CN115403909A - Biodegradable film and preparation method thereof - Google Patents
Biodegradable film and preparation method thereof Download PDFInfo
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- CN115403909A CN115403909A CN202211268565.9A CN202211268565A CN115403909A CN 115403909 A CN115403909 A CN 115403909A CN 202211268565 A CN202211268565 A CN 202211268565A CN 115403909 A CN115403909 A CN 115403909A
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- 238000002360 preparation method Methods 0.000 title abstract description 14
- 229920008262 Thermoplastic starch Polymers 0.000 claims abstract description 41
- 239000004628 starch-based polymer Substances 0.000 claims abstract description 41
- 239000004626 polylactic acid Substances 0.000 claims abstract description 32
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 31
- 239000000463 material Substances 0.000 claims abstract description 23
- 235000009024 Ceanothus sanguineus Nutrition 0.000 claims abstract description 16
- 240000003553 Leptospermum scoparium Species 0.000 claims abstract description 16
- 235000015459 Lycium barbarum Nutrition 0.000 claims abstract description 16
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000341 volatile oil Substances 0.000 claims abstract description 16
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000001768 carboxy methyl cellulose Substances 0.000 claims abstract description 14
- 239000002131 composite material Substances 0.000 claims abstract description 14
- 239000002245 particle Substances 0.000 claims abstract description 14
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims abstract description 14
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 22
- QZCLKYGREBVARF-UHFFFAOYSA-N Acetyl tributyl citrate Chemical compound CCCCOC(=O)CC(C(=O)OCCCC)(OC(C)=O)CC(=O)OCCCC QZCLKYGREBVARF-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 235000012424 soybean oil Nutrition 0.000 claims description 12
- 239000003549 soybean oil Substances 0.000 claims description 12
- 229960000583 acetic acid Drugs 0.000 claims description 11
- 239000012362 glacial acetic acid Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 239000011347 resin Substances 0.000 claims description 10
- 229920005989 resin Polymers 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 8
- 238000010096 film blowing Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 5
- 238000001125 extrusion Methods 0.000 claims description 5
- 238000005096 rolling process Methods 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 2
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 10
- 235000013305 food Nutrition 0.000 abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 4
- 239000001569 carbon dioxide Substances 0.000 abstract description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 2
- 239000007857 degradation product Substances 0.000 abstract description 2
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 abstract description 2
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- 235000021485 packed food Nutrition 0.000 abstract description 2
- 238000004321 preservation Methods 0.000 abstract description 2
- 238000003912 environmental pollution Methods 0.000 abstract 1
- 238000006731 degradation reaction Methods 0.000 description 11
- 230000015556 catabolic process Effects 0.000 description 10
- 230000001580 bacterial effect Effects 0.000 description 8
- 239000000725 suspension Substances 0.000 description 6
- 229920006381 polylactic acid film Polymers 0.000 description 5
- 238000007664 blowing Methods 0.000 description 4
- 229920002472 Starch Polymers 0.000 description 3
- 239000012785 packaging film Substances 0.000 description 3
- 229920006280 packaging film Polymers 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000008107 starch Substances 0.000 description 3
- 235000019698 starch Nutrition 0.000 description 3
- 230000003385 bacteriostatic effect Effects 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229920000704 biodegradable plastic Polymers 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000001963 growth medium Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000009630 liquid culture Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000008055 phosphate buffer solution Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000002504 physiological saline solution Substances 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 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
-
- 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
- C08J2300/00—Characterised by the use of unspecified polymers
- C08J2300/16—Biodegradable polymers
-
- 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
- C08J2400/00—Characterised by the use of unspecified polymers
- C08J2400/16—Biodegradable polymers
-
- 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
- C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2401/08—Cellulose derivatives
- C08J2401/26—Cellulose ethers
- C08J2401/28—Alkyl ethers
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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
- C08J2403/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
- C08J2403/02—Starch; Degradation products thereof, e.g. dextrin
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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
- C08J2491/00—Characterised by the use of oils, fats or waxes; Derivatives thereof
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- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- 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
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Abstract
The invention discloses a biodegradable film and a preparation method thereof, wherein the biodegradable film is prepared from the following raw materials in parts by mass: 40-50 parts of polylactic acid particles, 20-25 parts of modified food-grade thermoplastic starch, 1-1.5 parts of nano titanium dioxide, 2-3 parts of sodium carboxymethyl cellulose and 3.5-4.5 parts of tea tree essential oil. All materials of the composite film are in food grade, are non-toxic and harmless to human bodies, can perform ideal antibacterial preservation performance on packaged food, can be rapidly degraded in natural environment after being used and discarded, and are free of environmental pollution as degradation products are carbon dioxide and water.
Description
Technical Field
The invention belongs to the technical field of polylactic acid materials, and particularly relates to a biodegradable film and a preparation method thereof.
Background
Polylactic acid (PLA) film is a novel biodegradable material, has the basic characteristics of biodegradable plastics, can be disposed of safely after using, can not produce any harmful substance, and compared with polyethylene film, PLA film has high film forming ability, high transparency and high water vapor permeability to the raw materials source is extensive. In addition, PLA films also have the same printing properties as traditional film materials. Therefore, the polylactic acid is widely applied in various fields, including the fields of clothing, medical use, electronics, packaging and the like, wherein the food fresh-keeping film prepared from the polylactic acid has higher water vapor transmission rate and good gas selective permeability, so that the polylactic acid has good application prospect in the field of food films.
Although polylactic acid is widely applied, pure polylactic acid material has poor hydrophilic performance, and takes a long time for complete degradation in natural environment, the polylactic acid packaging material is modified through processing and compounding, so that not only can the tensile property, transparency and air permeability be enhanced, but also the hydrophilic performance of the polylactic acid film material can be enhanced, and the degradation rate of the polylactic acid film material is accelerated. Meanwhile, in the field of food packaging films, the antibacterial performance of the film is also one of important parameters, so that the good antibacterial and antibacterial performance of the packaging film can be ensured, and the shelf life and shelf life of food can be prolonged more effectively.
Disclosure of Invention
The invention aims to make up the defects of the prior art and provides a biodegradable film and a preparation method thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
a biodegradable film is prepared from the following raw materials in parts by mass: 40-50 parts of polylactic acid particles, 20-25 parts of modified food-grade thermoplastic starch, 1-1.5 parts of nano titanium dioxide, 2-3 parts of sodium carboxymethyl cellulose and 3.5-4.5 parts of tea tree essential oil.
Preferably, the biodegradable film is prepared from the following raw materials in parts by weight: 45 parts of polylactic acid particles, 23 parts of modified food-grade thermoplastic starch, 1.2 parts of nano titanium dioxide, 2.5 parts of sodium carboxymethylcellulose and 3 parts of tea tree essential oil.
Further, the modified food-grade thermoplastic starch is prepared from food-grade thermoplastic starch, acetyl tributyl citrate, epoxidized soybean oil and glacial acetic acid in a mass ratio of (75-80): (10-15): (5-10): 1, preparing the composition.
Further, the preparation method of the modified food-grade thermoplastic starch comprises the following steps: the modified food-grade thermoplastic starch is obtained by drying food-grade thermoplastic starch in a drying oven at 70-80 ℃ for 6-12 hours, and then adding the dried food-grade thermoplastic starch, acetyl tributyl citrate, epoxidized soybean oil and glacial acetic acid into a blender respectively according to the mass ratio for blending.
Furthermore, the temperature is controlled to be 140-160 ℃ during blending, the rotating speed of a blending rotor is 40-50 r/min, and the blending time is 10-30 min.
A preparation method of the biodegradable film comprises the following steps:
(1) Weighing polylactic acid particles, modified food-grade thermoplastic starch, nano titanium dioxide, sodium carboxymethyl cellulose and tea tree essential oil according to parts by weight, and then sending the weighed materials into a high-speed mixer to be uniformly mixed to obtain a mixture for later use;
(2) Feeding the mixture into a double-screw extruder for melt extrusion to obtain a resin material;
(3) And feeding the resin material into a film blowing machine set, and performing inflation, cooling, traction and rolling to obtain the polylactic acid composite film.
Further, the rotating speed of the high-speed mixer in the step 1 is 240-300 r/min, and the mixing time is 4-8 min.
Further, the temperature of the barrel of the extruder in the step 2 is controlled to be 165-175 ℃, the rotating speed of a screw is 200-300rpm, the length-diameter ratio of the screw is 55:1.
further, the set temperature of the film blowing unit in the step 3 is as follows: a first area: 145-155 ℃, zone two: 155-160 ℃, three zones: 160-165 ℃, four zones: 165-170 ℃, five zones: 170-175 ℃, the traction speed is 2.5-5m/min, and the blow-up ratio is 2-5.
The invention has the advantages that:
according to the polylactic acid composite film, modified food-grade thermoplastic starch is adopted to reinforce polylactic acid particles, wherein acetyl tributyl citrate and epoxidized soybean oil are added into starch components as plasticizing components, molecules of the acetyl tributyl citrate and the epoxidized soybean oil can be inserted into system gaps of polylactic acid and starch, intermolecular stress is reduced, chain segment mobility is improved, and the crystalline state of a blending system is reduced, so that the interface bonding strength of the composite material is enhanced, the breaking elongation of the composite film is increased, the compatibility of the two plasticizing components is improved through the use of glacial acetic acid, the synergistic effect is fully exerted, the problem of the compatibility of the starch and the polylactic acid is solved, the contact sites between the polylactic acid and water are further increased through the use of sodium carboxymethylcellulose, and the degradation time of the polylactic acid composite film is finally remarkably shortened.
The composite film is added with components such as nano titanium dioxide and tea tree essential oil, wherein the nano titanium dioxide has a photocatalytic sterilization effect, the tea tree essential oil contains terpenes, alcohols, phenols, aldehydes and other substances, the growth of bacteria can be effectively inhibited, and the antibacterial effect of the composite film is obviously improved by combining the nano titanium dioxide and the tea tree essential oil.
All materials of the composite film are in food grade, are nontoxic and harmless to human bodies, can perform ideal antibacterial preservation performance on packaged food, can be rapidly degraded in natural environment after being used and discarded, are carbon dioxide and water as degradation products, have no pollution to the environment, are simple in film preparation raw materials and process, are easy for industrial production, are superior to the existing food packaging film, and have good market prospect.
Detailed Description
The technical scheme of the invention is further explained by combining the specific examples as follows:
example 1
A biodegradable film is prepared from the following raw materials in parts by mass: 45 parts of polylactic acid particles, 23 parts of modified food-grade thermoplastic starch, 1.2 parts of nano titanium dioxide, 2.5 parts of sodium carboxymethylcellulose and 3 parts of tea tree essential oil.
The modified food-grade thermoplastic starch is prepared from food-grade thermoplastic starch, acetyl tributyl citrate, epoxidized soybean oil and glacial acetic acid in a mass ratio of 78:14:7:1, the preparation method comprises the following steps: the modified food-grade thermoplastic starch is obtained by drying food-grade thermoplastic starch in a drying oven at 75 ℃ for 9 hours, then adding the dried food-grade thermoplastic starch, acetyl tributyl citrate, epoxidized soybean oil and glacial acetic acid into a blending machine according to the mass ratio respectively, and blending while controlling the temperature at 150 ℃, the rotation speed of a blending rotor at 45 revolutions per minute and the blending time at 20 minutes.
A preparation method of the biodegradable film comprises the following steps:
(1) Weighing polylactic acid particles, modified food-grade thermoplastic starch, nano titanium dioxide, sodium carboxymethyl cellulose and tea tree essential oil according to parts by weight, and then sending the weighed materials into a high-speed mixer to mix for 6 minutes at 270 revolutions per minute to obtain a mixture for later use;
(2) And (2) feeding the mixture into a double-screw extruder for melt extrusion, wherein the temperature of a charging barrel of the extruder is controlled to be 170 ℃, the rotating speed of a screw is 250rpm, and the length-diameter ratio of the screw is 55:1, obtaining a resin material;
(3) Feeding the resin material into a film blowing unit, wherein the set temperature is as follows: a first area: 150 ℃, zone two: 156 ℃, three zones: 163 ℃, four zones: 169 ℃, five zones: the polylactic acid composite film is obtained by blowing, cooling, drawing and rolling at the temperature of 172 ℃, the drawing speed of 3.5m/min and the blowing-up ratio of 3.5.
Example 2
A biodegradable film is prepared from the following raw materials in parts by mass: 40 parts of polylactic acid particles, 20 parts of modified food-grade thermoplastic starch, 1 part of nano titanium dioxide, 2 parts of sodium carboxymethyl cellulose and 3.5 parts of tea tree essential oil.
The modified food-grade thermoplastic starch is prepared from food-grade thermoplastic starch, acetyl tributyl citrate, epoxidized soybean oil and glacial acetic acid in a mass ratio of 75:15:9:1, the preparation method comprises the following steps: drying food-grade thermoplastic starch in a drying oven at 70 ℃ for 12 hours, then adding the dried food-grade thermoplastic starch, acetyl tributyl citrate, epoxidized soybean oil and glacial acetic acid into a blending machine according to the mass ratio respectively, and blending at the controlled temperature of 140 ℃ for 30 minutes at the blending rotor rotating speed of 40 revolutions per minute to obtain the modified food-grade thermoplastic starch.
A preparation method of the biodegradable film comprises the following steps:
(1) Weighing polylactic acid particles, modified food-grade thermoplastic starch, nano titanium dioxide, sodium carboxymethyl cellulose and tea tree essential oil according to parts by weight, and then sending the weighed materials into a high-speed mixer to mix for 8 minutes at a speed of 240 revolutions per minute to obtain a mixture for later use;
(2) And (2) feeding the mixture into a double-screw extruder for melt extrusion, wherein the temperature of a charging barrel of the extruder is controlled to be 165 ℃, the rotating speed of a screw is 200rpm, and the length-diameter ratio of the screw is 55:1, obtaining a resin material;
(3) Feeding the resin material into a film blowing unit, wherein the set temperature is as follows: a first region: 145 ℃, two zones: 155 ℃, three zones: 160 ℃, four zones: 165 ℃, five zones: the polylactic acid composite film is obtained by blowing, cooling, drawing and rolling at the temperature of 170 ℃, the drawing speed of 2.5m/min and the blowing-up ratio of 2.
Example 3
A biodegradable film is prepared from the following raw materials in parts by weight: 50 parts of polylactic acid particles, 25 parts of modified food-grade thermoplastic starch, 1.5 parts of nano titanium dioxide, 3 parts of sodium carboxymethyl cellulose and 4.5 parts of tea tree essential oil.
The modified food-grade thermoplastic starch is prepared from food-grade thermoplastic starch, acetyl tributyl citrate, epoxidized soybean oil and glacial acetic acid in a mass ratio of 80:14:5:1, the preparation method comprises the following steps: drying food-grade thermoplastic starch in a drying oven at 80 ℃ for 6 hours, then adding the dried food-grade thermoplastic starch, acetyl tributyl citrate, epoxidized soybean oil and glacial acetic acid into a blender respectively according to the mass ratio for blending, wherein the blending temperature is controlled to be 160 ℃, the rotating speed of a blending rotor is 50 revolutions per minute, and the blending time is 10 minutes, so as to obtain the modified food-grade thermoplastic starch.
A preparation method of the biodegradable film comprises the following steps:
(1) Weighing polylactic acid particles, modified food-grade thermoplastic starch, nano titanium dioxide, sodium carboxymethyl cellulose and tea tree essential oil according to parts by weight, and then sending the weighed materials into a high-speed mixer to mix for 4 minutes at a speed of 300 revolutions per minute to obtain a mixture for later use;
(2) And (2) feeding the mixture into a double-screw extruder for melt extrusion, wherein the barrel temperature of the extruder is controlled to be 175 ℃, the rotating speed of a screw is 300rpm, and the length-diameter ratio of the screw is 55:1, obtaining a resin material;
(3) Feeding the resin material into a film blowing unit, wherein the set temperature is as follows: a first area: 155 ℃, zone two: 160 ℃, three zones: 165 ℃, four zones: 170 ℃, five zones: the polylactic acid composite film is obtained by blowing, cooling, drawing and rolling at 175 ℃ and at the drawing speed of 5m/min and the blowing ratio of 5.
The degradation performance of the film products obtained in examples 1, 2 and 3 was measured, and the degradation test was performed by completely immersing the samples in a phosphate buffer solution (pH =7.4 ± 0.2) and storing the samples at 37 ℃. The degradation rate of the film is calculated by measuring the change of the mass loss rate of the film, and experiments show that the average degradation rate of the obtained product in 30 days reaches 6.6%, the average degradation rate in 60 days reaches 31.7%, the average degradation rate in 90 days reaches 58.1%, while the degradation rate of the conventional polylactic acid film only reaches 3.4% in 90 days, and meanwhile, the film shows a tendency of first-speed and then-fast in the whole degradation process.
And then the antibacterial performance of the film products obtained in the examples 1, 2 and 3 is measured, a plate counting method is adopted, a liquid culture medium containing strains is cultured for 24 hours at 37 ℃, 10mL of bacterial suspension is taken out to be put in a centrifuge tube, centrifugation is carried out for 5 minutes at 4000r/min, the supernatant is discarded, and sterile normal saline is used for adjusting the concentration of the initial bacterial suspension to be 10 6 -10 8 CFU/mL (i.e., OD) 600 The value is 0.5). 2g of the minced membrane sample was added to 20mL of the bacterial suspension, and the non-membrane-added bacterial suspension was used as a control. Culturing at 37 deg.C for 12h, taking 1mL bacterial suspension, and gradually diluting to 10 with sterile physiological saline -6 And (4) doubling. 0.1mL of the bacterial suspension with proper dilution times is respectively and evenly coated on a PDA plate and cultured for 24h at 37 ℃. The plate with the colony number of 30-300CFU is selected for counting,the calculation formula of the antibacterial rate is as follows:
I=（N 1 -N 2 ）/N 1
in the formula: i is the bacteriostatic rate (%); n1 is the colony number of the control; n2 is the number of colonies of the membrane-containing sample. The total number of the bacterial colonies is determined by referring to a method of GB 4789.2-2016 (national food safety Standard for testing Total number of bacterial colonies for food microorganism inspection).
Experimental results show that the antibacterial rates of the examples 1, 2 and 3 are more than 98%, and the composite film has excellent antibacterial and bacteriostatic properties.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. The biodegradable film is characterized by being prepared from the following raw materials in parts by mass: 40-50 parts of polylactic acid particles, 20-25 parts of modified food-grade thermoplastic starch, 1-1.5 parts of nano titanium dioxide, 2-3 parts of sodium carboxymethyl cellulose and 3.5-4.5 parts of tea tree essential oil.
2. The biodegradable film as set forth in claim 1, which is prepared from the following raw materials in parts by mass: 45 parts of polylactic acid particles, 23 parts of modified food-grade thermoplastic starch, 1.2 parts of nano titanium dioxide, 2.5 parts of sodium carboxymethylcellulose and 3 parts of tea tree essential oil.
3. The biodegradable film according to claim 1, characterized in that said modified food-grade thermoplastic starch consists of food-grade thermoplastic starch, tributyl acetylcitrate, epoxidized soybean oil, glacial acetic acid in mass ratios (75-80): (10-15): (5-10): 1, preparing the composition.
4. The biodegradable film according to claim 3, characterized in that said modified food-grade thermoplastic starch is prepared by a process comprising: the modified food-grade thermoplastic starch is obtained by drying food-grade thermoplastic starch in a drying oven at 70-80 ℃ for 6-12 hours, and then adding the dried food-grade thermoplastic starch, acetyl tributyl citrate, epoxidized soybean oil and glacial acetic acid into a blender respectively according to the mass ratio for blending.
5. The biodegradable film according to claim 4, wherein the blending temperature is controlled to be 140-160 ℃, the blending rotor speed is 40-50 rpm, and the blending time is 10-30 minutes.
6. A method for preparing a biodegradable film according to any one of claims 1 to 5, characterized in that it comprises the following steps:
(1) Weighing polylactic acid particles, modified food-grade thermoplastic starch, nano titanium dioxide, sodium carboxymethyl cellulose and tea tree essential oil according to parts by weight, and then sending the weighed materials into a high-speed mixer to be uniformly mixed to obtain a mixture for later use;
(2) Feeding the mixture into a double-screw extruder for melt extrusion to obtain a resin material;
(3) And feeding the resin material into a film blowing machine set, and performing inflation, cooling, traction and rolling to obtain the polylactic acid composite film.
7. The method of claim 6, wherein the rotation speed of the high speed mixer in step 1 is 240-300 rpm, and the mixing time is 4-8 minutes.
8. The method for preparing biodegradable film according to claim 6, wherein the barrel temperature of the extruder in step 2 is controlled to be 165-175 ℃, the screw rotation speed is 200-300rpm, and the screw length-diameter ratio is 55:1.
9. the method for preparing biodegradable film according to claim 6, wherein the set temperature of the film blowing unit in step 3 is: a first region: 145-155 ℃, zone two: 155-160 ℃, three region: 160-165 ℃, four zones: 165-170 ℃, five zones: 170-175 ℃, the traction speed is 2.5-5m/min, and the blow-up ratio is 2-5.
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