CN114106531A - starch-PBAT degradable composite material and preparation method thereof - Google Patents
starch-PBAT degradable composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a starch-PBAT degradable composite material and a preparation method thereof, wherein the main raw materials comprise: 20-40 parts of superfine starch, 40-50 parts of poly (butylene adipate/terephthalate) (PBAT), 18-27 parts of double-crosslinked regenerated cellulose, 2-3 parts of frankincense powder, 5-8 parts of plasticizer, 3-5 parts of lubricant, 1-3 parts of dispersing agent and 1-3 parts of ionic liquid. Compared with the prior art, the starch-PBAT degradable composite material prepared by the formula has good tensile property, hydrophobic property, antibacterial property and degradable property.
Description
Technical Field
The invention relates to the technical field of degradable plastics, in particular to a starch-PBAT degradable composite material and a preparation method thereof.
Background
As a novel lightweight chemical material, plastic is called as four large pillars in the material field together with steel, wood and cement. Because of its advantages of light weight, durability, good formability and low processing cost, the usage amount has leaping the top of the world in terms of volume. Plastic products, often used as food packaging materials, play an important role in extending the shelf life of food, protecting food quality and hygiene, etc. While plastic products are widely used in life and production, they put a lot of pressure on the living environment of the human society. On one hand, along with the excessive exploitation and utilization of petrochemical resources, the storage capacity of the petrochemical resources is gradually reduced, and even the petrochemical resources face the danger of exhaustion; on the other hand, plastic products prepared from the traditional petroleum-based plastics are long in degradation time period and easy to generate white pollution, and the large amount of disposable non-degradable plastic products cause great negative effects on soil and environment, seriously damage the environment and harm human health. Therefore, the development and popularization of environment-friendly biodegradable materials are urgent needs for relieving the current ecological pressure of the environment. Because the development and application of the environment-friendly biodegradable material have wide market prospect, the social benefit and the ecological benefit are very obvious, and the technology upgrading and updating of the production and processing industry of packaging, medicines, foods and disposable consumption articles for women and children can be promoted. Therefore, the novel ecological green packaging material which is degradable, renewable and sustainable is concerned more and more by the production industry and society.
Starch is the most common storage form of carbohydrates in plant cells, and is present in higher amounts in corn, tapioca, potato, wheat, and other plants. Starch, which is degraded and returns to nature in the form of carbon dioxide and water, is considered as the most promising biodegradable material and can replace the traditional petroleum energy source by reasonable utilization. However, starch granules have a partially crystalline structure, and have strong intermolecular hydrogen bonding force, so that when the starch granules are subjected to heat and force simultaneously, the starch granules have extremely poor fluidity and are difficult to process and mold, cannot be subjected to thermoplastic processing such as melt extrusion, and are difficult to be used alone as a high polymer material, and therefore, starch is generally required to be modified or prepared by blending with other polymers.
Currently, many reports about the research of starch-PBAT degradable composite materials are reported.
In the early days, the semi-biodegradable plastic products were prepared by mixing biodegradable raw materials such as starch with plastic components, and only the starch component of the semi-biodegradable plastic products could be degraded, but the plastic components could not be degraded and could not be recycled easily. The semi-biodegradable plastic cannot fundamentally solve the environmental problem and is eliminated. The starch is subjected to physical or chemical treatment, so that the thermoplastic processability of the starch is improved, the starch has good plastic film forming performance, and meanwhile, the starch can be rapidly degraded in a proper environment, and complete biodegradation can be really realized. In addition, the starch is blended and compounded with polymers such as polylactic acid, gelatin, cellulose, chitosan, cellulose acetate, bacterial cellulose and the like, so that the completely biodegradable material for food containers and packaging materials can be prepared.
Among these, cellulose is a polyhydroxyglucose polymer, and this structure gives cellulose a number of unique advantages: (1) the cellulose macromolecular chain has a plurality of hydroxyl groups, so that the cellulose macromolecular chain has stronger reaction performance and interaction performance, and has simple process, low cost and no pollution in the processing process; (2) can be completely degraded by microorganisms; (3) the cellulose material is nontoxic and can be widely applied; (4) the biocompatibility is good. Therefore, cellulose has a wide application prospect in composite materials, and in recent years, research reports on cellulose reinforced polymer matrix composite materials are increasing, and common fibers mainly comprise natural fibers, plant fibers, synthetic fibers and micro/nano fibers. Chinese patent CN 108530855A discloses a cellulose/starch-based degradable plastic film material, which selects a biodegradable high polymer material as a base material, and the prepared plastic film can be completely decomposed into water and carbon dioxide in 6 to 12 months under the action of soil and microorganisms through reasonable proportion, thereby being green, environment-friendly and pollution-free; chinese patent CN 106832432A discloses a cellulose-reinforced starch-based plastic and a preparation method and application thereof, and the preparation raw materials comprise: 20-60% of polyolefin; 25-70% of cellulose or lignin modified starch, 5-10% of additive, 0-5% of extrusion aid and 0-15% of filler, wherein the cellulose or lignin modified starch is used as renewable raw material to blend polyolefin, the modified starch can be uniformly dispersed in a polyolefin matrix, and compared with the use of single starch or cellulose, the mechanical property of the obtained plastic product is remarkably improved. However, in the prior art, the cellulose and the thermoplastic starch are blended to only play a role in enhancing the blending, and the water resistance, the heat resistance and the antibacterial property of the plastic are obviously weaker. Chinese patent CN 113121964A discloses an environment-friendly degradable packaging bag and a preparation method thereof, wherein the raw materials comprise 5-10 parts of polylactic acid (PLA), 60-70 parts of poly adipic acid/butylene terephthalate (PBAT), 25-30 parts of corn starch and 0.1-0.3 part of cross-linking agent; however, the compatibility between the interface of the common starch and the interface of the PBAT is poor, so that the prepared packaging bag has poor gas barrier property and cannot meet the use requirement of a specific scene, such as vacuum packaging of cold chain food. Therefore, it is very important to prepare a degradable plastic with good antibacterial performance and gas barrier performance.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a starch-PBAT degradable composite material. The specific technical scheme is as follows:
a starch-PBAT degradable composite material comprises the following raw materials: 20-40 parts of superfine starch, 40-50 parts of poly (butylene adipate)/terephthalate, 18-27 parts of double-crosslinked regenerated cellulose, 2-3 parts of frankincense powder, 5-8 parts of plasticizer, 3-5 parts of lubricant, 1-3 parts of dispersant and 1-3 parts of ionic liquid.
Preferably, the preparation method of the ultrafine starch comprises the following steps: selecting common starch, drying for 15-18 hours at 55-60 ℃ in an oven to reduce the water content to 5-8%, and then carrying out superfine grinding, wherein the feeding amount is 1-2 kg, the feeding frequency is 2-3 Hz, the grinding working medium pressure is 0.6-0.8 MPa, the rotating speed of a classifier is 3000-3600 r/min, and the grinding time is 90-120 min, so as to obtain the superfine starch.
Preferably, the common starch is one of corn starch, glutinous rice starch, cassava starch, potato starch, rice starch, wheat starch, barley starch, acorn starch, sago starch, sweet potato starch and pea starch.
Preferably, the double-crosslinked regenerated cellulose is prepared by adopting the following method:
dissolving cellulose in pre-cooled sodium hydroxide/urea aqueous solution to form 4-6 wt% of transparent cellulose solution; adding epoxy chloropropane with the volume 3-4 times that of the transparent cellulose solution, and violently stirring at-15 to-10 ℃; removing bubbles through centrifugation, sealing in a glass mold, and storing at 2-5 ℃ for 24-36 h to obtain cellulose gel; then, soaking the obtained cellulose gel into 70-75% ethanol water solution, reacting for 2-4 h at 2-5 ℃ to generate solvent exchange, and finishing the physical crosslinking process; removing residual epoxy chloropropane, thoroughly washing the obtained product with water, and then carrying out hot pressing at the temperature of 105-110 ℃ and the pressure of 0.1-0.2 MPa for 25-30 min to obtain the double-crosslinking regenerated cellulose.
The invention adopts the combination of double-crosslinking regenerated cellulose and starch, and enhances the performance of the starch-PBAT degradable composite material. The double-crosslinking regenerated cellulose is prepared by modifying natural cellulose by a chemical/physical double-crosslinking method, and obviously changing the arrangement and orientation distribution of the internal structure of the cellulose by combining a plane hot pressing process and a water molecule auxiliary forming process, thereby obviously improving the toughness, thermodynamic stability and hydrophobicity of the cellulose.
Preferably, the plasticizer is epoxidized soybean oil.
Preferably, the lubricant is zinc stearate.
Preferably, the dispersant is selected from one or a combination of more than two of titanate, stearic acid and oleic acid.
Preferably, the milk powder is prepared by the following method: crushing the solidified frankincense, sieving the crushed frankincense through a 60-mesh sieve to obtain frankincense coarse powder, freezing the frankincense coarse powder at the low temperature of-20 to-18 ℃ for 3 to 4 hours, taking out the frankincense coarse powder, performing superfine grinding, and sieving the obtained product through a 200-260-mesh sieve to obtain the frankincense powder.
Olibanum, which is resin exuded from bark of Boswellia serrata of Burseraceae, mainly contains active ingredients such as lactobionic acid and volatile oil, and has effects of promoting blood circulation, relieving pain, eliminating swelling and promoting granulation. The frankincense extracted from the agave serrata has wide application prospects in many countries, and researches show that the frankincense powder also has antibacterial and antifungal effects, and the biological material composite material taking the frankincense as the filler is not applied to the production of biological plastics. According to the invention, the mastic powder and the double-crosslinking regenerated cellulose are combined and applied to the starch-PBAT degradable composite material, so that the plastic is further endowed with good antibacterial performance, and in addition, the plasticizer and the frankincense generate strong interaction through intermolecular bonding, so that the tensile strength of the starch-PBAT degradable composite material is further enhanced, the comprehensive performance of the starch-PBAT degradable composite material is improved, and the starch-PBAT degradable composite material can be particularly well applied to the field of food packaging.
The inventor finds that the starch-PBAT degradable composite material has certain effect on prolonging the quality guarantee period of cold fresh meat, but the effect is not ideal when the starch-PBAT degradable composite material is prepared into the vacuum package of cold chain food, particularly the vacuum package of the cold fresh meat. After intensive research on vacuum preservation of cold fresh meat, the gas barrier property of a vacuum packaging bag made of the starch-PBAT degradable composite material is found to be deficient. The inventor finds that the oxygen barrier property of the starch-PBAT degradable composite material can be effectively improved by adding the specific ionic liquid with sulfo groups into the starch-PBAT degradable composite material, so that the quality guarantee period of the vacuum packaging bag for the cold fresh meat is effectively prolonged. The reason for this may be: the ionic liquid with sulfo groups can reduce the surface energy of vacuum packaging prepared from the starch-PBAT degradable composite material, so that the solubility coefficient of water vapor on the surface of the vacuum packaging is reduced, and the oxygen barrier property of the vacuum packaging is improved.
Preferably, the ionic liquid is an ionic liquid with sulfo groups, and the preparation method comprises the following steps:
(1) dissolving 3-5 g N-methylimidazole in 10-30 mL of anhydrous toluene to obtain an N-methylimidazole solution; dissolving 5-7 g of 1, 3-propane sultone in 10-30 mL of anhydrous toluene to obtain a 1, 3-propane sultone solution; slowly dripping a 1, 3-propane sultone solution into an N-methylimidazole solution in an ice water bath, slowly heating to room temperature after dripping is finished, stirring at the speed of 500r/min for 1-3 h, filtering, washing a filter cake with 10-30 mL of anhydrous toluene for 2-5 times, and performing vacuum drying on the filter cake at the temperature of 80-120 ℃ for 3-6 h to obtain a white crystal product, namely 1-methyl-3- (3-sulfopropyl) imidazole inner salt;
(2) adding 5-10 g of 1-methyl-3- (3-sulfopropyl) imidazole inner salt prepared in the step (1) into 10-50 mL of water to obtain 1-methyl-3- (3-sulfopropyl) imidazole inner salt water solution; adding 6-10 g of p-toluenesulfonic acid monohydrate into 10-50 mL of deionized water to obtain a p-toluenesulfonic acid aqueous solution; slowly dripping p-toluenesulfonic acid water solution into 1-methyl-3- (3-sulfopropyl) imidazole inner salt at room temperature and at the rotating speed of 300-600 r/min; and after the dropwise addition is finished, stirring for 1-3 h at room temperature and at the rotating speed of 50-200 r/min, performing rotary evaporation until no water is evaporated out, and then performing vacuum drying on the product at 90-120 ℃ for 2-5 h to obtain a light yellow viscous liquid, thus obtaining the ionic liquid with sulfo groups.
The invention also discloses a preparation method of the starch-PBAT degradable composite material, which comprises the following steps:
weighing 20-40 parts by weight of superfine starch, 40-50 parts by weight of poly (butylene adipate/terephthalate), 18-27 parts by weight of double-crosslinked regenerated cellulose, 2-3 parts by weight of frankincense powder, 5-8 parts by weight of plasticizer, 3-5 parts by weight of lubricant, 1-3 parts by weight of dispersant and 1-3 parts by weight of ionic liquid, uniformly mixing at 110-120 ℃, cooling the mixed materials to room temperature, and finally granulating to obtain the starch-PBAT degradable composite material.
In another aspect, the invention also discloses application of the starch-PBAT degradable composite material in preparing food packaging bags. The food packaging bag can be a degradable handbag, a degradable garbage bag and a vacuum food packaging bag.
Compared with the prior art, the invention has the following beneficial effects:
the invention adopts the combination of double-crosslinking regenerated cellulose and starch, and enhances the performance of the starch-PBAT degradable composite material. The double-crosslinking regenerated cellulose is prepared by modifying natural cellulose by a chemical/physical double-crosslinking method, and obviously changing the arrangement and orientation distribution of the internal structure of the cellulose by combining a plane hot pressing process and a water molecule auxiliary forming process, thereby obviously improving the toughness, thermodynamic stability and hydrophobicity of the cellulose. Olibanum, which is resin exuded from bark of Boswellia serrata of Burseraceae, mainly contains active ingredients such as lactobionic acid and volatile oil, and has effects of promoting blood circulation, relieving pain, eliminating swelling and promoting granulation. The frankincense extracted from the agave serrata has wide application prospects in many countries, and researches show that the frankincense powder also has antibacterial and antifungal effects, and the biological material composite material taking the frankincense as the filler is not applied to the production of biological plastics. According to the invention, the mastic powder and the double-crosslinking regenerated cellulose are combined and applied to the starch-PBAT degradable composite material, so that the plastic is further endowed with good antibacterial performance, and in addition, the plasticizer and the frankincense generate strong interaction through intermolecular bonding, so that the tensile strength of the starch-PBAT degradable composite material is further enhanced, the comprehensive performance of the starch-PBAT degradable composite material is improved, and the starch-PBAT degradable composite material can be particularly well applied to the field of food packaging.
Detailed Description
Introduction of raw materials in the examples:
corn starch: purchased from Guang blue Biotech, Inc., Anhui.
Poly (butylene adipate/terephthalate): CAS number 55231-08-8, available from Suzhou Huaze environmental protection technology, Inc.
Epoxidized soybean oil: CAS number 8013-07-8, available from Jinan Ming Wei chemical Co.
Zinc stearate: CAS number 557-05-1, available from Shandong Xinjiang Ice cream science and technology Co.
Oleic acid: CAS number 112-80-1, available from Shandong Xingqi technology Co., Ltd.
Hemp fiber, available from Qiangli hemp, Inc., Guangxi Longzhou.
Olibanum, available from Yuelin pharmaceuticals, Inc., Bozhou.
Epichlorohydrin, CAS number 106-89-8, available from Shandong Xingqi technical Co.
Example 1
A preparation method of a starch-PBAT degradable composite material comprises the following steps:
s1 preparation of superfine starch: drying corn starch in an oven at 55 ℃ for 16h to reduce the moisture content to 5%, crushing by adopting a fluidized bed airflow crushing system, setting the feeding quantity to be 12kg, the feeding frequency to be 2Hz, the crushing working medium pressure to be 0.6MPa, the rotating speed of a classifier to be 3500r/min, and the crushing time to be 90min to obtain superfine corn starch;
preparation of S2 starch-PBAT degradable composite material: and (2) mixing 30 parts by weight of the superfine corn starch prepared in the step S1, 40 parts by weight of poly (butylene adipate)/terephthalate, 25 parts by weight of double-crosslinked regenerated cellulose, 5 parts by weight of epoxidized soybean oil, 3 parts by weight of zinc stearate and 1 part by weight of oleic acid, putting the mixture into a high-speed mixer, mixing for 15min at 110 ℃, cooling the mixed material to 35 ℃, standing the mixed material for 48 hours at room temperature, and finally putting the mixed material into a reciprocating single-screw granulator with the length-diameter ratio of 1:26 for granulation to prepare the starch-PBAT degradable composite material.
The double-crosslinking regenerated cellulose is prepared according to the following method: dissolving hemp fiber in a pre-cooled sodium hydroxide/urea aqueous solution to form a 6wt% transparent cellulose solution; adding epoxy chloropropane with the volume 4 times that of the transparent cellulose solution, and violently stirring at-15 ℃; removing bubbles by centrifugation, sealing the transparent cellulose solution in a glass mold, preserving at 5 ℃ for 36 hours, and chemically crosslinking hydroxyl on cellulose and epoxy chloropropane to obtain cellulose gel; meanwhile, the epichlorohydrin is hydrolyzed in an alkaline solution to generate glycerol and salt; then, soaking the obtained cellulose gel into 75% ethanol water solution, performing solvent exchange at 5 ℃ to complete a physical crosslinking process, and removing the residual chemical crosslinking agent; the obtained product is thoroughly washed by deionized water and then is hot-pressed for 30min at the temperature of 110 ℃ and the pressure of 0.1MPa to obtain the double-crosslinking regenerated cellulose.
Example 2
A preparation method of a starch-PBAT degradable composite material comprises the following steps:
s1 preparation of superfine starch: drying corn starch in an oven at 55 ℃ for 16h to reduce the moisture content to 5%, crushing by adopting a fluidized bed airflow crushing system, setting the feeding quantity to be 12kg, the feeding frequency to be 2Hz, the crushing working medium pressure to be 0.6MPa, the rotating speed of a classifier to be 3500r/min, and the crushing time to be 90min to obtain superfine corn starch;
preparation of S2 starch-PBAT degradable composite material: and (2) mixing 30 parts by weight of the superfine corn starch prepared in the step S1, 40 parts by weight of poly (butylene adipate)/terephthalate, 22.5 parts by weight of double-crosslinked regenerated cellulose, 2.5 parts by weight of frankincense powder, 5 parts by weight of epoxidized soybean oil, 3 parts by weight of zinc stearate and 1 part by weight of oleic acid, putting the mixture into a high-speed mixer, mixing for 15min at 110 ℃, cooling the mixed material to 35 ℃, standing the mixture for 48 hours at room temperature, and finally putting the mixture into a reciprocating single-screw granulator with the length-diameter ratio of 1:26 for granulation to prepare the starch-PBAT degradable composite material.
The double-crosslinking regenerated cellulose is prepared according to the following method: dissolving hemp fiber in a pre-cooled sodium hydroxide/urea aqueous solution to form a 6wt% transparent cellulose solution; adding epoxy chloropropane with the volume 4 times that of the transparent cellulose solution, and violently stirring at-15 ℃; removing bubbles by centrifugation, sealing the transparent cellulose solution in a glass mold, preserving at 5 ℃ for 36 hours, and chemically crosslinking hydroxyl on cellulose and epoxy chloropropane to obtain cellulose gel; meanwhile, the epichlorohydrin is hydrolyzed in an alkaline solution to generate glycerol and salt; then, soaking the obtained cellulose gel into 75% ethanol water solution, performing solvent exchange at 5 ℃ to complete a physical crosslinking process, and removing the residual chemical crosslinking agent; the obtained product is thoroughly washed by deionized water and then is hot-pressed for 30min at the temperature of 110 ℃ and the pressure of 0.1MPa to obtain the double-crosslinking regenerated cellulose.
The milk powder is prepared by the following method: pulverizing solidified Olibanum with a high-speed pulverizer, sieving with 60 mesh sieve to obtain Olibanum coarse powder, freezing at-18 deg.C for 4 hr, taking out, pulverizing with a high-speed micronizer, and sieving with 220 mesh sieve to obtain Olibanum powder.
Example 3
A preparation method of a starch-PBAT degradable composite material comprises the following steps:
s1 preparation of superfine starch: drying corn starch in an oven at 55 ℃ for 16h to reduce the moisture content to 5%, crushing by adopting a fluidized bed airflow crushing system, setting the feeding quantity to be 12kg, the feeding frequency to be 2Hz, the crushing working medium pressure to be 0.6MPa, the rotating speed of a classifier to be 3500r/min, and the crushing time to be 90min to obtain superfine corn starch;
preparation of S2 starch-PBAT degradable composite material: and (2) mixing 30 parts by weight of the superfine corn starch prepared in the step S1, 40 parts by weight of poly (butylene adipate)/terephthalate, 25 parts by weight of frankincense powder, 5 parts by weight of epoxidized soybean oil, 3 parts by weight of zinc stearate and 1 part by weight of oleic acid, putting the mixture into a high-speed mixer, mixing for 15min at 110 ℃, cooling the mixed material to 35 ℃, standing the mixture for 48 hours at room temperature, and finally putting the mixture into a reciprocating single-screw granulator with the length-diameter ratio of 1:26 for granulation to prepare the starch-PBAT degradable composite material.
The milk powder is prepared by the following method: pulverizing solidified Olibanum with a high-speed pulverizer, sieving with 60 mesh sieve to obtain Olibanum coarse powder, freezing at-18 deg.C for 4 hr, taking out, pulverizing with a high-speed micronizer, and sieving with 220 mesh sieve to obtain Olibanum powder.
Example 4
A preparation method of a starch-PBAT degradable composite material comprises the following steps:
mixing 30 parts by weight of corn starch, 40 parts by weight of poly (butylene adipate/terephthalate), 22.5 parts by weight of double-crosslinked regenerated cellulose, 2.5 parts by weight of milk powder, 5 parts by weight of epoxidized soybean oil, 3 parts by weight of zinc stearate and 1 part by weight of oleic acid, putting the mixture into a high-speed mixer, mixing for 15min at 110 ℃, cooling the mixed material to 35 ℃, standing the mixed material at room temperature for 48 hours, and finally putting the mixed material into a reciprocating single-screw granulator with the length-diameter ratio of 1:26 for granulation to prepare the starch-PBAT degradable composite material.
The double-crosslinking regenerated cellulose is prepared according to the following method: dissolving hemp fiber in a pre-cooled sodium hydroxide/urea aqueous solution to form a 6wt% transparent cellulose solution; adding epoxy chloropropane with the volume 4 times that of the transparent cellulose solution, and violently stirring at-15 ℃; removing bubbles by centrifugation, sealing the transparent cellulose solution in a glass mold, preserving at 5 ℃ for 36 hours, and chemically crosslinking hydroxyl on cellulose and epoxy chloropropane to obtain cellulose gel; meanwhile, the epichlorohydrin is hydrolyzed in an alkaline solution to generate glycerol and salt; then, soaking the obtained cellulose gel into 75% ethanol water solution, performing solvent exchange at 5 ℃ to complete a physical crosslinking process, and removing the residual chemical crosslinking agent; the obtained product is thoroughly washed by deionized water and then is hot-pressed for 30min at the temperature of 110 ℃ and the pressure of 0.1MPa to obtain the double-crosslinking regenerated cellulose.
The milk powder is prepared by the following method: pulverizing solidified Olibanum with a high-speed pulverizer, sieving with 60 mesh sieve to obtain Olibanum coarse powder, freezing at-18 deg.C for 4 hr, taking out, pulverizing with a high-speed micronizer, and sieving with 220 mesh sieve to obtain Olibanum powder.
Comparative example 1
A preparation method of a starch-PBAT degradable composite material comprises the following steps:
s1 preparation of superfine starch: drying corn starch in an oven at 55 ℃ for 16h to reduce the moisture content to 5%, crushing by adopting a fluidized bed airflow crushing system, setting the feeding quantity to be 12kg, the feeding frequency to be 2Hz, the crushing working medium pressure to be 0.6MPa, the rotating speed of a classifier to be 3500r/min, and the crushing time to be 90min to obtain superfine corn starch;
preparation of S2 starch-PBAT degradable composite material: and (2) mixing 30 parts by weight of the superfine corn starch prepared in the step S1, 40 parts by weight of poly (butylene adipate)/terephthalate, 5 parts by weight of epoxidized soybean oil, 3 parts by weight of zinc stearate and 1 part by weight of oleic acid, putting the mixture into a high-speed mixer, mixing for 15min at 110 ℃, cooling the mixed material to 35 ℃, standing the mixture at room temperature for 48 hours, and finally putting the mixture into a reciprocating single-screw granulator with the length-diameter ratio of 1:26 for granulation to prepare the starch-PBAT degradable composite material.
Comparative example 2
A preparation method of a starch-PBAT degradable composite material comprises the following steps:
s1 preparation of superfine starch: drying corn starch in an oven at 55 ℃ for 16h to reduce the moisture content to 5%, crushing by adopting a fluidized bed airflow crushing system, setting the feeding quantity to be 12kg, the feeding frequency to be 2Hz, the crushing working medium pressure to be 0.6MPa, the rotating speed of a classifier to be 3500r/min, and the crushing time to be 90min to obtain superfine corn starch;
preparation of S2 starch-PBAT degradable composite material: and (2) mixing 30 parts by weight of the superfine corn starch prepared in the step S1, 40 parts by weight of poly (butylene adipate)/terephthalate, 25 parts by weight of hemp fiber, 5 parts by weight of epoxidized soybean oil, 3 parts by weight of zinc stearate and 1 part by weight of oleic acid, putting the mixture into a high-speed mixer, mixing for 15min at 110 ℃, cooling the mixed material to 35 ℃, standing the mixture for 48 hours at room temperature, and finally putting the mixture into a reciprocating single-screw granulator with the length-diameter ratio of 1:26 for granulation to prepare the starch-PBAT degradable composite material.
Example 5
A preparation method of a starch-PBAT degradable composite material comprises the following steps:
s1 preparation of superfine starch: drying corn starch in an oven at 55 ℃ for 16h to reduce the moisture content to 5%, crushing by adopting a fluidized bed airflow crushing system, setting the feeding quantity to be 12kg, the feeding frequency to be 2Hz, the crushing working medium pressure to be 0.6MPa, the rotating speed of a classifier to be 3500r/min, and the crushing time to be 90min to obtain superfine corn starch;
preparation of S2 starch-PBAT degradable composite material: and (2) mixing 30 parts by weight of the superfine corn starch prepared in the step S1, 40 parts by weight of poly (butylene adipate)/terephthalate, 22.5 parts by weight of double-crosslinked regenerated cellulose, 2.5 parts by weight of frankincense powder, 5 parts by weight of epoxidized soybean oil, 3 parts by weight of zinc stearate, 1 part by weight of oleic acid and 2 parts by weight of ionic liquid, putting the mixture into a high-speed mixer, mixing for 15min at 110 ℃, cooling the mixed material to 35 ℃, standing the mixed material for 48 hours at room temperature, and finally putting the mixed material into a reciprocating single-screw granulator with the length-diameter ratio of 1:26 for granulation to prepare the starch-PBAT degradable composite material.
The preparation method of the double-crosslinked regenerated cellulose is the same as that of example 2, and the details are not repeated herein.
The preparation method of the mastic powder is the same as that of example 2, and the details are not repeated here.
The ionic liquid is an ionic liquid with sulfo groups, and the preparation method comprises the following steps:
(1) 4.105 g N-methylimidazole is dissolved in 20mL of anhydrous toluene to obtain an N-methylimidazole solution; 6.107g of 1, 3-propane sultone is dissolved in 20mL of anhydrous toluene to obtain a 1, 3-propane sultone solution; dripping 1, 3-propane sultone solution into N-methylimidazole solution at the speed of 10mL/min in an ice water bath, slowly raising the temperature to 25 ℃ after dripping is finished, stirring for 2h at the speed of 500r/min, then filtering, washing a filter cake for 3 times by using 20mL of anhydrous toluene to obtain a filter cake, and performing vacuum drying for 5h at the temperature of 100 ℃ to obtain a product which is a white crystal, namely 1-methyl-3- (3-sulfopropyl) imidazole inner salt;
(2) adding 8.42 g of 1-methyl-3- (3-sulfopropyl) imidazole inner salt prepared in the step (1) into 25mL of deionized water to obtain 1-methyl-3- (3-sulfopropyl) imidazole inner salt aqueous solution; adding 8.95 g of p-toluenesulfonic acid monohydrate into 25mL of deionized water to obtain a p-toluenesulfonic acid aqueous solution; dripping p-toluenesulfonic acid aqueous solution into 1-methyl-3- (3-sulfopropyl) imidazole inner salt at the speed of 10mL/min at the conditions of room temperature of 25 ℃ and the rotating speed of 500 r/min; and after the dropwise addition is finished, stirring for 2.0 h at the room temperature of 25 ℃ and the rotation speed of 100 r/min, performing rotary evaporation until no water is evaporated out, and then performing vacuum drying on the product at the temperature of 100 ℃ for 4.0h to obtain a light yellow viscous liquid, namely the ionic liquid with sulfo groups.
Example 6
A vacuum packaging bag based on starch-PBAT degradable composite material: blowing a film of the starch-PBAT degradable composite material prepared in the embodiment 5 on a blow molding machine, and performing compression molding; the vacuum packaging bag is manufactured by adopting a heat sealing machine through cutting and roll dividing processes.
Test example 1
The starch-PBAT degradable composites prepared in examples 1 to 4 and comparative examples 1 and 2 were subjected to tensile strength test. The mechanical property test can visually reflect the mechanical property of the composite material when the composite material bears the action of external load such as stretching, bending and the like. The starch-PBAT degradable composites were tested for tensile properties using a universal materials tester model 3369, Instron, usa. The specific test method comprises the steps of carrying out a tensile test on a universal material testing machine according to a plastic tensile property test standard GB/T1040.2-2006 Plastic tensile property, wherein the tensile rate is 2mm/min, each group is tested for 5 times, and the average value of the tests is calculated. The specific test results are shown in table 1, and the tensile strength is calculated according to the following formula:
in the formula:
: tensile strength, MPa;
f: maximum load, N;
b: sample width, mm;
h: specimen thickness, mm.
Table 1 tensile Strength test results table
The table 1 shows that the tensile property of the starch-PBAT degradable composite material added with the double-crosslinking regenerated cellulose as the reinforcing agent is obviously improved, the double-crosslinking regenerated cellulose is used for modifying natural cellulose by a chemical/physical double-crosslinking method, and the arrangement and orientation distribution of the internal structure of the cellulose are obviously changed by combining a plane hot pressing and water molecule auxiliary forming process, so that the toughness of the cellulose is obviously improved. Comparing example 1 and example 2, it was found that the addition of mastic further enhances the tensile properties of the plastic, since mastic, in addition to being bound to the double cross-linked regenerated cellulose, also interacts strongly with the plasticizer through intermolecular binding, thereby further enhancing the tensile strength of the starch-PBAT degradable composite.
Test example 2
The starch-PBAT degradable composite materials prepared in examples 1-4 and comparative examples 1 and 2 were tested for antibacterial performance according to the test method specified in the standards of QB/T2591-2003 antibacterial plastic antibacterial performance test method and antibacterial effect, the bacteria test strains were Staphylococcus aureus ATCC 6538 and Escherichia coli ATCC 25922, the mold test strain was Candida albicans ATCC 10231, and the test results are shown in Table 2.
Table 2 antibacterial property test results table
As a novel plastic, especially a degradable plastic applied to the food field, the novel plastic has good antibacterial performance and safety and durability, the added antibacterial component can effectively kill or inhibit microorganisms, and the used antibacterial component has no adverse effect on the human body and has durability in the repeated use process. According to the invention, the mastic powder and the double-crosslinking regenerated cellulose are combined, so that the starch-PBAT degradable composite material has good antibacterial performance, and the starch-PBAT degradable composite material has high inhibition rate on bacteria and can also act on fungi.
Test example 3
The starch-PBAT degradable composite materials prepared in examples 1-4 and comparative examples 1 and 2 are subjected to water absorption performance measurement, an immersion method is selected for water absorption performance measurement, prepared starch-PBAT degradable composite material sheets are uniformly cut into squares of 50 multiplied by 50mm in each group according to GB/T1034-2008 determination of plastic water absorption, the squares are dried in a drying oven at 50 +/-2 ℃ for 24 hours, and the weight is weighed and recorded as ml. Placing the sample into a container or room with a relative humidity of 50% +/-5% and controlling the temperature at 23.0 deg.C + -1.0 deg.C, standing for 24 hr + -1 hr, and weighing to obtain sample with an accuracy of 0.1 mg. After the sample is taken out of the container or room with a relative humidity of 50% +/-5%, the weighing should be completed within 1min and recorded as m2。
The water absorption mass fraction c of the sample is calculated according to the following formula:
in the formula:
c: the water absorption mass fraction of the sample, the numerical value being expressed in%;
ml: weight before and after drying before soaking in milligrams (mg);
m2: the weight of the soaked sample is in milligrams (mg).
Table 3 water absorption property test result table
The water absorption properties of plastic packaging are an important physical quantity characterizing the water absorption properties of a material. The water absorbed by the starch-PBAT degradable composite material is mainly accumulated in three areas inside the plastic: starch matrix, cellulose and the interfacial region between starch and cellulose. The starch matrix is more hygroscopic and the double cross-linked regenerated cellulose is less hygroscopic than starch. As can be seen from table 3, the addition of the double-crosslinked regenerated cellulose can significantly reduce the water absorption of the starch-PBAT degradable composite material, which is probably because the interaction between the double-crosslinked regenerated cellulose molecules and starch inside the starch-PBAT degradable composite material replaces the action between starch and water molecules, and with the addition of the mastic, the action is more significant, so that the moisture absorption rate of the whole system is reduced.
Test example 4
After the starch-PBAT degradable composite materials of the embodiments 1 to 5 are subjected to film blowing and compression molding, the biodegradability is tested according to the biodegradability test method of the biodegradable material recorded in appendix D of GB/T18006.2-1999 degradation performance test method of disposable degradable tableware. Test results show that the biodegradation rate of the packaging bags prepared from the starch-PBAT degradable composite materials of the embodiments 1-5 is more than 89%.
Test example 5
The oxygen barrier performance test refers to the GB/T1038-; blowing a film on the starch-PBAT degradable composite materials of the embodiments 2 and 5, and pressing and forming the materials according to requirements; the conditions of the size, the thickness and the like of the sample are kept consistent. The test temperature is 23 ℃, the relative humidity is 50 +/-5%, and the test area is 50 cm2Each group was 3 replicates and the average was taken.
TABLE 4 oxygen barrier Properties
As can be seen from table 4, in example 5, when the specific ionic liquid with a sulfo group is added to the starch-PBAT degradable composite material, the oxygen transmission rate of the starch-PBAT degradable composite material can be effectively reduced, and the shelf life of the vacuum packaging bag for the chilled fresh meat can be further effectively prolonged. The reason for this may be: the ionic liquid with sulfo groups can reduce the surface energy of vacuum packaging prepared from the starch-PBAT degradable composite material, so that the solubility coefficient of water vapor on the surface of the vacuum packaging is reduced, and the oxygen barrier property of the vacuum packaging is improved.
Claims (10)
1. A starch-PBAT degradable composite material is characterized by comprising the following raw materials: 20-40 parts of superfine starch, 40-50 parts of poly (butylene adipate)/terephthalate, 18-27 parts of double-crosslinked regenerated cellulose, 2-3 parts of frankincense powder, 5-8 parts of plasticizer, 3-5 parts of lubricant, 1-3 parts of dispersant and 1-3 parts of ionic liquid.
2. The starch-PBAT degradable composite material of claim 1, wherein the ultrafine starch is prepared by the method comprising: selecting common starch, drying for 15-18 hours at 55-60 ℃ in an oven to reduce the water content to 5-8%, and then carrying out superfine grinding, wherein the feeding amount is 1-2 kg, the feeding frequency is 2-3 Hz, the grinding working medium pressure is 0.6-0.8 MPa, the rotating speed of a classifier is 3000-3600 r/min, and the grinding time is 90-120 min, so as to obtain the superfine starch.
3. The starch-PBAT degradable composite of claim 2, characterized in that: the common starch is one of corn starch, glutinous rice starch, cassava starch, potato starch, rice starch, wheat starch, barley starch, acorn starch, sago starch, sweet potato starch and pea starch.
4. The starch-PBAT degradable composite of claim 1 wherein the double cross-linked regenerated cellulose is prepared by the following method:
dissolving cellulose in pre-cooled sodium hydroxide/urea aqueous solution to form 4-6 wt% of transparent cellulose solution; adding epoxy chloropropane with the volume 3-4 times that of the transparent cellulose solution, and violently stirring at-15 to-10 ℃; removing bubbles through centrifugation, sealing in a glass mold, and storing at 2-5 ℃ for 24-36 h to obtain cellulose gel; then, soaking the obtained cellulose gel into 70-75% ethanol water solution, reacting for 2-4 h at 2-5 ℃ to generate solvent exchange, and finishing the physical crosslinking process; removing residual epoxy chloropropane, thoroughly washing the obtained product with water, and then carrying out hot pressing at the temperature of 105-110 ℃ and the pressure of 0.1-0.2 MPa for 25-30 min to obtain the double-crosslinking regenerated cellulose.
5. The starch-PBAT degradable composite of claim 1, characterized in that: the plasticizer is epoxidized soybean oil.
6. The starch-PBAT degradable composite of claim 1, characterized in that: the lubricant is zinc stearate.
7. The starch-PBAT degradable composite of claim 1, characterized in that: the dispersant is selected from one or the combination of more than two of titanate, stearic acid and oleic acid.
8. The starch-PBAT degradable composite material of claim 1, wherein the ionic liquid is an ionic liquid with sulfo groups, and the preparation method is as follows:
(1) dissolving 3-5 g N-methylimidazole in 10-30 mL of anhydrous toluene to obtain an N-methylimidazole solution; dissolving 5-7 g of 1, 3-propane sultone in 10-30 mL of anhydrous toluene to obtain a 1, 3-propane sultone solution; slowly dripping a 1, 3-propane sultone solution into an N-methylimidazole solution in an ice water bath, slowly heating to room temperature after dripping is finished, stirring at the speed of 500r/min for 1-3 h, filtering, washing a filter cake with 10-30 mL of anhydrous toluene for 2-5 times, and performing vacuum drying on the filter cake at the temperature of 80-120 ℃ for 3-6 h to obtain a white crystal product, namely 1-methyl-3- (3-sulfopropyl) imidazole inner salt;
(2) adding 5-10 g of 1-methyl-3- (3-sulfopropyl) imidazole inner salt prepared in the step (1) into 10-50 mL of water to obtain 1-methyl-3- (3-sulfopropyl) imidazole inner salt water solution; adding 6-10 g of p-toluenesulfonic acid monohydrate into 10-50 mL of deionized water to obtain a p-toluenesulfonic acid aqueous solution; slowly dripping p-toluenesulfonic acid water solution into 1-methyl-3- (3-sulfopropyl) imidazole inner salt at room temperature and at the rotating speed of 300-600 r/min; and after the dropwise addition is finished, stirring for 1-3 h at room temperature and at the rotating speed of 50-200 r/min, performing rotary evaporation until no water is evaporated out, and then performing vacuum drying on the product at 90-120 ℃ for 2-5 h to obtain a light yellow viscous liquid, thus obtaining the ionic liquid with sulfo groups.
9. The preparation method of the starch-PBAT degradable composite material according to any one of claims 1 to 8, comprising the following steps: taking 20-40 parts by weight of superfine starch, 40-50 parts by weight of poly (butylene adipate/terephthalate), 18-27 parts by weight of double-crosslinked regenerated cellulose, 2-3 parts by weight of frankincense powder, 5-8 parts by weight of plasticizer, 3-5 parts by weight of lubricant, 1-3 parts by weight of dispersant and 1-3 parts by weight of ionic liquid, uniformly mixing at 110-120 ℃, cooling the mixed materials to room temperature, and finally granulating to obtain the starch-PBAT degradable composite material.
10. Use of the starch-PBAT degradable composite material according to any of claims 1 to 8 for the preparation of food packaging bags.
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