is complete, the quaternary ammonium salt chitosan after double screw reaction extrusion modification is conveyed into the single screw extruder, fully stirred and uniformly mixed, finally extruded into a film under the conditions that the die head temperature of a machine head is 90 ℃ and the internal pressure of the machine head is 9.8MPa, and immediately placed into a vacuum drying box and fully dried for 4 hours at 60 ℃, so that the PVA film modified by the one-step reaction extrusion method is finally obtained.
Example 8
(1) Twin-screw reactive extrusion modification: setting the screw speed of a double-screw extruder to be 50rpm, heating the melting zone, the reaction zone and the conveying zone to be 60 ℃, 65 ℃ and 70 ℃ respectively, slowly adding 5 parts of epoxy chloropropane and 5 parts of cetyl dimethyl ammonium through a charging port, then adding 5 parts of chitosan and 10 parts of 50% isopropanol solution, slowly stirring and dispersing uniformly, adding 10 parts of 1mol/L sodium hydroxide solution, reacting at constant temperature for 2-4 hours, and obtaining the modified quaternary ammonium salt chitosan after nucleophilic substitution reaction is completed;
(2) Single screw extrusion film forming: the screw speed of a single screw extruder is regulated to 80rpm, the heating temperatures of each area of a banburying area, a conveying area and a pressure building area are respectively 80, 85 and 90 ℃, 10 parts of PVA, 3 parts of glycerol and 50 parts of water are added into a charging port, after PVA plasticization is complete, the quaternary ammonium salt chitosan after double screw reaction extrusion modification is conveyed into the single screw extruder, fully stirred and uniformly mixed, finally extruded into a film under the conditions that the die head temperature of a machine head is 90 ℃ and the internal pressure of the machine head is 9.8MPa, and immediately placed into a vacuum drying box and fully dried for 4 hours at 60 ℃, so that the PVA film modified by the one-step reaction extrusion method is finally obtained.
Example 9
(1) Twin-screw reactive extrusion modification: setting the screw speed of a double-screw extruder to be 50rpm, heating the melting zone, the reaction zone and the conveying zone to be 60 ℃, 65 ℃ and 70 ℃ respectively, slowly adding 5 parts of epoxy chloropropane and 5 parts of cetyl dimethyl ammonium through a charging port, then adding 5 parts of chitosan and 10 parts of 50% isopropanol solution, slowly stirring and dispersing uniformly, adding 15 parts of 1mol/L sodium hydroxide solution, reacting at constant temperature for 2-4 hours, and obtaining the modified quaternary ammonium salt chitosan after nucleophilic substitution reaction is completed;
(2) Single screw extrusion film forming: the screw speed of a single screw extruder is regulated to 80rpm, the heating temperatures of each area of a banburying area, a conveying area and a pressure building area are respectively 80, 85 and 90 ℃, 10 parts of PVA, 3 parts of glycerol and 50 parts of water are added into a charging port, after PVA plasticization is complete, the quaternary ammonium salt chitosan after double screw reaction extrusion modification is conveyed into the single screw extruder, fully stirred and uniformly mixed, finally extruded into a film under the conditions that the die head temperature of a machine head is 90 ℃ and the internal pressure of the machine head is 9.8MPa, and immediately placed into a vacuum drying box and fully dried for 4 hours at 60 ℃, so that the PVA film modified by the one-step reaction extrusion method is finally obtained.
Example 10
(1) Twin-screw reactive extrusion modification: setting the screw speed of a double-screw extruder to be 50rpm, heating the melting zone, the reaction zone and the conveying zone to be 60 ℃, 65 ℃ and 70 ℃ respectively, slowly adding 5 parts of epoxy chloropropane and 5 parts of cetyl dimethyl ammonium through a charging port, then adding 5 parts of chitosan and 10 parts of 50% isopropanol solution, slowly stirring and dispersing uniformly, adding 5 parts of 1mol/L sodium hydroxide solution, reacting at constant temperature for 2-4 hours, and obtaining the modified quaternary ammonium salt chitosan after nucleophilic substitution reaction is completed;
(2) Single screw extrusion film forming: the screw speed of a single screw extruder is regulated to 80rpm, the heating temperatures of each area of a banburying area, a conveying area and a pressure building area are respectively 80, 85 and 90 ℃, 20 parts of PVA, 3 parts of glycerol and 50 parts of water are added into a charging port, after PVA plasticization is complete, the quaternary ammonium salt chitosan after double screw reaction extrusion modification is conveyed into the single screw extruder, fully stirred and uniformly mixed, finally extruded into a film under the conditions that the die head temperature of a machine head is 90 ℃ and the internal pressure of the machine head is 9.8MPa, and immediately placed into a vacuum drying box and fully dried for 4 hours at 60 ℃, so that the PVA film modified by the one-step reaction extrusion method is finally obtained.
Example 11
(1) Twin-screw reactive extrusion modification: setting the screw speed of a double-screw extruder to be 50rpm, heating the melting zone, the reaction zone and the conveying zone to be 60 ℃, 65 ℃ and 70 ℃ respectively, slowly adding 5 parts of epoxy chloropropane and 5 parts of cetyl dimethyl ammonium through a charging port, then adding 5 parts of chitosan and 10 parts of 50% isopropanol solution, slowly stirring and dispersing uniformly, adding 5 parts of 1mol/L sodium hydroxide solution, reacting at constant temperature for 2-4 hours, and obtaining the modified quaternary ammonium salt chitosan after nucleophilic substitution reaction is completed;
(2) Single screw extrusion film forming: the screw speed of a single screw extruder is regulated to 80rpm, the heating temperatures of each area of a banburying area, a conveying area and a pressure building area are respectively 80, 85 and 90 ℃, 30 parts of PVA, 3 parts of glycerol and 50 parts of water are added into a charging port, after PVA plasticization is complete, the quaternary ammonium salt chitosan after double screw reaction extrusion modification is conveyed into the single screw extruder, fully stirred and uniformly mixed, finally extruded into a film under the conditions that the die head temperature of a machine head is 90 ℃ and the internal pressure of the machine head is 9.8MPa, and immediately placed into a vacuum drying box and fully dried for 4 hours at 60 ℃, so that the PVA film modified by the one-step reaction extrusion method is finally obtained.
The water absorption, transmittance, hydrophobic contact angle, thickness, tear resistance, minimum Inhibitory Concentration (MIC) and Minimum Bactericidal Concentration (MBC) against escherichia coli (e.coli) and staphylococcus aureus (s.aureus) and the like of examples 1 to 11 and commercially available polyethylene film (PE), polypropylene film (PP), PVA/chitosan film (PVA-CS) and PVA/hydroxypropyl trimethyl ammonium chloride chitosan film (PVA-HACC), respectively, were measured.
Table 1: compared with the performance of common plastic films in the market, the embodiment of the invention
Figure BDA0003481630460000081
As can be seen from Table 1, the thickness, density and light transmittance of the modified film material prepared by the embodiment of the invention are basically similar to those of PE film and PP film which are common in the market, and the tensile strength and elongation at break of the modified film of each embodiment are basically similar to those of the PE film and the PP film, and the mechanical property and the practical property of the modified film material are not obviously reduced. It is worth mentioning that the minimum water absorption rate of the chitosan modified by the epoxypropyl dimethyl polyalkyl ammonium chloride is 8%, the maximum hydrophobic contact angle reaches 97 degrees, and the chitosan has stronger hydrophobic performance. Therefore, the PVA film modified by the one-step reaction extrusion method obviously improves the hydrophobic property of the film, reduces the water vapor transmittance of the film, and improves the fresh-keeping capability of the film in the fresh-keeping of fruits, vegetables and meat products. In addition, the modified film has strong inhibition capability to colibacillus and staphylococcus aureus, and the reaction extrusion modified quaternary ammonium salt chitosan solution with the concentration of 2.1 mug/ml and 3.1 mug/ml can respectively kill 10 6 CFU/ml of E.coli and S.aureusThe sterilization capability of the coccus is improved by about 200 times compared with that of the unmodified PVA/chitosan film; compared with the PVA film modified by hydroxypropyl trimethyl ammonium chloride chitosan, the sterilization capability of the PVA film is improved by about 150 times. Therefore, after the novel antibacterial film prepared by the invention is subjected to reactive extrusion modification by the quaternary ammonium salt chitosan, the mechanical property and the practical property of the film are not reduced while the water resistance of the film is improved, and compared with the common PVA/chitosan film and the hydroxypropyl trimethyl ammonium chloride chitosan modified PVA film, the modified film has stronger spectrum antibacterial and sterilizing capability, can be widely applied to the fields of fruit and vegetable fresh-keeping and meat product fresh-keeping, greatly prolongs the shelf life of foods, and can completely replace the common PE film and PP film in the market.
The test method of the hydrophobic contact angle of the modified PVA film comprises the following steps:
the contact angle measurement of the modified PVA film is carried out by using a contact angle analyzer, all samples to be measured are dried in vacuum at 60 ℃ for 2-4 hours before measurement, and when liquid is dripped on the surface of the samples, a certain included angle, namely a contact angle, is formed between the liquid and the solid surface, and is expressed by theta. The magnitude of the contact angle is a key factor in analyzing wettability. When θ <90 °, the solid surface exhibits hydrophilicity. When θ is between 90 ° and 180 °, the solid surface exhibits high hydrophobicity. A drop of distilled water was placed on the film surface and its contact angle was measured after holding for 5 seconds. Each reported contact angle is an average of at least 10 measurements taken at different locations on the film.
The method for testing the tearing resistance of the modified PVA film comprises the following steps:
firstly, placing a film material in a constant temperature and humidity box with the room temperature relative humidity of 60% for balancing for 24 hours, then cutting a film sample into dumbbell-shaped standard strips, analyzing the tensile strength and the elongation at break by a universal mechanical tester, setting the tensile rate to be 20mm/min, testing each sample for three times, and recording test data to obtain the tensile strength (P) and the elongation at break (E).
P＝F/a×b (1)
Wherein F is a tensile force (N), and a and b are the width and thickness of the film, respectively
Figure BDA0003481630460000091
Wherein E is elongation at break (%), L and L0 are the distance from the standard line and the original distance from the standard line, respectively, when the film breaks.
The antibacterial and bacteriostatic ability test method of the modified PVA film comprises the following steps:
determination of Minimum Inhibitory Concentration (MIC) and Minimum Bactericidal Concentration (MBC) of the modified PVA film on escherichia coli/staphylococcus aureus: culture media containing different sample concentrations were first prepared by the sesquidilution method. 100 μl of each diluted to 10 were added by a pipette 6 cfu/ml of escherichia coli or staphylococcus aureus bacterial liquid is subjected to constant-temperature shaking culture at 37 ℃ for 48 hours. The absorbance was measured at 600nm using a microplate reader using the same sample concentration without the addition of the broth as a blank. The minimum inhibitory concentration is a concentration which is different from the light absorption value of the previous low concentration by two orders of magnitude and the culture solution is clear and transparent; the minimum bactericidal concentration refers to the minimum antimicrobial concentration required to kill 99.9% of the microorganisms, and the concentration of the sample medium in which the microorganisms are no longer growing is the minimum bactericidal concentration. Each sample was tested at least three times and the results averaged.
Determination of antibacterial growth curve of modified PVA film on coliform/staphylococcus aureus: firstly, the concentration gradient dilution of coliform bacteria or staphylococcus aureus bacteria liquid is carried out under the aseptic condition to obtain 10 6 The cfu/ml concentration bacterial liquid is then cut into 2X 2cm samples, the samples are placed in prepared liquid culture mediums under aseptic conditions after sterilization, 50 mu l of bacterial liquid is inoculated respectively, the liquid culture mediums without added sample antibacterial agents and only inoculated with the bacterial liquid are used as blank Control, all samples are cultivated at the constant temperature of 37 ℃ for 48 hours, and each sample is subjected to at least two parallel experiments.
As can be seen from FIG. 2, 3400-3500cm -1 Acetyl and amino groups exist in the molecule of chitosan for intermolecular hydrogen bond and-OH telescopic vibration absorption peak, and the acetyl characteristic spectrum of chitosan appears at 1650cm -1 This is the common amide I band, and the amino profile of chitosan appears at 1600cm -1 And the quaternary ammonium salt chitosan after reaction extrusion modification is 1600cm -1 No characteristic peak, which indicates that the modified quaternary ammonium salt chitosan is grafted and modified successfully. Furthermore, at 2925cm -1 And 1100cm -1 C-H stretching vibration peak and C-O stretching vibration absorption peak of alkyl respectively, which are just appeared on the quaternary ammonium salt compound and the modified quaternary ammonium salt chitosan. In the infrared spectrum of the modified quaternary ammonium salt chitosan, 1475cm of the modified quaternary ammonium salt chitosan -1 The same-CH as the quaternary ammonium salt appears 3 Bending vibration absorption peaks, which indicate that it completed a high degree of methylation reaction, and that epoxypropyldimethyl hexadecyl ammonium chloride was successfully grafted onto chitosan.
As can be seen from fig. 3, examples 1, 6 and 7 correspond to cetyl quaternary ammonium salt chitosan modified PVA film, tetradecyl quaternary ammonium salt chitosan modified PVA film and dodecyl quaternary ammonium salt chitosan modified PVA film, respectively. The modified quaternary ammonium salt chitosan PVA film has good inhibition effect on escherichia coli and staphylococcus aureus, and the antibacterial effect of the modified quaternary ammonium salt chitosan PVA film is obviously enhanced along with the increase of alkyl chains. The inhibition effect of the quaternary ammonium salt chitosan modified PVA film after the reaction extrusion modification on escherichia coli is stronger than that of staphylococcus aureus, which shows that the quaternary ammonium salt chitosan modified PVA film has stronger inhibition effect on gram-positive bacteria. Therefore, the PVA film modified by the one-step reaction extrusion method has the advantages that the antibacterial effect and antibacterial stability are successfully enhanced, and the problems of compatibility of the antibacterial agent and release of the antibacterial stability in the current preparation process of the PVA antibacterial film are solved.
In conclusion, the thickness, density and light transmittance of the modified film material prepared by the embodiment of the invention are not obviously different from those of PE films and PP films commonly used in the market, and the tensile strength and elongation at break of the modified film are basically similar to those of the PE films and the PP films, so that the mechanical property and the practical property of the modified film material are not obviously reduced. After the polyalkyl ammonium chloride modified chitosan is added into PVA, the minimum water absorption rate is 8%, the maximum hydrophobic contact angle reaches 97 degrees, and the PVA has stronger hydrophobic performance, so that the hydrophobic performance of the film is improved to a certain extent, the water vapor permeability of the film is reduced, and the fresh-keeping capability of the film in fresh keeping of fruits, vegetables and meat products is improved. In addition, the modified film showed a high resistance to E.coli and golden yellowThe staphylococcus has stronger inhibition capability, wherein 2.1 mug/ml and 3.1 mug/ml of modified quaternary ammonium salt chitosan solution can respectively kill 10 6 The sterilization capability of the CFU/ml escherichia coli and staphylococcus aureus is improved by about 200 times compared with that of the unmodified PVA/chitosan film; compared with the PVA film modified by hydroxypropyl trimethyl ammonium chloride chitosan, the sterilization capability of the PVA film is improved by about 150 times. Compared with PVA/chitosan film and hydroxypropyl trimethyl ammonium chloride chitosan modified PVA film, the PVA film prepared by the one-step reaction extrusion method has stronger spectrum antibacterial and sterilizing capability and stronger sterilizing capability, can be widely applied to the fields of fruit and vegetable fresh-keeping and meat product fresh-keeping, and greatly prolongs the shelf life of foods.
The foregoing examples are merely illustrative of the principles of the invention and are provided to illustrate and explain the principles of the invention in more detail and are not to be construed as limiting the scope of the invention. It should be noted that any modifications, equivalent substitutions and improvements made by those skilled in the art without departing from the inventive concept, as well as other products such as plastic wrap, plastic bags, trays and jars, etc. processed by the inventive concept and method through processes such as blow molding, injection molding and suction molding, and all products prepared by processes such as cast film forming, electrospinning, etc., fall within the scope of the present invention. Accordingly, the scope of the present invention should be determined by the following claims.

Claims (10)

1. The PVA film modified by the one-step reaction extrusion method is characterized by comprising the following components in parts by mass:
10-30 parts of PVA
5-15 parts of chitosan
3-5 parts of alkyl compound
5-15 parts of halogenated epoxypropane
10-20 parts of isopropanol solution
5-15 parts of sodium hydroxide solution
3-5 parts of plasticizer
20-60 parts of water;
the alkyl compound is one or more than two of hexadecyldimethylamine, tetradecyldimethylamine and dodecyl dimethylamine;
the preparation method of the PVA film modified by the one-step reaction extrusion method comprises the following steps:
(1) Twin-screw reactive extrusion modification: slowly adding halogenated epoxypropane and an alkyl compound into a double-screw extruder, then adding chitosan and isopropanol solution, uniformly stirring, adding sodium hydroxide solution to adjust the pH to 8-9, and reacting for 2-4 hours at the constant temperature of 65-75 ℃ to obtain the reaction extrusion modified quaternary ammonium salt chitosan;
(2) Single screw extrusion film forming: adding PVA, plasticizer and water into a single screw extruder, after the PVA is completely plasticized, conveying the modified quaternary ammonium salt chitosan obtained in the step (1) into the single screw extruder, stirring and mixing uniformly, extruding the mixture into a film through a machine head, and drying the film in vacuum to obtain the PVA film modified by the one-step reaction extrusion method.
2. The one-step reactive extrusion process modified PVA film according to claim 1, wherein the PVA has an alcoholysis degree of 80% to 98%, a viscosity of 3 to 30 mPa-s, and a molecular weight of 20,000 to 200,000.
3. The one-step reactive extrusion modified PVA film according to claim 1, wherein the chitosan has a degree of deacetylation of 80% or more, a viscosity of 100 to 300 mPa.s, and a molecular weight of 30,000 to 500,000.
4. The one-step reactive extrusion-modified PVA film according to claim 1, wherein the halogenated propylene oxide is one or two or more of epichlorohydrin, epibromohydrin, and iodohydrin; the plasticizer is one or more than two of citric acid, glycerol, polyethylene glycol or water.
5. The method for preparing a PVA film modified by a one-step reactive extrusion method according to any one of claims 1 to 4, comprising the steps of:
(1) Twin-screw reactive extrusion modification: slowly adding halogenated epoxypropane and an alkyl compound into a double-screw extruder, then adding chitosan and isopropanol solution, uniformly stirring, adding sodium hydroxide solution to adjust the pH to 8-9, and reacting for 2-4 hours at the constant temperature of 65-75 ℃ to obtain the reaction extrusion modified quaternary ammonium salt chitosan;
(2) Single screw extrusion film forming: adding PVA, plasticizer and water into a single screw extruder, after the PVA is completely plasticized, conveying the modified quaternary ammonium salt chitosan obtained in the step (1) into the single screw extruder, stirring and mixing uniformly, extruding the mixture into a film through a machine head, and drying the film in vacuum to obtain the PVA film modified by the one-step reaction extrusion method.
6. The method for preparing a PVA film modified by a one-step reaction extrusion method according to claim 5, wherein the twin-screw extruder in step (1) has a screw speed of 20 to 100rpm, an extruder melting zone heating temperature of 60 to 70 ℃, a reaction zone heating temperature of 65 to 75 ℃, and a conveying zone heating temperature of 60 to 70 ℃.
7. The method for preparing a PVA film modified by a one-step reaction extrusion method according to claim 5, wherein the single screw extruder in step (2) has a screw speed of 20 to 100rpm, a melting zone heating temperature of 75 to 90℃and a conveying zone heating temperature of 75 to 85℃and a nip heating temperature of 80 to 90 ℃.
8. The method for preparing a PVA film modified by a one-step reactive extrusion process according to claim 5, wherein the vacuum drying temperature in step (2) is 50 to 60 ℃ and the drying time is 4 to 8 hours.
9. The method for preparing a PVA film modified by a one-step reactive extrusion method according to claim 5, wherein the conditions for extrusion film formation by the head in step (2) are: the temperature of the die head is 90-100 ℃, and the internal pressure of the die head is 8-15MPa.
10. The use of the PVA film modified by one-step reactive extrusion as claimed in any of claims 1 to 4 in food preservation and film packaging.
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