CN113429769B - Biomass antibacterial plastic and preparation method thereof - Google Patents
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/912—Polymers modified by chemical after-treatment derived from hydroxycarboxylic acids
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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Abstract
The invention relates to the technical field of biomass plastics, in particular to a biomass antibacterial plastic and a preparation method thereof. The antibacterial agent comprises, by mass, 30-60 parts of polylactic acid, 10-20 parts of polyhydroxyalkanoate, 20-40 parts of chitosan, 10-30 parts of an antibacterial agent, 5-20 parts of a plasticizer, 5-10 parts of a cross-linking agent, 1-5 parts of a pH buffering agent and 30-50 parts of a solvent; the prepared biomass plastic has improved strength and structural stability, has good antibacterial performance and good biodegradability in the using process, can be completely degraded by microorganisms in nature after being used, and finally generates carbon dioxide and water without polluting the environment.
Description
Technical Field
The invention relates to the technical field of biomass plastics, in particular to a biomass antibacterial plastic and a preparation method thereof.
Background
With the increase of the cognition of fossil energy and the enhancement of environmental protection consciousness, people realize that plastic products produced by chemical raw materials such as petroleum and the like not only need to consume a large amount of energy, but also have great pressure on the environment because of nondegradable or difficult degradation. At present, the micro-plastics of oceans and marine organisms, further make the public aware that non-degradable plastics may accumulate in the food chain and may affect human health. Based on environmental protection and ecological problems, a series of 'plastic limit orders' are provided, which are beneficial to controlling the spread of 'white pollution', reducing the use of non-degradable plastics and replacing the degradable plastics, and particularly in the aspect of food packaging, the biomass plastics or the degradable biomass gradually develops and replaces the traditional plastics, which becomes a trend.
However, the food packaging field can relate to the problems of preventing various bacteria from breeding and preventing food from deteriorating so as to ensure the food safety. The traditional problem of preventing the growth of bacteria in food and the deterioration of food is to add an antibacterial agent into the food, but the antibacterial agent in the prior art can affect the taste of the food on one hand, and on the other hand, the excessive antibacterial agent needs to be added into the food, which can affect the health of human beings. Therefore, the antibacterial agent is added into a food packaging bag or a packaging system, and compared with a packaging material, an antibacterial small bag and an antibacterial packaging system for food, the antibacterial agent added into the food packaging bag is more attractive, saves space and the like; in addition, consumers prefer natural, organic packaging materials and antimicrobial agents to be available for the food being packaged to be safer and healthier. Because the degradable plastic film material is added with natural antibacterial substances, the method is a good method which solves the problem of complaints, accords with cognition, and is environment-friendly, energy-saving and sustainable.
Disclosure of Invention
The invention aims to provide a biomass antibacterial plastic and a preparation method thereof, and aims to solve the problems that the existing fossil energy plastic is not degradable and can not be continuously utilized and the plastic packaging film/bag of food has poor antibacterial property. The prepared biomass plastic has improved strength and structural stability, has good antibacterial performance and good biodegradability in the using process, can be completely degraded by microorganisms in nature after being used, and finally generates carbon dioxide and water without polluting the environment.
In order to achieve the purpose, the invention provides the following technical scheme:
the biomass antibacterial plastic comprises the following raw materials in parts by mass:
the biomass antibacterial plastic comprises the following steps:
the method comprises the following steps: putting a solvent in parts by weight into a beaker, adding an antibacterial agent in parts by weight, stirring at a speed of 120r/min, after stirring for 30min, adding a pH buffering agent to adjust the pH value to make the solution be a neutral solution, adding chitosan in parts by weight, and continuously stirring for 2 h; putting the mixture into a vacuum drying oven, setting the temperature to be 60-100 ℃ and the vacuum degree to be-0.1 MPa, and drying for 6-8 hours to obtain a mixture A for later use;
step two: uniformly mixing polylactic acid and polyhydroxyalkanoate in parts by weight, crushing and sieving with a 200-mesh sieve to obtain a mixture B for later use;
step three: and (3) uniformly mixing the mixture A obtained in the step one and the mixture B obtained in the step two, putting the mixture into a pressurized internal mixer, adding a plasticizer and a cross-linking agent in parts by weight, mixing in a molten state, taking out the mixture after uniform mixing, putting the mixture into a forced air drying oven, drying the mixture for 6-12 hours at 80 ℃, and putting the mixture into a forming device to obtain the biomass antibacterial plastic.
The polylactic acid is modified polylactic acid, namely putting the polylactic acid into a high-pressure reaction kettle, then respectively and sequentially adding terephthalaldehyde, diethylenetriamine and tri (2-aminoethyl) amine, setting the temperature of the high-pressure reaction kettle to be 200 ℃, the pressure to be 10MPa, the stirring speed to be 180r/min, reacting for 4 hours, and cooling to room temperature to obtain the modified polylactic acid, wherein the mass ratio of the polylactic acid to the terephthalaldehyde to the diethylenetriamine to the tri (2-aminoethyl) amine is polylactic acid: terephthalaldehyde: diethylenetriamine: tris (2-aminoethyl) amine ═ 10:2:1: 2.
The polyhydroxy fatty acid ester is a mixture of 3-hydroxybutyric acid-3-hydroxyhexanoate copolymerized vinegar and 3-hydroxybutyric acid-4-hydroxybutanoate copolymerized vinegar, and the mass ratio of the 3-hydroxybutyric acid-3-hydroxyhexanoate copolymerized vinegar to the polyhydroxy fatty acid ester is as follows: 3-hydroxybutyrate-4-hydroxybutyrate copolymer vinegar 3: 5.
the antibacterial agent is a natural antibacterial agent, and is an animal-derived antibacterial agent and a microorganism-derived antibacterial agent according to the following ratio: the mass ratio of the microbial antibacterial agent is 1: 1.
The animal-derived antibacterial agent is one or a mixture of animal lysozyme and lactoperoxidase; the microbial antibacterial agent is one or more of nisin, pediocin, lactic acid bacteria, yeast and non-polyene antibiotics.
The plasticizer is a mixture of glycerol, isosorbide and dimethyl phthalate, and the mass ratio of the glycerol to the dimethyl phthalate is as follows: sorbitol: dimethyl phthalate 1: 1: 3.
the cross-linking agent is one or more of sodium alginate, triethylenetetramine, diacetone acrylamide and hydroxyethyl methacrylate.
The solvent is absolute ethyl alcohol or ultrapure water.
The antibacterial agent also comprises a plant-derived antibacterial agent, wherein the plant-derived antibacterial agent is one of thymol, cinnamon essential oil and clove essential oil, and the plant-derived antibacterial agent is an auxiliary antibacterial agent and is matched with other antibacterial agents to improve antibacterial performance and provide fragrance.
The invention has the beneficial effects that:
1. according to the invention, polylactic acid, polyhydroxyalkanoate and chitosan are used as main materials, the main materials are compatible and are non-toxic and non-irritant polymer materials, the main materials are blended and matched to prepare the biomass plastic, the biomass plastic has good biodegradability, can be completely degraded by microorganisms in nature after being used, and finally generates carbon dioxide and water without polluting the environment, and the antibacterial agent is added to ensure that the biomass plastic has antibacterial property, is natural and safe and can be applied to daily life or the field of food packaging.
2. The polyhydroxy fatty acid ester used in the invention is modified polyhydroxy fatty acid ester, phthalaldehyde (TPA), Diethylenetriamine (DETA) and tris (2-aminoethyl) amine (TREN) are compounded into a dynamic imine polymer, polylactic acid is modified, and the toughness of the polylactic acid plastic is improved on the basis of high strength of the polylactic acid plastic; meanwhile, the use of the polyhydroxyalkanoate improves the tensile strength of the biomass plastic, and the degradation condition becomes mild.
3. The main materials of the inventionThe chitosan is added, not only is a basic material for forming the film of the biomass plastic, but also is blended and matched with the polylactic acid and the polyhydroxyalkanoate to jointly prepare the biomass plastic, and the chitosan has a large amount of-NH +3 Has good antibacterial performance, is coordinated with an antibacterial agent, and improves the antibacterial capability of the biomass plastic.
4. The antibacterial agent is a natural antibacterial agent, and is an animal-derived antibacterial agent and a microorganism-derived antibacterial agent according to the following steps: the mass ratio of the microbial antibacterial agent is 1: 1. The animal-derived antibacterial agent is animal lysozyme and lactoperoxidase, and the microorganism-derived antibacterial agent is nisin, pediocin, lactobacillus, yeast and non-polyene antibiotic. The use of animal lysozyme and lactoperoxidase in the animal-derived antibacterial agent can make bacteria lose activity and cannot propagate in large quantities, thereby achieving antibacterial performance; the microbial source antibacterial agent is specific to specific bacteria, and has strong pertinence and good antibacterial effect.
5. The use of the plasticizer and the cross-linking agent ensures that the overall structure of the biomass plastic is stable, and the strength and the structural stability are improved.
Detailed Description
The technical solutions of the present invention will be described clearly and completely below, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive step based on the embodiments of the present invention, are within the scope of protection of the present invention.
Example 1
The biomass antibacterial plastic comprises the following raw materials in parts by mass: 30 parts of polylactic acid, 10 parts of polyhydroxyalkanoate, 20 parts of chitosan, 10 parts of an antibacterial agent, 5 parts of a plasticizer, 5 parts of a cross-linking agent, 1 part of a pH buffering agent and 30 parts of a solvent;
the antibacterial agent is a natural antibacterial agent, and is an animal-derived antibacterial agent and a microorganism-derived antibacterial agent, wherein the animal-derived antibacterial agent comprises the following components in parts by weight: the mass ratio of the microbial antibacterial agent is 1: 1; the animal source antibacterial agent is animal lysozyme; the microbial antibacterial agent is nisin;
the biomass antibacterial plastic comprises the following steps:
the method comprises the following steps: putting a solvent in parts by weight into a beaker, adding an antibacterial agent in parts by weight, stirring at a speed of 120r/min, after stirring for 30min, adding a pH buffering agent to adjust the pH value to make the solution be a neutral solution, adding chitosan in parts by weight, and continuously stirring for 2 h; putting into a vacuum drying oven, setting the temperature at 60 ℃ and the vacuum degree at-0.1 MPa, and drying for 6h to obtain a mixture A for later use;
step two: uniformly mixing polylactic acid and polyhydroxyalkanoate in parts by weight, crushing and sieving with a 200-mesh sieve to obtain a mixture B for later use;
step three: and (2) uniformly mixing the mixture A obtained in the step one and the mixture B obtained in the step two, putting the mixture into a pressurized internal mixer, adding a plasticizer and a cross-linking agent in parts by weight, mixing in a molten state, uniformly mixing, taking out, putting the mixture into a forced air drying oven, drying for 6 hours at 80 ℃, and putting the mixture into a molding device to obtain the biomass antibacterial plastic.
Example 2
The biomass antibacterial plastic comprises the following raw materials in parts by mass: 60 parts of polylactic acid, 20 parts of polyhydroxyalkanoate, 40 parts of chitosan, 30 parts of an antibacterial agent, 20 parts of a plasticizer, 10 parts of a cross-linking agent, 5 parts of a pH buffering agent and 50 parts of a solvent;
the antibacterial agent is a natural antibacterial agent, and is an animal-derived antibacterial agent and a microorganism-derived antibacterial agent, wherein the animal-derived antibacterial agent comprises the following components in parts by weight: the mass ratio of the microbial antibacterial agent is 1: 1.
The animal-derived antibacterial agent is lactoperoxidase; the microbial antibacterial agent is nisin or pediocin;
the biomass antibacterial plastic comprises the following steps:
the method comprises the following steps: putting a solvent in parts by weight into a beaker, adding an antibacterial agent in parts by weight, stirring at a speed of 120r/min, after stirring for 30min, adding a pH buffering agent to adjust the pH value to make the solution be a neutral solution, adding chitosan in parts by weight, and continuously stirring for 2 h; placing into a vacuum drying oven, setting the temperature at 100 deg.C and the vacuum degree at-0.1 MPa, and drying for 8 hr to obtain mixture A;
step two: uniformly mixing polylactic acid and polyhydroxyalkanoate in parts by weight, crushing and sieving with a 200-mesh sieve to obtain a mixture B for later use;
step three: and (2) uniformly mixing the mixture A obtained in the step one and the mixture B obtained in the step two, putting the mixture into a pressurized internal mixer, adding a plasticizer and a cross-linking agent in parts by weight, mixing in a molten state, uniformly mixing, taking out, putting the mixture into a forced air drying oven, drying for 12 hours at 80 ℃, and putting the mixture into a molding device to obtain the biomass antibacterial plastic.
Example 3
The biomass antibacterial plastic comprises the following raw materials in parts by mass: 45 parts of polylactic acid, 15 parts of polyhydroxyalkanoate, 30 parts of chitosan, 20 parts of an antibacterial agent, 15 parts of a plasticizer, 8 parts of a cross-linking agent, 3 parts of a pH buffering agent and 40 parts of a solvent;
the antibacterial agent is a natural antibacterial agent, and is an animal-derived antibacterial agent and a microorganism-derived antibacterial agent according to the following ratio: the mass ratio of the microbial antibacterial agent is 1: 1.
The animal source antibacterial agent is a mixture of animal lysozyme and lactoperoxidase; the microbial source antibacterial agent is nisin, lactic acid bacteria and non-polyene antibiotic;
the biomass antibacterial plastic comprises the following steps:
the method comprises the following steps: putting a solvent in parts by weight into a beaker, adding an antibacterial agent in parts by weight, stirring at the speed of 120r/min, after stirring for 30min, adding a pH buffering agent to adjust the pH value to make the solution be a neutral solution, adding chitosan in parts by weight, and continuously stirring for 2 h; placing into a vacuum drying oven, setting the temperature at 80 deg.C and the vacuum degree at-0.1 MPa, and drying for 7 hr to obtain mixture A;
step two: uniformly mixing polylactic acid and polyhydroxyalkanoate in parts by weight, crushing and sieving with a 200-mesh sieve to obtain a mixture B for later use;
step three: and (2) uniformly mixing the mixture A obtained in the step one and the mixture B obtained in the step two, putting the mixture into a pressurized internal mixer, adding a plasticizer and a cross-linking agent in parts by weight, mixing in a molten state, uniformly mixing, taking out, putting the mixture into a forced air drying oven, drying for 9 hours at 80 ℃, and putting the mixture into a molding device to obtain the biomass antibacterial plastic.
The results of the performance tests on examples 1 to 3 are shown in the following table
As can be seen from the table, the biomass antibacterial plastic prepared by the method and the formula has good mechanical property and antibacterial property.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (2)
1. The biomass antibacterial plastic is characterized by comprising the following raw materials in parts by mass:
60 parts of polylactic acid, 20 parts of polyhydroxyalkanoate, 40 parts of chitosan, 30 parts of an antibacterial agent, 20 parts of a plasticizer, 10 parts of a cross-linking agent, 5 parts of a pH buffering agent and 50 parts of a solvent;
the biomass antibacterial plastic comprises the following steps:
the method comprises the following steps: putting a solvent in parts by weight into a beaker, adding an antibacterial agent in parts by weight, stirring at a speed of 120r/min, after stirring for 30min, adding a pH buffering agent to adjust the pH value to make the solution be a neutral solution, adding chitosan in parts by weight, and continuously stirring for 2 h; putting the mixture into a vacuum drying oven, setting the temperature to be 60-100 ℃ and the vacuum degree to be 0.1MPa, and drying for 6-8 hours to obtain a mixture A for later use;
step two: uniformly mixing polylactic acid and polyhydroxyalkanoate in parts by weight, crushing and sieving with a 200-mesh sieve to obtain a mixture B for later use;
step three: uniformly mixing the mixture A obtained in the step one and the mixture B obtained in the step two, putting the mixture A and the mixture B into a pressurized internal mixer, adding a plasticizer and a cross-linking agent in parts by weight, mixing in a molten state, taking out the mixture after uniform mixing, putting the mixture into a forced air drying oven, drying the mixture for 6 to 12 hours at the temperature of 80 ℃, and putting the mixture into forming equipment to obtain the biomass antibacterial plastic;
the polylactic acid is modified polylactic acid, namely putting the polylactic acid into a high-pressure reaction kettle, then respectively and sequentially adding terephthalaldehyde, diethylenetriamine and tri (2 aminoethyl) amine, setting the temperature of the high-pressure reaction kettle to be 200 ℃, the pressure to be 10MPa, the stirring speed to be 180r/min, reacting for 4h, and cooling to room temperature to obtain the modified polylactic acid, wherein the mass ratio of the polylactic acid to the terephthalaldehyde to the diethylenetriamine to the tri (2 aminoethyl) amine is polylactic acid: terephthalaldehyde: diethylenetriamine: tris (2 aminoethyl) amine ═ 10:2:1: 2;
the polyhydroxy fatty acid ester is a mixture of 3-hydroxybutyrate 3-hydroxyhexanoate copolymerized vinegar and 3-hydroxybutyrate 4-hydroxybutanoate copolymerized vinegar, and the mass ratio of the 3-hydroxybutanoate 3-hydroxyhexanoate copolymerized vinegar is as follows: 3-hydroxybutyrate-4-hydroxybutyrate copolymer vinegar 3: 5;
the antibacterial agent is a natural antibacterial agent, and is an animal-derived antibacterial agent and a microorganism-derived antibacterial agent, wherein the animal-derived antibacterial agent comprises the following components in parts by weight: the mass ratio of the microbial antibacterial agent is 1: 1;
the animal source antibacterial agent is one or a mixture of animal lysozyme and lactoperoxidase; the microbial source antibacterial agent is one or more of nisin, pediocin, lactic acid bacteria, saccharomycetes and non-polyene antibiotics;
the plasticizer is a mixture of glycerol, isosorbide and dimethyl phthalate, and the mass ratio of the glycerol to the dimethyl phthalate is as follows: sorbitol: dimethyl phthalate 1: 1: 3;
the cross-linking agent is one or more of sodium alginate, triethylenetetramine, diacetone acrylamide and hydroxyethyl methacrylate;
the antibacterial agent also comprises a plant-derived antibacterial agent, wherein the plant-derived antibacterial agent is one of thymol, cinnamon essential oil and clove essential oil.
2. The biomass antibacterial plastic as claimed in claim 1, characterized in that: the solvent is absolute ethyl alcohol or ultrapure water.
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