CN113429769A - Biomass antibacterial plastic and preparation method thereof - Google Patents
Biomass antibacterial plastic and preparation method thereof Download PDFInfo
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- CN113429769A CN113429769A CN202110836911.8A CN202110836911A CN113429769A CN 113429769 A CN113429769 A CN 113429769A CN 202110836911 A CN202110836911 A CN 202110836911A CN 113429769 A CN113429769 A CN 113429769A
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- 229920003023 plastic Polymers 0.000 title claims abstract description 51
- 239000004033 plastic Substances 0.000 title claims abstract description 51
- 239000002028 Biomass Substances 0.000 title claims abstract description 44
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title abstract description 5
- 239000003242 anti bacterial agent Substances 0.000 claims abstract description 77
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 26
- 239000004626 polylactic acid Substances 0.000 claims abstract description 26
- 229920001661 Chitosan Polymers 0.000 claims abstract description 12
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 12
- 239000004014 plasticizer Substances 0.000 claims abstract description 12
- 239000005014 poly(hydroxyalkanoate) Substances 0.000 claims abstract description 12
- 229920000903 polyhydroxyalkanoate Polymers 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 10
- 244000005700 microbiome Species 0.000 claims abstract description 10
- 239000006179 pH buffering agent Substances 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims description 48
- 241001465754 Metazoa Species 0.000 claims description 25
- 238000002156 mixing Methods 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 17
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 claims description 12
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- 230000000813 microbial effect Effects 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 8
- MBYLVOKEDDQJDY-UHFFFAOYSA-N tris(2-aminoethyl)amine Chemical compound NCCN(CCN)CCN MBYLVOKEDDQJDY-UHFFFAOYSA-N 0.000 claims description 8
- 239000000052 vinegar Substances 0.000 claims description 8
- 235000021419 vinegar Nutrition 0.000 claims description 8
- 241000894006 Bacteria Species 0.000 claims description 7
- 108010023244 Lactoperoxidase Proteins 0.000 claims description 6
- 102000045576 Lactoperoxidases Human genes 0.000 claims description 6
- 102000016943 Muramidase Human genes 0.000 claims description 6
- 108010014251 Muramidase Proteins 0.000 claims description 6
- 108010062010 N-Acetylmuramoyl-L-alanine Amidase Proteins 0.000 claims description 6
- 108010053775 Nisin Proteins 0.000 claims description 6
- NVNLLIYOARQCIX-MSHCCFNRSA-N Nisin Chemical compound N1C(=O)[C@@H](CC(C)C)NC(=O)C(=C)NC(=O)[C@@H]([C@H](C)CC)NC(=O)[C@@H](NC(=O)C(=C/C)/NC(=O)[C@H](N)[C@H](C)CC)CSC[C@@H]1C(=O)N[C@@H]1C(=O)N2CCC[C@@H]2C(=O)NCC(=O)N[C@@H](C(=O)N[C@H](CCCCN)C(=O)N[C@@H]2C(NCC(=O)N[C@H](C)C(=O)N[C@H](CC(C)C)C(=O)N[C@H](CCSC)C(=O)NCC(=O)N[C@H](CS[C@@H]2C)C(=O)N[C@H](CC(N)=O)C(=O)N[C@H](CCSC)C(=O)N[C@H](CCCCN)C(=O)N[C@@H]2C(N[C@H](C)C(=O)N[C@@H]3C(=O)N[C@@H](C(N[C@H](CC=4NC=NC=4)C(=O)N[C@H](CS[C@@H]3C)C(=O)N[C@H](CO)C(=O)N[C@H]([C@H](C)CC)C(=O)N[C@H](CC=3NC=NC=3)C(=O)N[C@H](C(C)C)C(=O)NC(=C)C(=O)N[C@H](CCCCN)C(O)=O)=O)CS[C@@H]2C)=O)=O)CS[C@@H]1C NVNLLIYOARQCIX-MSHCCFNRSA-N 0.000 claims description 6
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 6
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 claims description 6
- 229960001826 dimethylphthalate Drugs 0.000 claims description 6
- 229930195729 fatty acid Natural products 0.000 claims description 6
- 239000000194 fatty acid Substances 0.000 claims description 6
- -1 fatty acid ester Chemical class 0.000 claims description 6
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 6
- 229940057428 lactoperoxidase Drugs 0.000 claims description 6
- 239000004325 lysozyme Substances 0.000 claims description 6
- 235000010335 lysozyme Nutrition 0.000 claims description 6
- 229960000274 lysozyme Drugs 0.000 claims description 6
- 239000004309 nisin Substances 0.000 claims description 6
- 235000010297 nisin Nutrition 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 claims description 6
- 241000196324 Embryophyta Species 0.000 claims description 5
- 238000007605 air drying Methods 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 238000007873 sieving Methods 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- RRWWOSSPAGCJFO-UHFFFAOYSA-N 3-hydroxybutanoic acid;3-hydroxyhexanoic acid Chemical compound CC(O)CC(O)=O.CCCC(O)CC(O)=O RRWWOSSPAGCJFO-UHFFFAOYSA-N 0.000 claims description 4
- 108010080032 Pediocins Proteins 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000002459 polyene antibiotic agent Substances 0.000 claims description 4
- MGSRCZKZVOBKFT-UHFFFAOYSA-N thymol Chemical compound CC(C)C1=CC=C(C)C=C1O MGSRCZKZVOBKFT-UHFFFAOYSA-N 0.000 claims description 4
- 239000000341 volatile oil Substances 0.000 claims description 4
- 240000004808 Saccharomyces cerevisiae Species 0.000 claims description 3
- 239000004310 lactic acid Substances 0.000 claims description 3
- 235000014655 lactic acid Nutrition 0.000 claims description 3
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 2
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 2
- FHUDZSGRYLAEKR-UHFFFAOYSA-N 3-hydroxybutanoic acid;4-hydroxybutanoic acid Chemical compound CC(O)CC(O)=O.OCCCC(O)=O FHUDZSGRYLAEKR-UHFFFAOYSA-N 0.000 claims description 2
- 244000223760 Cinnamomum zeylanicum Species 0.000 claims description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 2
- KLDXJTOLSGUMSJ-JGWLITMVSA-N Isosorbide Chemical compound O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 KLDXJTOLSGUMSJ-JGWLITMVSA-N 0.000 claims description 2
- 244000223014 Syzygium aromaticum Species 0.000 claims description 2
- 235000016639 Syzygium aromaticum Nutrition 0.000 claims description 2
- 239000005844 Thymol Substances 0.000 claims description 2
- 235000017803 cinnamon Nutrition 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- 229960005150 glycerol Drugs 0.000 claims description 2
- 229960002479 isosorbide Drugs 0.000 claims description 2
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 claims description 2
- 239000000661 sodium alginate Substances 0.000 claims description 2
- 235000010413 sodium alginate Nutrition 0.000 claims description 2
- 229940005550 sodium alginate Drugs 0.000 claims description 2
- 239000000600 sorbitol Substances 0.000 claims description 2
- 229960000790 thymol Drugs 0.000 claims description 2
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 2
- 239000012498 ultrapure water Substances 0.000 claims description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 6
- 239000001569 carbon dioxide Substances 0.000 abstract description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 3
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- 235000013305 food Nutrition 0.000 description 14
- 239000000463 material Substances 0.000 description 6
- 238000004806 packaging method and process Methods 0.000 description 6
- 229920006238 degradable plastic Polymers 0.000 description 4
- 238000000465 moulding Methods 0.000 description 3
- 241000282414 Homo sapiens Species 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000019771 cognition Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 241000186660 Lactobacillus Species 0.000 description 1
- 239000004599 antimicrobial Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 239000002085 irritant Substances 0.000 description 1
- 231100000021 irritant Toxicity 0.000 description 1
- 229940039696 lactobacillus Drugs 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 235000021485 packed food Nutrition 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- ZWLUXSQADUDCSB-UHFFFAOYSA-N phthalaldehyde Chemical compound O=CC1=CC=CC=C1C=O ZWLUXSQADUDCSB-UHFFFAOYSA-N 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Biological Depolymerization Polymers (AREA)
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 put forward, which is beneficial to controlling the spread of 'white pollution', reducing the use of non-degradable plastics and replacing the degradable plastics, especially in the aspect of food packaging, the biomass plastics or the degradable biomass gradually develops and replaces the traditional plastics, and the trend is.
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 the food packaging bag or the packaging system, and compared with the packaging material, the antibacterial small bag and the antibacterial packaging system for food, the antibacterial agent is more attractive, saves space and the like; in addition, consumers prefer natural, organic packaging materials and antimicrobial agents to render packaged foods 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 at 200 ℃, the pressure at 10MPa, the stirring speed at 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, 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 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 high 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 the nature after being used, and finally generates carbon dioxide and water, so that the environment is not polluted, and the biomass plastic is added with the antibacterial agent, so that the biomass plastic has antibacterial property, and the antibacterial agent 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 increased 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 invention adds chitosan into the main material, which is not only a basic material for film formation of the biomass plastic, but also is blended and matched with polylactic acid and polyhydroxyalkanoate to jointly prepare the biomass plastic, and the chitosan has a large amount of-NH+3Has 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, 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 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 derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope 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, 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 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 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 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 (9)
1. The biomass antibacterial plastic is characterized by comprising 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.
2. The biomass antibacterial plastic as claimed in claim 1, characterized in that: 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 at 200 ℃, the pressure at 10MPa, the stirring speed at 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.
3. The biomass antibacterial plastic as claimed in claim 1, characterized in that: 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.
4. the biomass antibacterial plastic as claimed in claim 1, characterized in that: 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.
5. The biomass antibacterial plastic as claimed in claim 4, wherein: the animal source 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.
6. The biomass antibacterial plastic as claimed in claim 1, characterized in that: 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.
7. the biomass antibacterial plastic as claimed in claim 1, characterized in that: the cross-linking agent is one or more of sodium alginate, triethylenetetramine, diacetone acrylamide and hydroxyethyl methacrylate.
8. The biomass antibacterial plastic as claimed in claim 1, characterized in that: the solvent is absolute ethyl alcohol or ultrapure water.
9. The biomass antibacterial plastic as claimed in claim 1, characterized in that: 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.
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