CN115403909B - Biodegradable film and preparation method thereof - Google Patents
Biodegradable film and preparation method thereof Download PDFInfo
- Publication number
- CN115403909B CN115403909B CN202211268565.9A CN202211268565A CN115403909B CN 115403909 B CN115403909 B CN 115403909B CN 202211268565 A CN202211268565 A CN 202211268565A CN 115403909 B CN115403909 B CN 115403909B
- Authority
- CN
- China
- Prior art keywords
- parts
- thermoplastic starch
- film
- food
- grade thermoplastic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 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 34
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 33
- 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 11
- 238000002156 mixing Methods 0.000 claims description 27
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 15
- 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
- 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
- 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
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 9
- 238000000034 method Methods 0.000 abstract description 9
- 235000013305 food Nutrition 0.000 abstract description 8
- 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
- 239000012785 packaging film Substances 0.000 abstract description 4
- 229920006280 packaging film Polymers 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 3
- 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
- 238000009776 industrial production Methods 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
- 238000006731 degradation reaction Methods 0.000 description 17
- 230000015556 catabolic process Effects 0.000 description 16
- 229920002472 Starch Polymers 0.000 description 8
- 229920006381 polylactic acid film Polymers 0.000 description 8
- 239000008107 starch Substances 0.000 description 8
- 235000019698 starch Nutrition 0.000 description 8
- 230000001580 bacterial effect Effects 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- 230000035699 permeability Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002504 physiological saline solution Substances 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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 230000003385 bacteriostatic effect Effects 0.000 description 1
- 229920000704 biodegradable plastic Polymers 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 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
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 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
- 239000008055 phosphate buffer solution Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 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
- 238000002834 transmittance Methods 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
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 weight: 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 carboxymethylcellulose and 3.5-4.5 parts of tea tree essential oil. The composite film disclosed by the invention is food-grade, is nontoxic and harmless to human bodies, can perform ideal antibacterial preservation performance on packaged foods, can be rapidly degraded in natural environment after being used and abandoned, has no pollution to the environment due to carbon dioxide and water as degradation products, is simple in film-making raw materials and process, is easy to realize industrial production, is superior to the existing food packaging film, and has a good market prospect.
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 safely disposed of after use, does not generate any harmful substances, and has high film forming property, high transparency and high water vapor permeability compared with polyethylene film, and wide raw material sources. In addition, PLA films also have the same printing properties as conventional film materials. Therefore, the polylactic acid is widely applied in various fields including clothing, medical, electronic and packaging fields, wherein the food fresh-keeping film prepared from the polylactic acid has higher water vapor transmittance 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 property, and in natural environment, the polylactic acid packaging material is modified by processing and compounding, so that the tensile property, transparency and air permeability can be enhanced, the hydrophilic property of the polylactic acid film material can be enhanced, the degradation rate of the polylactic acid film material is accelerated, hydrophilic starch is used for processing the polylactic acid film material, but the hydrophilic starch and hydrophobic polylactic acid are poor in direct blending compatibility, so that the interface bonding strength of the composite material is low, the brittleness is high, and the processing property is poor, and the wide development and application of the material are limited. Meanwhile, in the field of food packaging films, the antibacterial performance of the film is one of important parameters, so that the good antibacterial performance of the packaging film is ensured, and the shelf life of foods can be effectively prolonged.
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 weight: 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 carboxymethylcellulose 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 carboxymethyl cellulose 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 according to the mass ratio of (75-80): (10-15): (5-10): 1.
Further, the preparation method of the modified food-grade thermoplastic starch comprises the following steps: firstly, 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 according to the mass ratio respectively for blending to obtain the modified food-grade thermoplastic starch.
Further, the control temperature of the blending is 140-160 ℃, the rotating speed of a blending rotor is 40-50 rpm, and the blending time is 10-30 minutes.
A method for preparing a biodegradable film as described above, comprising the steps of:
(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 mixture into a high-speed mixer to be uniformly mixed to obtain a mixture for standby;
(2) Feeding the mixture into a double-screw extruder for melt extrusion to obtain a resin material;
(3) And (3) sending the resin material into a film blowing unit, 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 rpm, and the mixing time is 4-8 minutes.
Further, in the step 2, the temperature of the extruder barrel is controlled to be 165-175 ℃, the rotating speed of the screw is 200-300rpm, and 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 region: 145-155 ℃, two areas: 155-160 ℃, three regions: 160-165 ℃, four regions: 165-170 ℃, five regions: 170-175 ℃, the traction speed is 2.5-5m/min, and the blow-up ratio is 2-5.
The invention has the advantages that:
the polylactic acid composite film adopts modified food-grade thermoplastic starch to strengthen polylactic acid particles, wherein the starch component is added with acetyl tributyl citrate and epoxy soybean oil as plasticizing components, molecules of the starch component and the acetyl tributyl citrate and the epoxy soybean oil can be inserted into a system gap of polylactic acid and starch, so that the intermolecular stress is reduced, the segment activity is improved, the crystallization state of a blending system is reduced, the interface bonding strength of a composite material is enhanced, the elongation at break of the composite film is increased, the compatibility of the two plasticizing components is improved through the use of glacial acetic acid on the basis, the synergistic effect of the two plasticizing components is fully exerted, the problem of the compatibility of the starch and the polylactic acid is solved, the contact site between the polylactic acid and water is further increased through the use of sodium carboxymethyl cellulose, and finally the degradation time of the polylactic acid composite film is obviously shortened.
The nano titanium dioxide and tea tree essential oil are added simultaneously, wherein the nano titanium dioxide has a photocatalytic sterilization effect, the tea tree essential oil contains terpene, alcohol, phenol, aldehyde 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 with the tea tree essential oil.
The composite film disclosed by the invention is food-grade, is nontoxic and harmless to human bodies, can perform ideal antibacterial preservation performance on packaged foods, can be rapidly degraded in natural environment after being used and abandoned, has no pollution to the environment due to carbon dioxide and water as degradation products, is simple in film-making raw materials and process, is easy to realize industrial production, is superior to the existing food packaging film, and has a good market prospect.
Detailed Description
The technical scheme of the invention is further described below with reference to specific examples:
example 1
A 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 carboxymethyl cellulose 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 according to a mass ratio of 78:14:7:1, the preparation method comprises the following steps: firstly, drying food-grade thermoplastic starch in a drying oven at 75 ℃ for 9 hours, and then adding the dried food-grade thermoplastic starch, acetyl tributyl citrate, epoxidized soybean oil and glacial acetic acid into a blender according to the mass ratio respectively for blending, wherein the blending control temperature is 150 ℃, the rotational speed of a blending rotor is 45 revolutions per minute, and the blending time is 20 minutes, so as to obtain the modified food-grade thermoplastic starch.
A method for preparing a biodegradable film as described above, comprising the steps of:
(1) Weighing polylactic acid particles, modified food-grade thermoplastic starch, nano titanium dioxide, sodium carboxymethylcellulose and tea tree essential oil according to parts by weight, and then sending the mixture into a high-speed mixer for mixing for 6 minutes at 270 revolutions per minute to obtain a mixture for standby;
(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) The resin material is sent into a film blowing unit, and the set temperature is as follows: a region: 150 ℃, two areas: 156 ℃, three regions: 163 ℃, four zones: 169 ℃, five regions: the polylactic acid composite film is obtained through blowing, cooling, traction and rolling at 172 ℃ at a traction speed of 3.5m/min and a blowing ratio of 3.5.
Example 2
A biodegradable film is prepared from the following raw materials in parts by weight: 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 according to a mass ratio of 75:15:9:1, the preparation method comprises the following steps: firstly, drying food-grade thermoplastic starch in a drying oven at 70 ℃ for 12 hours, and then adding the dried food-grade thermoplastic starch, acetyl tributyl citrate, epoxidized soybean oil and glacial acetic acid into a blender according to the mass ratio respectively for blending, wherein the blending control temperature is 140 ℃, the rotational speed of a blending rotor is 40 r/min, and the blending time is 30 min, so as to obtain the modified food-grade thermoplastic starch.
A method for preparing a biodegradable film as described above, comprising the steps of:
(1) Weighing polylactic acid particles, modified food-grade thermoplastic starch, nano titanium dioxide, sodium carboxymethylcellulose and tea tree essential oil according to parts by weight, and then sending the mixture into a high-speed mixer for mixing for 8 minutes at 240 revolutions per minute to obtain a mixture for standby;
(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) The resin material is sent into a film blowing unit, and the set temperature is as follows: a region: 145 ℃, two regions: 155 ℃, three regions: 160 ℃, four regions: 165 ℃, five regions: the polylactic acid composite film is obtained through inflation, cooling, traction and rolling at 170 ℃ at a traction speed of 2.5m/min and an inflation 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 according to the mass ratio of 80:14:5:1, the preparation method comprises the following steps: firstly, drying food-grade thermoplastic starch in a drying oven at 80 ℃ for 6 hours, and then adding the dried food-grade thermoplastic starch, acetyl tributyl citrate, epoxidized soybean oil and glacial acetic acid into a blender according to the mass ratio respectively for blending, wherein the blending control temperature is 160 ℃, the rotational 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 method for preparing a biodegradable film as described above, comprising the steps of:
(1) Weighing polylactic acid particles, modified food-grade thermoplastic starch, nano titanium dioxide, sodium carboxymethylcellulose and tea tree essential oil according to parts by weight, and then sending the mixture into a high-speed mixer for mixing for 4 minutes at 300 revolutions per minute to obtain a mixture for standby;
(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 175 ℃, the rotating speed of a screw is controlled to be 300rpm, and the length-diameter ratio of the screw is controlled to be 55:1, obtaining a resin material;
(3) The resin material is sent into a film blowing unit, and the set temperature is as follows: a region: 155 ℃, two areas: 160 ℃, three regions: 165 ℃, four zones: 170 ℃, five regions: the polylactic acid composite film is obtained through inflation, cooling, traction and rolling at 175 ℃ at a traction speed of 5m/min and an inflation ratio of 5.
The degradation properties of the film products obtained in examples 1, 2 and 3 were measured, and the samples were completely immersed in a phosphate buffer solution (ph=7.4±0.2) and stored at 37 ℃ for degradation experiments. The degradation rate is calculated by measuring the change of the mass loss rate of the film, and the experiment shows that the average degradation rate of the obtained product reaches 6.6% in 30 days, the average degradation rate reaches 31.7% in 60 days, the average degradation rate of the conventional polylactic acid film reaches 58.1% in 90 days, and the degradation rate of the conventional polylactic acid film only reaches 3.4% in 90 days, meanwhile, the degradation rate of the conventional polylactic acid film is in a trend of being quick after slow and quick after long in the whole degradation process of the film, because of the existence of hydrophilic starch, the initial degradation rate is quick, when the starch content is reduced along with the degradation time, the degradation rate starts to be reduced, but more holes are generated along with the degradation of the polylactic acid film in the process, so that the degradation rate is easier to enter the inside of the polylactic acid material, and the degradation rate is increased.
Then the antibacterial properties of the film products obtained in examples 1, 2 and 3 were measured, a plate counting method was used to culture 24h in a liquid medium containing the strain at 37℃and 10mL of the bacterial suspension was taken in a centrifuge tube, centrifuged at 4000r/min for 5min, the supernatant was discarded, and the initial bacterial suspension concentration was adjusted to 10 with sterile physiological saline 6 -10 8 CFU/mL (i.e. OD 600 A value of 0.5). 2g of the sheared film sample was added to 20mL of the bacterial suspension, and the bacterial suspension without the film was used as a control. Culturing at 37deg.C for 12 hr, collecting 1mL of bacterial suspension, and gradually diluting with sterile physiological saline to 10 -6 Multiple times. 0.1mL of bacterial suspension with proper dilution ratio is respectively and evenly coated on a PDA plate, and the culture is carried out for 24 hours at 37 ℃. The plate count with colony count of 30-300CFU is selected, and the antibacterial rate is calculated as follows:
I=（N 1 -N 2 ）/N 1
wherein: i is the bacteriostasis rate (%); n1 is the colony count of the control; n2 is the colony count of the membrane-containing samples. The colony count was measured by the method of GB 4789.2-2016 "food safety national Standard food microorganism test colony count measurement".
The test results show that the antibacterial rates of the examples 1, 2 and 3 are above 98%, and the composite film has excellent antibacterial and bacteriostatic properties.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (2)
1. The biodegradable film is characterized by being prepared from the following raw materials in parts by weight: 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 carboxymethylcellulose and 3.5-4.5 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 according to the mass ratio (75-80): (10-15): (5-10): 1, preparing;
the preparation method of the modified food-grade thermoplastic starch comprises the following steps: firstly, 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 according to mass ratio respectively for blending to obtain modified food-grade thermoplastic starch; the control temperature of the blending is 140-160 ℃, the rotating speed of a blending rotor is 40-50 rpm, and the blending time is 10-30 minutes;
the preparation method 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 mixture into a high-speed mixer to be uniformly mixed to obtain a mixture for standby;
(2) Feeding the mixture into a double-screw extruder for melt extrusion to obtain a resin material;
(3) The resin material is sent into a film blowing unit, and a polylactic acid composite film is obtained through inflation, cooling, traction and rolling;
the rotating speed of the high-speed mixer in the step (1) is 240-300 revolutions per minute, and the mixing time is 4-8 minutes;
in the step (2), the temperature of the extruder barrel is controlled to be 165-175 ℃, the rotating speed of the screw is 200-300rpm, and the length-diameter ratio of the screw is 55:1, a step of;
the set temperature of the film blowing unit in the step (3) is as follows: a region: 145-155 ℃, two areas: 155-160 ℃, three regions: 160-165 ℃, four regions: 165-170 ℃, five regions: 170-175 ℃, the traction speed is 2.5-5m/min, and the blow-up ratio is 2-5.
2. The biodegradable film according to claim 1, characterized in that it 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 carboxymethyl cellulose and 3 parts of tea tree essential oil.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211268565.9A CN115403909B (en) | 2022-10-17 | 2022-10-17 | Biodegradable film and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211268565.9A CN115403909B (en) | 2022-10-17 | 2022-10-17 | Biodegradable film and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115403909A CN115403909A (en) | 2022-11-29 |
| CN115403909B true CN115403909B (en) | 2023-11-03 |
Family
ID=84168081
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211268565.9A Active CN115403909B (en) | 2022-10-17 | 2022-10-17 | Biodegradable film and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115403909B (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102599030A (en) * | 2012-01-19 | 2012-07-25 | 北京化工大学 | Degradable sludge-based mulching film and preparation method of degradable sludge-based mulching film |
| CN103284974A (en) * | 2013-04-03 | 2013-09-11 | 中国人民解放军广州军区武汉总医院 | Phencynonate hydrochloride double-layer osmotic pump controlled release tablet and preparation method thereof |
| CN103450648A (en) * | 2012-06-05 | 2013-12-18 | 上海杰事杰新材料(集团)股份有限公司 | Biodegradable polylactic acid/starch compound material and preparation method thereof |
| CN104910426A (en) * | 2015-05-27 | 2015-09-16 | 铜陵方正塑业科技有限公司 | Full-degradable plastic film taking surface hydrophobically modified starch as base material and preparation method thereof |
| CN105440606A (en) * | 2014-09-02 | 2016-03-30 | 允友成(宿迁)复合新材料有限公司 | Preparation method of fully biodegradable starch/polylactic acid base resin |
| CN111890769A (en) * | 2020-08-09 | 2020-11-06 | 刘军林 | Antibacterial composite polylactic acid preservative film material and preparation method thereof |
| CN112876828A (en) * | 2021-02-22 | 2021-06-01 | 安徽双津实业有限公司 | Degradable electronic film and preparation method thereof |
| CN113788991A (en) * | 2021-09-08 | 2021-12-14 | 广州绿徽新材料研究院有限公司 | Biodegradable high-performance modified particle material and preparation method thereof |
| WO2021258760A1 (en) * | 2020-06-24 | 2021-12-30 | 上海昶法新材料有限公司 | Biodegradable material, and raw material composition, preparation method, and application of biodegradable material |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100379800C (en) * | 2003-05-27 | 2008-04-09 | 旭化成化学株式会社 | Biodegradable resin film or sheet and process for producing the same |
| JP6287832B2 (en) * | 2013-03-26 | 2018-03-07 | 東レ株式会社 | the film |
-
2022
- 2022-10-17 CN CN202211268565.9A patent/CN115403909B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102599030A (en) * | 2012-01-19 | 2012-07-25 | 北京化工大学 | Degradable sludge-based mulching film and preparation method of degradable sludge-based mulching film |
| CN103450648A (en) * | 2012-06-05 | 2013-12-18 | 上海杰事杰新材料(集团)股份有限公司 | Biodegradable polylactic acid/starch compound material and preparation method thereof |
| CN103284974A (en) * | 2013-04-03 | 2013-09-11 | 中国人民解放军广州军区武汉总医院 | Phencynonate hydrochloride double-layer osmotic pump controlled release tablet and preparation method thereof |
| CN105440606A (en) * | 2014-09-02 | 2016-03-30 | 允友成(宿迁)复合新材料有限公司 | Preparation method of fully biodegradable starch/polylactic acid base resin |
| CN104910426A (en) * | 2015-05-27 | 2015-09-16 | 铜陵方正塑业科技有限公司 | Full-degradable plastic film taking surface hydrophobically modified starch as base material and preparation method thereof |
| WO2021258760A1 (en) * | 2020-06-24 | 2021-12-30 | 上海昶法新材料有限公司 | Biodegradable material, and raw material composition, preparation method, and application of biodegradable material |
| CN111890769A (en) * | 2020-08-09 | 2020-11-06 | 刘军林 | Antibacterial composite polylactic acid preservative film material and preparation method thereof |
| CN112876828A (en) * | 2021-02-22 | 2021-06-01 | 安徽双津实业有限公司 | Degradable electronic film and preparation method thereof |
| CN113788991A (en) * | 2021-09-08 | 2021-12-14 | 广州绿徽新材料研究院有限公司 | Biodegradable high-performance modified particle material and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 三种添加物对聚乳酸复合膜性能影响;刘文龙等;包装工程;第41卷(第17期);第71-77页 * |
| 增塑剂对聚乳酸/热塑淀粉复合膜性能的影响;于力等;包装工程;第41卷(第5期);第121-127页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115403909A (en) | 2022-11-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhang et al. | Effects of ultrasonication duration and graphene oxide and nano-zinc oxide contents on the properties of polyvinyl alcohol nanocomposites | |
| CN102504345B (en) | Disposable controlled completely-degradable plastic packing bag and preparation method thereof | |
| CN113698646B (en) | Transparent moisture-preserving antibacterial degradable packaging film and preparation method and application thereof | |
| CN108299711B (en) | Antibacterial packaging film and processing method | |
| CN111057289A (en) | LDPE/corn starch/TiO2Antibacterial composite membrane and preparation method thereof | |
| CN109206645A (en) | A kind of edible film-coating and preparation method thereof | |
| CN115449199B (en) | High-molecular material antibacterial plastic bubble bag and preparation method thereof | |
| CN116218173A (en) | New packaging bag material with strong antibacterial property and preparation method thereof | |
| CN115403909B (en) | Biodegradable film and preparation method thereof | |
| CN111019170A (en) | Preparation method of completely degradable biomass food packaging film | |
| CN112175361B (en) | High-barrier stretch-resistant antibacterial film type degradable material and preparation method thereof | |
| CN115785609A (en) | Transparent ABS resin composition and preparation method and application thereof | |
| CN114395221B (en) | Quaternary blending degradable intercalation antibacterial high-permeability preservative film and preparation method thereof | |
| CN115710409A (en) | Bio-based antibacterial packaging film and preparation method thereof | |
| CN115302934A (en) | Full-biodegradable double-layer antibacterial composite film and preparation method thereof | |
| CN111012954B (en) | PVC composition for antibacterial hydrophilic catheter and preparation method thereof | |
| CN112159578A (en) | Medical high-molecular antibacterial material and preparation process thereof | |
| CN113801448B (en) | Biodegradable color master batch and preparation method thereof | |
| CN117511149B (en) | Antibacterial breathable film and preparation method and application thereof | |
| CN109679188B (en) | Antibacterial functional polymer master batch and packaging film | |
| CN115139596B (en) | High-transparency cellulose acetate biodegradable composite film and preparation method thereof | |
| CN118546509A (en) | Fiber-based packaging material for medical packaging bag and preparation method thereof | |
| CN107141662A (en) | A kind of preparation method for the polyvinylidene chloride composition for extending the food fresh keeping phase | |
| CN107216580B (en) | Preparation method of PVDC composition for self-adhesion preservation | |
| CN116239833A (en) | Preparation method of mildew-proof modified atmosphere preservative film for fruits |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |