CN110894346A - Controlled-release antioxidant active polylactic acid packaging film and preparation method thereof - Google Patents
Controlled-release antioxidant active polylactic acid packaging film and preparation method thereof Download PDFInfo
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- CN110894346A CN110894346A CN201911162819.7A CN201911162819A CN110894346A CN 110894346 A CN110894346 A CN 110894346A CN 201911162819 A CN201911162819 A CN 201911162819A CN 110894346 A CN110894346 A CN 110894346A
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- 239000003963 antioxidant agent Substances 0.000 title claims abstract description 67
- 230000003078 antioxidant effect Effects 0.000 title claims abstract description 67
- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 60
- 239000004626 polylactic acid Substances 0.000 title claims abstract description 60
- 239000012785 packaging film Substances 0.000 title claims abstract description 36
- 229920006280 packaging film Polymers 0.000 title claims abstract description 36
- 238000013270 controlled release Methods 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims description 10
- 239000002048 multi walled nanotube Substances 0.000 claims abstract description 45
- 239000011159 matrix material Substances 0.000 claims abstract description 28
- 239000011347 resin Substances 0.000 claims abstract description 26
- 229920005989 resin Polymers 0.000 claims abstract description 26
- 239000000203 mixture Substances 0.000 claims abstract description 24
- 238000002156 mixing Methods 0.000 claims abstract description 23
- 239000002245 particle Substances 0.000 claims abstract description 20
- -1 polytrimethylene carbonate Polymers 0.000 claims abstract description 11
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 7
- 238000011068 loading method Methods 0.000 claims abstract description 6
- 238000001125 extrusion Methods 0.000 claims abstract description 3
- 239000000155 melt Substances 0.000 claims abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 45
- 239000000284 extract Substances 0.000 claims description 17
- 238000002844 melting Methods 0.000 claims description 9
- 230000008018 melting Effects 0.000 claims description 9
- 244000269722 Thea sinensis Species 0.000 claims description 8
- 235000002532 grape seed extract Nutrition 0.000 claims description 8
- 150000008442 polyphenolic compounds Chemical class 0.000 claims description 8
- 235000013824 polyphenols Nutrition 0.000 claims description 8
- 229940087603 grape seed extract Drugs 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 239000001717 vitis vinifera seed extract Substances 0.000 claims description 7
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 3
- 238000007664 blowing Methods 0.000 claims description 2
- 241000628997 Flos Species 0.000 claims 1
- 235000013305 food Nutrition 0.000 abstract description 12
- 238000004806 packaging method and process Methods 0.000 abstract description 5
- 230000003064 anti-oxidating effect Effects 0.000 abstract description 4
- 238000006065 biodegradation reaction Methods 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 230000001186 cumulative effect Effects 0.000 description 10
- 239000002131 composite material Substances 0.000 description 8
- 244000223014 Syzygium aromaticum Species 0.000 description 7
- 235000016639 Syzygium aromaticum Nutrition 0.000 description 7
- 241000246358 Thymus Species 0.000 description 7
- 235000007303 Thymus vulgaris Nutrition 0.000 description 7
- 235000020230 cinnamon extract Nutrition 0.000 description 7
- 239000012528 membrane Substances 0.000 description 7
- 239000001585 thymus vulgaris Substances 0.000 description 7
- 238000009456 active packaging Methods 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 5
- 238000010096 film blowing Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000000338 in vitro Methods 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 239000005022 packaging material Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 235000012055 fruits and vegetables Nutrition 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
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- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 229930003935 flavonoid Natural products 0.000 description 1
- 235000017173 flavonoids Nutrition 0.000 description 1
- 150000002215 flavonoids Chemical class 0.000 description 1
- 235000019261 food antioxidant Nutrition 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
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- 230000001590 oxidative effect Effects 0.000 description 1
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- 230000002000 scavenging effect Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D65/38—Packaging materials of special type or form
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2469/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/041—Carbon nanotubes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/005—Stabilisers against oxidation, heat, light, ozone
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
- Y02A40/90—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in food processing or handling, e.g. food conservation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
Abstract
The invention discloses a controlled-release antioxidant active polylactic acid packaging film, which comprises 80-98% of matrix resin and 2-20% of multi-walled carbon nanotube particles loaded with natural antioxidants in percentage by mass; the method comprises the steps of loading natural antioxidant on a multi-walled carbon nanotube, mixing the natural antioxidant with matrix resin, and preparing the controlled-release antioxidant active polylactic acid packaging film by a melt extrusion method; wherein the matrix resin is a blend of polylactic acid and polytrimethylene carbonate; the raw materials used by the method can realize biodegradation, and the production process is simple; the multi-wall carbon nano tube is used for loading the natural antioxidant, so that the slow release of the natural antioxidant can be effectively controlled, the anti-oxidation timeliness of the packaging film is improved, and the multi-wall carbon nano tube can be applied to the field of food active anti-oxidation packaging.
Description
Technical Field
The invention relates to a controlled-release antioxidant active polylactic acid packaging film and a preparation method thereof, belonging to the technical field of food active packaging.
Background
Chemically synthesized plastics have become the material of choice worldwide for food packaging applications because of their performance, cost effectiveness, and durability. However, the use of a large amount of chemically synthesized plastics has caused a serious global pollution problem, and therefore, research in recent decades has focused on finding a solution that can replace conventional plastics with biodegradable materials, in which polylactic acid obtained by fermentation from renewable resources has been widely used in many applications such as food packaging in recent years due to its superior properties of biodegradability, processability, mechanical strength, and the like.
Consumer preference for safer, healthier, and more convenient foods has led to innovations in packaging technology. In this case, the concept of active packaging has emerged, based on the positive interaction between the packaging and the food or its environment, in order to provide them with active protection. Active materials and articles are intended to extend shelf life or to maintain or improve the packaged state, where bio-packaging and active packaging with antioxidant properties are new areas of technology. Antioxidants can retard or prevent food deterioration through oxidative mechanisms. They may act as scavengers by preventing the formation of free radicals or by scavenging them before they begin the process of destroying food. Currently, there is a general trend in the food industry to replace synthetic antioxidants, such as flavonoids in medicinal plants, with natural antioxidants. Natural compounds have recently been investigated as effective antioxidants, and once they are incorporated into packaging materials, these can be used as antioxidants in various fields, such as food, pharmaceuticals or cosmetics. It has been studied to add natural antioxidants, such as tea polyphenols, grape seed extract, clove extract, thyme extract, cinnamon extract, etc., to polylactic acid, and after adding natural antioxidants, the polylactic acid film not only has a certain antioxidant activity, but also can enhance the mechanical properties of the composite film to a certain extent, and has a good fresh-keeping effect. However, the instability of the natural antioxidant is easily influenced by factors such as temperature, illumination or pH, and the natural antioxidant is mixed with the polylactic acid matrix only by a simple mixing mode, so that the antioxidant aging of the polylactic acid composite membrane is shortened or even lost.
Although a great deal of research is carried out at home and abroad on adding natural antioxidant active substances to prepare the polylactic acid antioxidant active packaging material, no research is carried out on adding multi-wall carbon nano tubes to load natural antioxidant and adding the multi-wall carbon nano tubes to a polylactic acid base material to prepare a controlled-release food antioxidant active packaging material.
Disclosure of Invention
The invention aims to provide a controlled-release antioxidant active polylactic acid packaging film which comprises, by mass, 80-98% of matrix resin and 2-20% of multiwalled carbon nanotube particles loaded with natural antioxidants.
The natural antioxidant is one of tea polyphenol, grape seed extract, clove extract, thyme extract and cinnamon extract which are commercially available.
The multi-walled carbon nanotubes are commercially available products.
The matrix resin is prepared by mixing and drying 80-95 wt% of polylactic acid and 5-20 wt% of polytrimethylene carbonate, wherein the weight average molecular weight of the polylactic acid is 10-30 ten thousand, and the weight average molecular weight of the polytrimethylene carbonate is 10-20 ten thousand.
The invention also aims to provide a preparation method of the controlled-release antioxidant active polylactic acid packaging film, which comprises the steps of firstly, loading a natural antioxidant by using the multi-wall carbon nano tube, then mixing the natural antioxidant with matrix resin, and preparing the controlled-release antioxidant active polylactic acid packaging film by using a melt extrusion method.
The multi-wall carbon nano tube has the diameter of 10-50 nm and the length of 5-20 microns, has a regular multi-sheet layer hollow tubular structure, can control the natural antioxidant to slowly release to fruits and vegetables in a fresh-keeping package by loading the natural antioxidant through the multi-wall carbon nano tube, and maintains long-term stable antioxidant activity in the package, thereby achieving the purpose of antioxidation; the multi-wall carbon nano tube can be used as a nucleating agent of polylactic acid to improve the crystallization rate of the polylactic acid and effectively improve the mechanical property of the polylactic acid food packaging film.
The method specifically comprises the following steps:
(1) mixing a natural antioxidant with the multi-walled carbon nano-tube to prepare a blend, wherein the natural antioxidant accounts for 2-20% of the weight of the blend;
(2) adding the blend obtained in the step (1) into dichloromethane, performing ultrasonic dispersion for 15-25 min, and then stirring at room temperature to fully volatilize a dichloromethane solvent to obtain multi-walled carbon nanotube particles loaded with natural antioxidants;
the mass-volume ratio g: mL of the blend to dichloromethane is 1: 4-1: 8;
(3) uniformly mixing multi-wall carbon nano tube particles loaded with natural antioxidant with matrix resin, adding the mixture into a double-screw extruder for blending, melting, extruding and blowing the mixture to obtain a controlled-release antioxidant active polylactic acid packaging film; wherein the polylactic acid matrix resin accounts for 80-98% by mass, and the multiwalled carbon nanotube particles loaded with natural antioxidant account for 2-20% by mass;
(4) in the processing process of the packaging film, the blending melting temperature of the materials is the common processing temperature of the polylactic acid and polytrimethylene carbonate matrix film, and the temperature is selected to be 150-175 ℃ in consideration of melting the matrix resin and not degrading the matrix resin.
Compared with the prior art, the invention has the following advantages:
the controlled-release antioxidant activity polylactic acid packaging film prepared by the invention can control the natural antioxidant to slowly release to fruits and vegetables in a fresh-keeping package through the pore canal of the multi-walled carbon nano tube, and maintain long-term stable antioxidant activity in the package, thereby achieving the purpose of antioxidation; the toughness of the polylactic acid composite membrane prepared by the invention is also increased due to the addition of the multi-wall carbon nano tube particles; the controlled-release antioxidant active polylactic acid packaging film prepared by loading natural antioxidant through the multi-wall carbon nano tube and adding the natural antioxidant into matrix resin can be effectively applied to the technical field of food active packaging.
Detailed Description
The present invention is further illustrated by the following examples, but the scope of the present invention is not limited to the above-described contents, and reagents and methods used in the examples are conventional reagents and conventional methods, unless otherwise specified.
Example 1: the preparation method of the controlled release type antioxidant active polylactic acid packaging film comprises the following steps:
(1) uniformly mixing 9500g of polylactic acid (with the weight average molecular weight of 10 ten thousand) and 500g of polytrimethylene carbonate (with the weight average molecular weight of 20 ten thousand), and drying in a vacuum drying oven at 25 ℃ for 10 hours to prepare matrix resin;
(2) 1600g of multi-walled carbon nanotubes and 400g of tea polyphenol are mixed to prepare a blend;
(3) adding the blend obtained in the step (2) into 16000mL of dichloromethane, ultrasonically dispersing for 20min, stirring for 12h at room temperature, and fully volatilizing a dichloromethane solvent to obtain multi-walled carbon nanotube particles loaded with tea polyphenol;
(4) and (3) adding 8kg of matrix resin in the step (1) and 2kg of multi-wall carbon nano tube particles loaded with tea polyphenol in the step (3) into a double-screw extruder for blending, melting (the temperature of a four-stage heating area is controlled to be 150-160-175-160 ℃), extruding, and preparing the controlled-release antioxidant active polylactic acid packaging film by a film blowing machine.
The in vitro release experiment of the controlled release type antioxidant activity polylactic acid packaging film prepared by the embodiment shows that the release rate of tea polyphenol at 1 day is 13.5%, the cumulative release rate at 35 days is 82.3%, and the cumulative release rate tends to be stable thereafter; compared with the polylactic acid composite membrane which does not use multi-wall carbon nano tubes to load tea polyphenol, the slow release time is increased by 15 days.
Example 2: the preparation method of the controlled release type antioxidant active polylactic acid packaging film comprises the following steps:
(1) 8000g of polylactic acid (with weight average molecular weight of 10 ten thousand) and 2000g of polytrimethylene carbonate (with weight average molecular weight of 10 ten thousand) are uniformly mixed, and then dried for 10 hours in a vacuum drying oven at 25 ℃ to prepare matrix resin;
(2) mixing 980g of multi-walled carbon nanotubes and 20g of grape seed extract to obtain a blend;
(3) adding the blend obtained in the step (2) into 4000mL of dichloromethane, performing ultrasonic dispersion for 25min, stirring at room temperature for 12h, and fully volatilizing a dichloromethane solvent to obtain multiwalled carbon nanotube particles loaded with grape seed extracts;
(4) and (3) adding 9.8kg of matrix resin obtained in the step (1) and 0.2kg of multi-wall carbon nano tube particles loaded with the grape seed extract obtained in the step (3) into a double-screw extruder for blending, melting (the temperature of a four-stage heating area is controlled to be 150-160-175-160 ℃), extruding, and preparing the controlled-release antioxidant active polylactic acid packaging film by a film blowing machine.
The in vitro release experiment of the controlled release type antioxidant activity polylactic acid packaging film prepared by the embodiment shows that the release rate of the grape seed extract at day 1 is 10.0%, the cumulative release rate at day 28 is 80.9%, and the cumulative release rate tends to be stable thereafter; compared with the polylactic acid composite membrane without using the multiwalled carbon nanotube to load the grape seed extract, the slow release time is increased by 8 days.
Example 3: the preparation method of the controlled release type antioxidant active polylactic acid packaging film comprises the following steps:
(1) 9000g of polylactic acid (with weight average molecular weight of 30 ten thousand) and 1000g of polytrimethylene carbonate (with weight average molecular weight of 25 ten thousand) are uniformly mixed, and then dried in a vacuum drying oven at 25 ℃ for 10 hours to prepare matrix resin;
(2) mixing 1700g of multi-walled carbon nanotubes and 300g of clove extract to obtain a blend;
(3) adding the blend obtained in the step (2) into 10000mL of dichloromethane, performing ultrasonic dispersion for 15min, stirring at room temperature for 12h, and fully volatilizing a dichloromethane solvent to obtain multi-walled carbon nanotube particles loaded with the clove extract;
(4) and (3) adding 8.5kg of matrix resin in the step (1) and 1.5kg of multi-wall carbon nano tube particles loaded with the clove extracts in the step (3) into a double-screw extruder, blending, melting (the temperature of a four-stage heating area is controlled to be 150-160-175-160 ℃), extruding, and preparing the controlled-release antioxidant active polylactic acid packaging film by a film blowing machine.
The in vitro release experiment of the controlled release type antioxidant activity polylactic acid packaging film prepared by the embodiment shows that the release rate of the clove extract on the 1 st day is 11.2%, the cumulative release rate on the 32 th day is 83.1%, and the cumulative release rate tends to be stable thereafter. Compared with the polylactic acid composite membrane without using multi-wall carbon nano tubes to load clove extract, the slow release time is increased by 10 days.
Example 4: the preparation method of the controlled release type antioxidant active polylactic acid packaging film comprises the following steps:
(1) 8500g of polylactic acid (with the weight average molecular weight of 15 ten thousand) and 1500g of polytrimethylene carbonate (with the weight average molecular weight of 15 ten thousand) are uniformly mixed and dried in a vacuum drying oven at 25 ℃ for 10 hours to prepare matrix resin;
(2) mixing 900g of multi-walled carbon nanotubes and 100g of thyme extract to obtain a blend;
(3) adding the blend obtained in the step (2) into 6000mL of dichloromethane, performing ultrasonic dispersion for 18min, stirring at room temperature for 12h, and fully volatilizing a dichloromethane solvent to obtain multi-wall carbon nano tube particles loaded with the thyme extract;
(4) and (3) adding 9kg of matrix resin obtained in the step (1) and 1kg of multi-wall carbon nano tube particles loaded with the thyme extract obtained in the step (3) into a double-screw extruder for blending, melting (the temperature of a four-stage heating area is controlled to be 150-160-175-160 ℃), extruding, and preparing the controlled-release antioxidant active polylactic acid packaging film through a film blowing machine.
The in vitro release experiment of the controlled release type antioxidant activity polylactic acid packaging film prepared by the embodiment shows that the release rate of the thyme extract on the 1 st day is 10.7%, the cumulative release rate on the 36 th day is 80.7%, and the cumulative release rate tends to be stable thereafter. Compared with the polylactic acid composite membrane which does not use multi-wall carbon nano tubes to load thyme extract, the slow release time is increased by 13 days.
Example 5: the preparation method of the controlled release type antioxidant active polylactic acid packaging film comprises the following steps:
(1) after 8800g of polylactic acid (weight average molecular weight: 10 ten thousand) and 1200g of polytrimethylene carbonate (weight average molecular weight: 20 ten thousand) are mixed uniformly, the mixture is dried in a vacuum drying oven for 10 hours at 25 ℃ to prepare matrix resin;
(2) mixing 950g of multi-walled carbon nanotubes and 50g of cinnamon extract to prepare a blend;
(3) adding the blend obtained in the step (2) into 7000mL of dichloromethane, performing ultrasonic dispersion for 22min, stirring at room temperature for 12h, and fully volatilizing a dichloromethane solvent to obtain multiwalled carbon nanotube particles loaded with a cinnamon extract;
(4) and (3) adding 9.5kg of matrix resin in the step (1) and 0.5kg of multi-wall carbon nano tube particles loaded with cinnamon extract in the step (3) into a double-screw extruder, blending, melting (the temperature of a four-stage heating area is controlled to be 150-160-175-160 ℃), extruding, and preparing the controlled-release antioxidant active polylactic acid packaging film by a film blowing machine.
The in vitro release experiment of the controlled release type antioxidant activity polylactic acid packaging film prepared by the embodiment shows that the release rate of the cinnamon extract is 9.8% at the 1 st day, the cumulative release rate is 81.6% at the 30 th day, and the cumulative release rate tends to be stable thereafter. Compared with the polylactic acid composite membrane without using multi-wall carbon nano tubes to load cinnamon extract, the slow release time is increased by 12 days.
Claims (5)
1. A controlled release type antioxidant active polylactic acid packaging film is characterized in that: the composition and the mass percentage are 80-98% of matrix resin and 2-20% of multi-wall carbon nano tube particles loaded with natural antioxidant.
2. The controlled release antioxidant active polylactic acid packaging film according to claim 1, wherein: the natural antioxidant is one of tea polyphenols, grape seed extract, flos Caryophylli extract, herba Thymi extract, and cortex Cinnamomi extract.
3. The controlled release antioxidant active polylactic acid packaging film according to claim 1, wherein: the matrix resin is prepared by mixing and drying 80-95 wt% of polylactic acid and 5-20 wt% of polytrimethylene carbonate, wherein the weight average molecular weight of the polylactic acid is 10-30 ten thousand, and the weight average molecular weight of the polytrimethylene carbonate is 10-20 ten thousand.
4. The method for preparing the controlled-release antioxidant active polylactic acid packaging film according to any one of claims 1 to 3, which is characterized in that: the controlled-release antioxidant active polylactic acid packaging film is prepared by loading natural antioxidant on a multi-wall carbon nano tube, then mixing the natural antioxidant with matrix resin and adopting a melt extrusion method.
5. The preparation method of the controlled-release type antioxidant activity polylactic acid packaging film according to claim 4, which is characterized by comprising the following steps:
(1) mixing a natural antioxidant with the multi-walled carbon nano-tube to prepare a blend, wherein the natural antioxidant accounts for 2-20% of the weight of the blend;
(2) adding the blend obtained in the step (1) into dichloromethane, performing ultrasonic dispersion for 15-25 min, and then stirring at room temperature to fully volatilize a dichloromethane solvent to obtain multi-walled carbon nanotube particles loaded with natural antioxidants;
(3) uniformly mixing multi-wall carbon nano tube particles loaded with natural antioxidant with matrix resin, adding the mixture into a double-screw extruder for blending, melting, extruding and blowing the mixture to obtain a controlled-release antioxidant active polylactic acid packaging film; wherein the mass percent of the matrix resin is 80-98%, and the mass percent of the multiwall carbon nanotube particles loaded with the natural antioxidant is 2-20%.
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| CN113002099A (en) * | 2021-02-26 | 2021-06-22 | 杭州拜迪戈雷生物材料有限公司 | Composite antibacterial film and preparation method thereof |
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