CN114573963A - Biodegradable breathable film and preparation method thereof - Google Patents
Biodegradable breathable film and preparation method thereof Download PDFInfo
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Abstract
The invention provides a biodegradable breathable film and a preparation method thereof, wherein the biodegradable breathable film comprises the following raw materials in parts by weight: 80-100 parts of PLA resin; 15-25 parts of PCL resin; 20-30 parts of PBSA resin; 3-8 parts of an antibacterial agent; 2-5 parts of an antioxidant; 4-10 parts of functional filler; 2-5 parts of a plasticizer; 1-3 parts of a chain extender; the antibacterial agent is prepared by compounding tea polyphenols, thymol and chitosan; the functional filler is formed by compounding calcareous bentonite, glycerol and titanium dioxide; the biodegradable breathable film prepared by double-screw extrusion granulation and single-screw extrusion film blowing machine blow molding not only meets the requirements of food contact materials, but also has good mechanical property, antibacterial property and air permeability, high safety and good transparency, and can be applied to the fields of food freshness protection bags and supermarket rolling bags.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a biodegradable breathable film and a preparation method thereof.
Background
In recent years, with the increasing demand of global plastic markets, the problem of white pollution caused by non-degradable waste plastic packages has attracted people's attention. With the increasing importance of people on environmental protection and food safety, it is very important to improve the packaging quality by using biodegradable high molecular packaging materials. Chinese patent document publication No. CN106317474A discloses a high-breathability caprolactone grafted starch degradable film, which is prepared from the following raw materials in parts by weight: 100 parts of corn starch, 8-10 parts of wheat starch, 10101-2 parts of antioxidant, 1-2 parts of isopropyl tri (dioctyl pyrophosphato acyloxy) titanate, 15-20 parts of polyvinyl alcohol, 803-4 parts of polysorbate, 80-100 parts of DMF, 8-10 parts of acetic anhydride, 120 parts of pyridine 100-; although the degradable film prepared by the invention has high air permeability, the film has the characteristics of low transparency, poor mechanical property, toxicity and high risk of partial used raw materials, the safety of the invention in practical application is reduced, and the possibility of secondary environmental pollution exists after degradation.
Therefore, the biodegradable breathable film with high safety, high transparency, good mechanical property and antibacterial property is researched and developed, and has important significance for keeping freshness and prolonging shelf life of food.
Disclosure of Invention
The invention provides a biodegradable breathable film and a preparation method thereof, aiming at solving the problems of poor safety, low transparency and poor mechanical property of a degradable film.
In order to solve the technical problems, the invention adopts a technical scheme that:
a biodegradable breathable film comprises the following raw materials in parts by weight: 80-100 parts of polylactic acid resin (PLA); 15-25 parts of polycaprolactone resin (PCL); 20-30 parts of poly (butylene succinate-adipate) resin (PBSA); 3-8 parts of an antibacterial agent; 2-5 parts of an antioxidant; 4-10 parts of functional filler; 2-5 parts of a plasticizer; 1-3 parts of a chain extender;
the antibacterial agent is compounded by tea polyphenol, thymol and chitosan, wherein the mass ratio of the tea polyphenol to the thymol to the chitosan is 2.4: 1.7: 5.2;
the functional filler is formed by compounding calcium bentonite, glycerol and titanium dioxide, wherein the mass ratio of the calcium bentonite to the glycerol to the titanium dioxide is 10: 4: 3.
further, the antibacterial agent comprises the following composite components:
according to the parts by weight, dissolving tea polyphenol, thymol and chitosan in a round-bottom flask filled with acetic acid solution, and hermetically soaking and mixing for 10-12h at room temperature to obtain a soaked mixture;
putting the round-bottom flask filled with the soaking mixture into an ultrasonic water bath, and introducing inert gas N into the round-bottom flask2Heating the soaking mixture in the round-bottom flask in water bath at the temperature of 80 ℃ and under 240W ultrasonic power for 0.5-1h, and stopping adding N in the round-bottom flask2Introducing, placing the mixture in the round-bottom flask in a vacuum suction filter for suction filtration separation, placing the mixture after suction filtration separation in an oven for drying at 60 ℃ to obtain the antibacterial agent compounded by chitosan-loaded tea polyphenol and thymol; the obtained composite antibacterial agent effectively improves thymol and teaDue to the utilization of polyphenol, the condition that the tea polyphenol, the thymol and the raw materials are directly mixed and are lost in the preparation process of the biodegradable breathable film is avoided, and the antibacterial effect of the film is effectively enhanced.
Further, the total amount of the tea polyphenol, the thymol and the chitosan accounts for 20-35 wt% of the acetic acid solution.
Further, the functional filler is compounded and composed by the following steps:
adding calcium bentonite into distilled water according to the parts by weight, magnetically stirring at the temperature of 60 ℃ and the rotating speed of 200rpm for 10-15min, adding glycerol and titanium dioxide, and continuously magnetically stirring at the temperature of 85 ℃ and the rotating speed of 500rpm for 0.5-1h to obtain a suspended mixed solution;
and pouring the suspended mixed solution into a round culture dish, placing the round culture dish into a forced air drying oven, and drying the round culture dish for 18 to 24 hours at the temperature of 60 ℃ to obtain the functional filler compounded by the calcareous bentonite, the glycerol and the titanium dioxide.
Further, the total amount of the calcareous bentonite, the glycerol and the titanium dioxide accounts for 12 to 35 weight percent of the suspension mixed liquor.
Further, the antioxidant is a mixture of an antioxidant 1010 and an antioxidant 168, and the mass ratio of the antioxidant 1010 to the antioxidant 168 is 1.3: 1;
the plasticizer is plasticizer DOP.
Further, the chain extender is a mixture of glycerol and an ADR-4368C chain extender, wherein the mass ratio of the glycerol to the ADR-4368C chain extender is 1: 1.5.
further, the preparation method of the biodegradable breathable film comprises the following steps:
step (1): placing the PLA resin into a forced air drying oven, drying for 3-4h at 75-85 ℃ to remove water, and taking out for later use; placing the PCL resin in an air-blast drying oven, drying at 50-60 deg.C for 2.5-3h to remove water, and taking out for use; putting the PBSA resin into a blast drying oven, drying for 3-4h at 50-55 ℃ to remove water, and taking out for later use;
step (2): adding the PLA resin, the PCL resin and the PBSA resin obtained by drying in the step (1) into a vacuum stirrer, continuously adding an antibacterial agent, an antioxidant, a functional filler, a plasticizer and a chain extender according to the parts by weight, and uniformly stirring at the temperature of 50 ℃ and the rotating speed of 80rpm for 10-15min to obtain a premixed raw material;
and (3): placing the premixed raw materials obtained in the step (2) into a double-screw extruder, melting and blending at the rotating speed of 80-100rpm and the temperature of 160-175 ℃, extruding, cooling with water, and cutting and granulating by a cutting machine to obtain composite master batches;
and (4): placing the composite master batch obtained in the step (3) in a container with a sample in a blast drying oven, spreading the composite master batch in the container, drying at 60-75 ℃ for 0.5-1.5h, and taking out; and (3) placing the dried composite master batch into a feeding hopper of a single-screw extrusion film blowing machine, and blowing at the screw rotating speed of 60-70rpm to prepare the biodegradable breathable film.
Further, the temperature of the single-screw extrusion zone in the step (4) is 160-175 ℃, and the mold temperature of the film blowing machine is 170 ℃.
Further, in the step (4), the composite master batch is dried by the air-blast drying oven, and the time for drying the composite master batch by the air-blast drying oven is determined by the following method:
wherein the content of the first and second substances,
m is the mass of the composite master batch, and unit kg;
a is the surface area of the composite master batch in the blast drying oven after being tiled in the container and the unit m2；
V is the drying air flow speed of the blast drying box and has the unit kg/(m)2·h)；
J is a preset error correction coefficient, and the value of J is 3.7-5.9;
r is a preset constant and takes a value of 4-8;
W0the moisture content of the composite master batch before drying;
W1the moisture content of the dried composite master batch；
WSIs the balance moisture content of the composite master batch.
Further, the biodegradable breathable film is applied to the fields of supermarket rolling bags and food fresh-keeping bags.
The invention has the beneficial effects that:
(1) according to the biodegradable breathable film provided by the invention, the functional components added in the biodegradable breathable film are efficiently compatible with the resin polymer and interact with the resin polymer, so that the comprehensive performance of the biodegradable breathable film is effectively improved, the requirements of food contact materials are met, the biodegradable breathable film also has good mechanical property, antibacterial property and air permeability, is high in safety and transparency, and can be applied to the fields of food freshness protection bags and supermarket rolling bags;
(2) the invention provides a biodegradable breathable film and a preparation method thereof, wherein the functional filler compounded by adding calcareous bentonite and titanium dioxide and other functional additives have obvious influence on the tensile strength and the elongation at break of the biodegradable breathable film, the tensile strength and the elongation at break of the biodegradable breathable film are both improved to a small extent along with the increase of the addition amount of the functional filler, the transparency of the film is not influenced or reduced, and the good appearance is still maintained; in the preparation process, the addition of the composite antibacterial agent and the functional filler fills up the space structure in the resin base material, prevents oxygen molecules from entering gaps among polymers, prevents the dynamic diameter of carbon dioxide and water vapor from being smaller than that of oxygen, influences the crystallization performance of the polymers by adding the functional filler, and enables the carbon dioxide and the water vapor to pass through the gaps among the polymer molecules, so that the biodegradable breathable film has the characteristics of high carbon dioxide and water vapor permeability and low oxygen permeability; in addition, in the functional filler for preparing the biodegradable breathable film, titanium dioxide adsorbed by calcareous bentonite further improves the air permeability and moisture permeability of the biodegradable breathable film due to the photocatalytic activity of the titanium dioxide;
(3) the invention provides a biodegradable breathable film and a preparation method thereof, along with the increase of the antibacterial dose in the biodegradable breathable film, the antibacterial performance of the biodegradable breathable film is gradually enhanced, and the biodegradable breathable film has good antibacterial effect on gram-positive bacteria such as staphylococcus aureus, listeria monocytogenes, gram-negative bacteria such as escherichia coli and salmonella; the preparation and addition of the composite antibacterial agent not only effectively improve the utilization of thymol and tea polyphenol, but also avoid the loss of the biodegradable breathable film due to the direct mixing of tea polyphenol and thymol with the biodegradable breathable film raw material, and the synergistic antibacterial effect of chitosan, thymol and tea polyphenol further effectively enhances the antibacterial effect of the film; meanwhile, in the functional filler for adsorbing titanium dioxide by bentonite, the excellent antibacterial property of the titanium dioxide further enhances the antibacterial effect of the biodegradable breathable film;
(4) the biodegradable breathable film provided by the invention is used as a food fresh-keeping bag for keeping fresh of cherry tomatoes, has a good fresh-keeping effect on the cherry tomatoes, slows down the rotting and deterioration of the cherry tomatoes, and can effectively prolong the shelf life of the cherry tomatoes; the respiration function is still performed when the cherry tomatoes are kept fresh at low temperature, in the process of keeping the cherry tomatoes fresh and refrigerating by the food fresh-keeping bag, oxygen and carbon dioxide in the bag can change along with the change of the respiration function, and the permeability of the biodegradable breathable film prepared by the invention to the oxygen and the carbon dioxide is different, so that the dynamic balance of gas exchange in the bag is maintained; with the prolonging of the storage time, oxygen in the bag is gradually consumed, and due to the characteristics of high carbon dioxide permeability and low oxygen permeability of the biodegradable breathable film, the respiration of the cherry tomatoes is inhibited, and the propagation of bacteria is reduced, so that the quality of the cherry tomatoes is delayed to be reduced, and the shelf life of the cherry tomatoes is prolonged;
(5) the invention provides a biodegradable breathable film and a preparation method thereof, which determine a calculation method for the time for drying a composite master batch by an air-blast drying oven, can directly calculate and determine the time for drying the composite master batch by the air-blast drying oven, shortens the effective time of a biodegradable breathable film preparation system, and avoids the problems that the quality cannot meet the requirement due to too long or too short time for drying the composite master batch and the processes of master batch preparation and drying need to be repeated; the method not only can effectively ensure the removal of water in the resin, but also is beneficial to processing the composite master batch to prepare the biodegradable breathable film with excellent performance.
Detailed Description
The following description of the preferred embodiments of the present invention is provided for the purpose of illustration and description, and is in no way intended to limit the invention.
Example 1
A biodegradable breathable film comprises the following raw materials in parts by weight: 85 parts of a PLA resin; 20 parts of a PCL resin; 25 parts of PBSA resin; 5 parts of an antibacterial agent; 3 parts of a mixture of antioxidant 1010 and antioxidant 168; 6 parts of functional filler; 2 parts of plasticizer DOP; 2 parts of a mixture of glycerol and ADR-4368C chain extender;
the antibacterial agent is compounded by tea polyphenol, thymol and chitosan, wherein the mass ratio of the tea polyphenol to the thymol to the chitosan is 2.4: 1.7: 5.2;
the functional filler is formed by compounding calcium bentonite, glycerol and titanium dioxide, wherein the mass ratio of the calcium bentonite to the glycerol to the titanium dioxide is 10: 4: 3.
the antibacterial agent comprises the following composite steps:
according to the parts by weight, dissolving tea polyphenol, thymol and chitosan in a round-bottom flask filled with acetic acid solution, and hermetically soaking and mixing for 12 hours at room temperature to obtain a soaked mixture;
placing the round-bottom flask containing the soaking mixture in an ultrasonic water bath, and introducing inert gas N into the round-bottom flask2Heating the soaking mixture in the round-bottom flask in water bath at 80 ℃ and 240W ultrasonic power for 0.5h, and stopping adding N in the round-bottom flask2Introducing, placing the mixture in the round-bottom flask in a vacuum suction filter for suction filtration separation, placing the mixture after suction filtration separation in an oven for drying at 60 ℃ to obtain the antibacterial agent compounded by chitosan-loaded tea polyphenol and thymol;
the total amount of the tea polyphenol, the thymol and the chitosan accounts for 30 wt% of the acetic acid solution.
The functional filler comprises the following composite components:
adding calcium bentonite into distilled water according to the parts by weight, magnetically stirring at the temperature of 60 ℃ and the rotating speed of 200rpm for 15min, adding glycerol and titanium dioxide, and continuously magnetically stirring at the temperature of 85 ℃ and the rotating speed of 500rpm for 1h to obtain a suspended mixed solution;
pouring the suspended mixed solution into a round culture dish, placing the round culture dish in a forced air drying oven, and drying the round culture dish for 24 hours at the temperature of 60 ℃ to obtain the functional filler compounded by the calcium bentonite, the glycerol and the titanium dioxide;
the total amount of the calcareous bentonite, the glycerol and the titanium dioxide accounts for 29 wt% of the suspension mixed liquor.
A preparation method of a biodegradable breathable film comprises the following steps:
step (1): placing the PLA resin into a forced air drying oven, drying for 3-4h at 75-85 ℃ to remove water, and taking out for later use; placing the PCL resin in an air-blast drying oven, drying at 50-60 deg.C for 2.5-3h to remove water, and taking out for use; putting the PBSA resin into a blast drying oven, drying for 3-4h at 50-55 ℃ to remove water, and taking out for later use;
step (2): adding the PLA resin, the PCL resin and the PBSA resin obtained by drying in the step (1) into a vacuum stirrer, continuously adding an antibacterial agent, an antioxidant, a functional filler, a plasticizer and a chain extender according to the parts by weight, and uniformly stirring at the temperature of 50 ℃ and the rotating speed of 80rpm for 15min to obtain a premixed raw material;
and (3): placing the premixed raw materials obtained in the step (2) into a double-screw extruder, melting and blending under the conditions that the screw rotation speed is 90rpm, and the temperature of each interval from a feeding end to a discharging end is 160 ℃, 165 ℃, 170 ℃, 175 ℃ and 175 ℃, extruding, cooling with water, and then cutting and granulating through a cutting machine to obtain composite master batches;
and (4): placing the composite master batch obtained in the step (3) in a container with a sample in a blast drying oven, spreading the composite master batch in the container, drying at 60-75 ℃ for 0.5-1.5h, and taking out; placing the dried composite master batch into a feeding hopper of a single-screw extrusion film blowing machine, and blowing at the screw rotating speed of 60rpm to prepare the biodegradable breathable film; the temperature of each interval from the feeding end of the single-screw extrusion film blowing machine to the die end is 160 ℃, 165 ℃, 175 ℃ and 170 ℃.
Example 2
A biodegradable breathable film comprises the following raw materials in parts by weight: 90 parts of a PLA resin; 15 parts of a PCL resin; 30 parts of PBSA resin; 6 parts of an antibacterial agent; 4 parts of a mixture of antioxidant 1010 and antioxidant 168; 8 parts of functional filler; 2 parts of plasticizer DOP; 3 parts of a mixture of glycerol and ADR-4368C chain extender;
the antibacterial agent is compounded by tea polyphenol, thymol and chitosan, wherein the mass ratio of the tea polyphenol to the thymol to the chitosan is 2.4: 1.7: 5.2;
the functional filler is formed by compounding calcium bentonite, glycerol and titanium dioxide, wherein the mass ratio of the calcium bentonite to the glycerol to the titanium dioxide is 10: 4: 3.
biodegradable breathable films were obtained by the preparation method in example 1.
A composite antibacterial agent was obtained in the same manner as in example 1; wherein, the total amount of the tea polyphenol, the thymol and the chitosan in the preparation of the composite antibacterial agent accounts for 33 wt% of the acetic acid solution.
A composite functional filler was obtained according to the method in example 1; wherein the total amount of the calcareous bentonite, the glycerol and the titanium dioxide accounts for 31 wt% of the suspension mixed liquor.
Example 3
A biodegradable breathable film comprises the following raw materials in parts by weight: 90 parts of a PLA resin; 25 parts of a PCL resin; 25 parts of PBSA resin; 7 parts of an antibacterial agent; 4 parts of a mixture of antioxidant 1010 and antioxidant 168; 9 parts of functional filler; 2 parts of plasticizer DOP; 3 parts of a mixture of glycerol and ADR-4368C chain extender;
the antibacterial agent is compounded by tea polyphenol, thymol and chitosan, wherein the mass ratio of the tea polyphenol to the thymol to the chitosan is 2.4: 1.7: 5.2;
the functional filler is formed by compounding calcium bentonite, glycerol and titanium dioxide, wherein the mass ratio of the calcium bentonite to the glycerol to the titanium dioxide is 10: 4: 3.
biodegradable breathable films were obtained by the preparation method in example 1.
A composite antibacterial agent was obtained according to the method in example 1; wherein the total amount of tea polyphenol, thymol and chitosan in the preparation of the composite antibacterial agent accounts for 35 wt% of the acetic acid solution.
A composite functional filler was obtained according to the method in example 1; wherein the total amount of the calcareous bentonite, the glycerol and the titanium dioxide accounts for 33 wt% of the suspension mixed liquor.
Comparative example 1
A biodegradable breathable film comprises the following raw materials in parts by weight: 85 parts of a PLA resin; 20 parts of a PCL resin; 25 parts of PBSA resin; 5 parts of a mixture of thymol and tea polyphenols; 3 parts of a mixture of antioxidant 1010 and antioxidant 168; 6 parts of functional filler; 2 parts of plasticizer DOP; 2 parts of a mixture of glycerol and ADR-4368C chain extender;
the mass ratio of the thymol to the tea polyphenol is 1: 1.
the functional filler is formed by compounding calcium bentonite, glycerol and titanium dioxide, wherein the mass ratio of the calcium bentonite to the glycerol to the titanium dioxide is 10: 4: 3.
biodegradable breathable films were obtained by the preparation method in example 1.
A composite functional filler was obtained according to the method in example 1; wherein the total amount of the calcareous bentonite, the glycerol and the titanium dioxide accounts for 29 wt% of the suspension mixed liquor.
Comparative example 2
A biodegradable breathable film comprises the following raw materials in parts by weight: 85 parts of a PLA resin; 20 parts of a PCL resin; 25 parts of PBSA resin; 5 parts of an antibacterial agent; 3 parts of a mixture of antioxidant 1010 and antioxidant 168; 6 parts of calcareous bentonite; 2 parts of plasticizer DOP; 2 parts of a mixture of glycerol and ADR-4368C chain extender;
the antibacterial agent is compounded by tea polyphenol, thymol and chitosan, wherein the mass ratio of the tea polyphenol to the thymol to the chitosan is 2.4: 1.7: 5.2.
biodegradable breathable films were obtained by the preparation method in example 1.
A composite antibacterial agent was obtained in the same manner as in example 1; wherein the total amount of tea polyphenol, thymol and chitosan in the preparation of the composite antibacterial agent accounts for 30 wt% of the acetic acid solution.
Comparative example 3
A biodegradable breathable film comprises the following raw materials in parts by weight: 85 parts of a PLA resin; 20 parts of a PCL resin; 25 parts of PBSA resin; 3 parts of a mixture of antioxidant 1010 and antioxidant 168; 2 parts of plasticizer DOP; 2 parts of a mixture of glycerol and ADR-4368C chain extender;
biodegradable breathable films were obtained by the preparation method in example 1.
Test examples
The biodegradable breathable films prepared in examples 1-3 and comparative examples 1-3 were tested for mechanical properties, transparency, air permeability and moisture permeability, and the test results are shown in table 1:
TABLE 1
As can be seen from the table 1, compared with the comparative example 3, the addition of the functional filler compounded by the calcareous bentonite and the titanium dioxide and other functional additives has a remarkable influence on the tensile strength and the elongation at break of the biodegradable breathable films in the examples 1-3 and the comparative example 1, and the tensile strength and the elongation at break are both improved to a small extent along with the increase of the addition amount of the functional filler; the biodegradable breathable films prepared in examples 1-3 and comparative examples 1-3 all had good light transmittance, which indicates that the added antibacterial agent and functional filler did not affect or reduce the transparency of the films and still maintained good appearance; from table 1, it can be seen that the main characteristics of the biodegradable breathable films of examples 1-3 are high carbon dioxide transmission, high moisture transmission and low oxygen transmission, with the highest carbon dioxide and Water Vapor Transmission Rates (WVTR) and the lowest oxygen transmission rates in example 3; compared with comparative example 3, the carbon dioxide transmission rate of the biodegradable breathable film of example 3 is increased by about 46.2%, the Water Vapor Transmission Rate (WVTR) is increased by about 34.9%, and the oxygen transmission rate is decreased by about 45.8%; the addition of the composite antibacterial agent and the functional filler fills the space structure in the resin base material, prevents oxygen molecules from entering gaps among polymers, prevents the dynamic diameter of carbon dioxide and water vapor from being smaller than that of oxygen, influences the crystallization performance of the polymers due to the addition of the functional filler, and enables the carbon dioxide and the water vapor to pass through the gaps among the polymer molecules, so that the biodegradable breathable films prepared in the embodiments 1-3 have the characteristics of high carbon dioxide and water vapor permeability and low oxygen permeability; in addition, in the functional filler for preparing the biodegradable breathable film, the titanium dioxide adsorbed by the calcareous bentonite further improves the air permeability and the moisture permeability of the biodegradable breathable film due to the photocatalytic activity of the titanium dioxide.
The biodegradable breathable films prepared in examples 1 to 3 and comparative examples 1 to 3 were subjected to an antibacterial property test by a vibration contact antibacterial test method, and the test results are shown in table 2:
TABLE 2
As can be seen from table 2, compared with the biodegradable breathable film prepared in the comparative example 3, in examples 1 to 3, the antibacterial performance of the biodegradable breathable film is gradually enhanced with the increase of the antibacterial dose in the biodegradable breathable film, and the biodegradable breathable film has good antibacterial effects on gram-positive bacteria staphylococcus aureus, listeria monocytogenes, gram-negative bacteria escherichia coli and salmonella, and meets the requirements of food contact materials;
compared with the comparative example 1 that the antibacterial agent added into the biodegradable breathable film is a mixture of thymol and tea polyphenol, the biodegradable breathable film in the example 1 added with the antibacterial agent compounded by tea polyphenol, thymol and chitosan has more remarkable inhibiting effects on staphylococcus aureus, listeria monocytogenes, escherichia coli and salmonella, and the inhibiting effects are respectively improved by 19.7%, 20.9%, 21.1% and 21.2%; this shows that in the preparation method of the biodegradable breathable film of examples 1-3, the preparation and addition of the composite antibacterial agent not only effectively improves the utilization of thymol and tea polyphenol, but also avoids the loss of the biodegradable breathable film due to direct mixing of tea polyphenol and thymol with the biodegradable breathable film raw material, and the antibacterial effect of the film is further effectively enhanced due to the synergistic antibacterial action of chitosan, thymol and tea polyphenol;
meanwhile, the antibacterial property of the biodegradable breathable film in example 1 is also better than that of comparative example 2, which also shows that in example 1, the composite of bentonite and titanium dioxide is used for adsorbing the titanium dioxide, so that the air permeability of the film is enhanced through the synergistic effect, and the antibacterial effect of the biodegradable breathable film is further enhanced through the excellent antibacterial property of the titanium dioxide.
Example 4
The prepared biodegradable breathable films of examples 1 to 3 and comparative examples 1 to 3 were applied to food freshness bags and used for storage and freshness preservation of cherry tomatoes: picking cherry tomatoes with the same quality and particle size, cleaning, and filling into food freshness protection bags with uniform size prepared by biodegradable breathable films in examples 1-3 and comparative examples 1-3, wherein the gram weights of the cherry tomatoes in the freshness protection bags are the same; sealing the opening of the packaging bag, placing the packaging bag in a refrigerating chamber at the temperature of 4 ℃ and the RH of 75 percent, refrigerating and preserving, sampling and detecting every other day, and taking the visible rot and deterioration of the cherry tomatoes as a storage terminal point; the index test results of the cherry tomato fresh keeping day 10 are shown in table 3:
TABLE 3
The working principle and the beneficial effects of the embodiment of the invention are as follows: as can be seen from the table 3, the biodegradable breathable films prepared in the embodiments 1 to 3 of the invention have good fresh-keeping effect on cherry tomatoes, slow down the decay and deterioration of the cherry tomatoes, and can effectively prolong the shelf life of the cherry tomatoes; the respiration effect is still performed when the cherry tomatoes are kept fresh at low temperature, in the process of keeping the cherry tomatoes fresh and refrigerating by the food fresh-keeping bag, the oxygen and the carbon dioxide in the bag change along with the change of the respiration effect, and as can be seen from the table 3, the permeability of the biodegradable breathable films prepared in the embodiments 1-3 and the comparative examples 1-3 of the invention to the oxygen and the carbon dioxide is different, so that the dynamic balance of gas exchange in the bag is maintained; with the prolonging of the storage time, oxygen in the bag is gradually consumed, and due to the characteristics of high carbon dioxide permeability and low oxygen permeability of the biodegradable breathable film, the respiration of the cherry tomatoes is inhibited, and the propagation of bacteria is reduced, so that the quality reduction of the cherry tomatoes is delayed, and the shelf life of the cherry tomatoes is prolonged.
Example 5
And (4) drying the composite master batches in an air-blast drying oven, wherein the time for drying the composite master batches in the air-blast drying oven is determined by the following method:
wherein, the first and the second end of the pipe are connected with each other,
m is the mass of the composite master batch in kg;
a is the surface area of the composite master batch in the blast drying oven after being tiled in the container and the unit m2；
V is the drying air flow speed of the blast drying box and has the unit kg/(m)2·h)；
J is a preset error correction coefficient, and the value of J is 3.7-5.9;
r is a preset constant and takes a value of 4-8;
W0the moisture content of the composite master batch before drying;
W1the moisture content required by the dried composite master batch;
WSis the equilibrium moisture content of the composite master batch.
Based on the preparation method of the biodegradable breathable film in example 1, the influence of the moisture content change of the composite master batch on the mechanical performance of the biodegradable breathable film is analyzed through experiments, and the detection results are shown in table 4:
TABLE 4
The working principle and the beneficial effects of the embodiment of the invention are as follows: the calculation method for determining the time for drying the composite master batches by the air-blast drying oven can directly calculate and determine the time for drying the composite master batches by the air-blast drying oven, shortens the effective time of a biodegradable breathable film preparation system, and avoids the problems that the quality cannot meet the requirement due to too long or too short time for drying the composite master batches, and the processes of master batch preparation and drying need to be repeated; the method not only can effectively ensure that the water in the resin is removed and the content requirement is met, but also is beneficial to processing the composite master batch to prepare the biodegradable breathable film with excellent performance.
The functional components added in the biodegradable breathable film prepared by the invention have high-efficiency compatibility with resin polymers and interaction, so that the comprehensive performance of the biodegradable breathable film is effectively improved.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (10)
1. The biodegradable breathable film is characterized by comprising the following raw materials in parts by weight: 80-100 parts of PLA resin; 15-25 parts of PCL resin; 20-30 parts of PBSA resin; 3-8 parts of an antibacterial agent; 2-5 parts of an antioxidant; 4-10 parts of functional filler; 2-5 parts of a plasticizer; 1-3 parts of a chain extender;
the antibacterial agent is compounded by tea polyphenol, thymol and chitosan, wherein the mass ratio of the tea polyphenol to the thymol to the chitosan is 2.4: 1.7: 5.2;
the functional filler is formed by compounding calcium bentonite, glycerol and titanium dioxide, wherein the mass ratio of the calcium bentonite to the glycerol to the titanium dioxide is 10: 4: 3.
2. the biodegradable breathable film of claim 1, wherein said antimicrobial agent is compounded by the steps of:
according to the parts by weight, dissolving tea polyphenol, thymol and chitosan in a round-bottom flask filled with acetic acid solution, and hermetically soaking and mixing for 10-12h at room temperature to obtain a soaked mixture;
placing the round-bottom flask containing the soaking mixture in an ultrasonic water bath, and introducing inert gas N into the round-bottom flask2Heating the soaking mixture in the round-bottom flask in water bath at 80 ℃ and 240W ultrasonic power for 0.5-1h, and stopping adding N in the round-bottom flask2And (3) introducing, transferring the mixture in the round-bottom flask into a vacuum suction filter, carrying out suction filtration separation, and drying the mixture subjected to suction filtration separation in an oven at 60 ℃ to obtain the antibacterial agent compounded by chitosan-loaded tea polyphenol and thymol.
3. A biodegradable breathable film according to claim 2, wherein said total amount of tea polyphenols, thymol and chitosan is 20-35% by weight of the acetic acid solution.
4. The biodegradable breathable film according to claim 1, wherein said functional filler is compounded by the steps of:
adding calcium bentonite into distilled water according to the parts by weight, magnetically stirring at the temperature of 60 ℃ and the rotating speed of 200rpm for 10-15min, adding glycerol and titanium dioxide, and continuously magnetically stirring at the temperature of 85 ℃ and the rotating speed of 500rpm for 0.5-1h to obtain a suspended mixed solution;
and pouring the suspended mixed solution into a round culture dish, placing the round culture dish into a forced air drying oven, and drying the round culture dish for 18 to 24 hours at the temperature of 60 ℃ to obtain the functional filler compounded by the calcareous bentonite, the glycerol and the titanium dioxide.
5. The biodegradable breathable film according to claim 4, wherein the total amount of said calcareous bentonite, glycerol and titanium dioxide is 12-35 wt% of said suspension mixture.
6. The preparation method of the biodegradable breathable film according to claim 1, wherein the antioxidant is a mixture of an antioxidant 1010 and an antioxidant 168, and the mass ratio of the antioxidant 1010 to the antioxidant 168 is 1.3: 1;
the plasticizer is plasticizer DOP.
7. The preparation method of the biodegradable breathable film according to claim 1, wherein the chain extender is a mixture of glycerol and an ADR-4368C chain extender, wherein the mass ratio of the glycerol to the ADR-4368C chain extender is 1: 1.5.
8. a method for the preparation of biodegradable breathable films according to claims 1 to 7, characterized in that it comprises the following preparation steps:
step (1): placing the PLA resin into a forced air drying oven, drying for 3-4h at 75-85 ℃, and taking out for later use; placing the PCL resin in an air-blast drying oven, drying at 50-60 deg.C for 2.5-3h, and taking out for use; putting the PBSA resin into a blast drying oven, drying for 3-4h at 50-55 ℃, and taking out for later use;
step (2): adding the PLA resin, the PCL resin and the PBSA resin obtained by drying in the step (1) into a vacuum stirrer, continuously adding an antibacterial agent, an antioxidant, a functional filler, a plasticizer and a chain extender according to the parts by weight, and uniformly stirring at the temperature of 50 ℃ and the rotating speed of 80rpm for 10-15min to obtain a premixed raw material;
and (3): placing the premixed raw materials obtained in the step (2) into a double-screw extruder, melting and blending at the rotating speed of 80-100rpm and the temperature of 160-175 ℃, extruding, cooling with water, and cutting and granulating by a cutting machine to obtain composite master batches;
and (4): placing the composite master batch obtained in the step (3) in a container with a sample in a blast drying oven, spreading the composite master batch in the container, drying at 60-75 ℃ for 0.5-1.5h, and taking out; and (3) placing the dried composite master batch into a feeding hopper of a single-screw extrusion film blowing machine, and blowing at the screw rotating speed of 60-70rpm to prepare the biodegradable breathable film.
9. The method as claimed in claim 8, wherein the temperature of the single-screw extrusion zone in step (4) is 160-175 ℃, and the mold temperature of the film blowing machine is 170 ℃.
10. Use of a biodegradable breathable film according to claims 1 to 9, in the field of supermarket rolling bags and food preservation bags.
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