CN112876745B - Antibacterial biodegradable tableware and preparation method thereof - Google Patents
Antibacterial biodegradable tableware and preparation method thereof Download PDFInfo
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
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- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Abstract
The invention provides antibacterial biodegradable tableware and a preparation method thereof, wherein the antibacterial biodegradable tableware comprises the following components in parts by weight: 40-70 parts of starch, 20-30 parts of PLA (polylactic acid), 5-15 parts of PBAT (poly (butylene adipate-co-terephthalate)), 10-15 parts of plant fiber, 10-15 parts of compatilizer, 1-3 parts of chain extender and 10-15 parts of antibacterial agent; the preparation method comprises the following steps: preparing modified starch, pretreating raw materials, mixing the raw materials, extruding and granulating, and performing injection molding to prepare the degradable tableware; the degradable tableware disclosed by the invention is prepared by taking modified starch as a main material, adding PLA (Poly lactic acid) and PBAT (Poly butylene adipate-co-butylene terephthalate) biodegradable materials to improve the performance and adding a specific type of compatilizer and antibacterial agent for use, and is environment-friendly, low in cost, excellent in degradable performance, excellent in antibacterial performance, good in mechanical property and excellent in puncture resistance.
Description
Technical Field
The invention relates to the technical field of biodegradable food packaging materials, in particular to antibacterial biodegradable tableware, especially a biodegradable lunch box and a preparation method thereof.
Background
With the development of economy, the pace of life is constantly accelerated, fast food is widely accepted, and the market of disposable biodegradable lunch boxes is brought forward to meet the requirement of environmental protection. At present, the economic and environment-friendly degradable snack box is mostly processed by filling inorganic fillers and the like with plant fibers such as straws, rice straws and the like and starch such as corn starch and the like as main materials.
For example, CN111423737A in the prior art discloses a bio-based degradable meal box and a preparation method thereof, which is prepared by using straw powder, a hydrophobic additive, a lubricant, a reactive additive, a biodegradable high molecular compound, an antioxidant, a grafting treatment additive/toughening compatibility additive, and an antibacterial agent as raw materials, and by performing gelation, plasticization, grafting, antioxidation, coupling, and antibacterial treatment on the straw powder, the degradable meal box material with excellent performance is obtained, can be degraded by 72.3% in 60 days, can be completely degraded in 144 days, and effectively solves white pollution.
The prior art CN108420166A discloses a special starch environment-friendly lunch box for high-speed rail, which adopts the mixture of starch and cellulose fiber as main material, uses the auxiliary materials which are food grade or feed grade, and is manufactured by hot-press molding technology, the prepared starch fully-degradable environment-friendly lunch box has the advantages of heat insulation, heat preservation and excellent service performance, can be used for microwave oven heating, can be degraded quickly after being discarded, does not pollute the environment, and the like.
Although the problem that the lunch box can be degraded and white pollution can be treated in a certain degree in the prior art, the degradable lunch box prepared by taking starch or plant fiber as the main material has the technical problems of poor tensile strength, easy fragmentation and the like. The existing degradable plastics begin to adopt biodegradable resins such as PLA, PBAT and other bio-based materials as additives, so that the problems of poor mechanical property, easy fragmentation and the like of the materials are solved. Polylactic acid (PLA) is an important bio-based degradable plastic, has great potential in replacing petroleum-based non-degradable plastics due to excellent properties such as easy processing, high mechanical strength and the like, and products such as food packaging bags, disposable tableware and the like prepared by taking the PLA as a raw material do not affect normal use, and meanwhile, the waste is degradable, so that no pollution is caused to the environment. Although PLA has good properties, PLA is a semi-crystalline polymer that often becomes amorphous after processing due to its extremely slow crystallization rate and fast cooling rate in conventional processing techniques, and thus is inherently brittle, and its properties (such as vapor/gas barrier, impact resistance, and melt viscosity) are often insufficient compared to traditional petroleum polymers, which limits its functional applications. At present, the modes for improving the toughness of PLA mainly comprise copolymerization modification, plasticization modification and melt blending modification, and the melt blending is widely adopted due to simple processing operation and low cost. Polybutylene adipate terephthalate (PBAT) is biodegradable aliphatic-aromatic copolyester, which is synthesized by taking adipic acid, terephthalic acid and 1, 4-butanediol as raw materials through a direct esterification or ester exchange method. PBAT is common biodegradable plastic like PLA, can be degraded in a short time, and cannot cause harm to the environment. Because the glass transition temperature of the PBAT is very low and the PBAT is in a rubber state at room temperature, the PBAT has very good flexibility, high tearing strength, easy processing and good thermal stability, and is widely applied to the fields of packaging bags, films and the like.
PLA and biodegradable flexible resin polybutylene adipate terephthalate (PBAT) are blended, the toughness of the PLA can be improved on the premise of not sacrificing the biodegradability of the blend, but the PLA and the PBAT are incompatible and cannot transfer stress between interfaces under stress, so that the further performance improvement of the material is influenced, and the selection of a proper solubilizer for modification has important significance for improving the compatibility of the blend.
The packaging bag, the film, the tableware and the like prepared from the degradable biological material have excellent antibacterial performance, and an antibacterial agent is usually added for use, wherein the common antibacterial agent comprises an inorganic antibacterial agent, an organic antibacterial agent and the like.
The prior art CN110358264A discloses a bio-based environment-friendly packaging bag and a preparation method thereof, starch, PBAT and PLA are used as raw materials, specifically 20-40 parts of corn starch, 50-70 parts of PBAT, 10-20 parts of PLA, 5-10 parts of glycerol, 0.1-1 part of maleic anhydride, 1-5 parts of ethylene-vinyl acetate copolymer, 0.1-1 part of an opening agent, 1-3 parts of an antibacterial agent, 1-3 parts of talcum powder, 1-3 parts of calcium carbonate and 0.1-1 part of a chain extender, so that the degradation performance of the packaging bag is improved, the packaging bag is green and environment-friendly, meanwhile, the cost is reduced, the antibacterial and mildew-proof performance of the packaging bag is improved by adding the antibacterial agent, and the packaging bag is prepared by the steps of raw material pretreatment, raw material mixing, extrusion granulation, granule mixing, extrusion film blowing and winding.
The prior art CN109401225A discloses a biodegradable preservative film and a preparation method thereof, the raw materials mainly comprise 50-60 parts of PBAT, 15-30 parts of modified starch, 20-40 parts of polylactic acid, 3-10 parts of biodegradable aliphatic-aromatic copolyester, 3-10 parts of methyl hydroxypropyl cellulose ether, 2-8 parts of nano talcum powder, 0.1-0.5 part of chain extender, 0.2-0.8 part of antioxidant and 0.2-0.6 part of lubricant, and the raw materials are prepared by the synergistic effect of the components, so that the cost is greatly reduced while the toughness, plasticity, strength and degradability of the preservative film product are improved, and the preparation method is favorable for large-scale production and application.
The prior art CN108752884A discloses a PLA/PBAT material with high antibacterial property and a preparation method and application thereof, and specifically, an inorganic filler is mixed with a zinc salt aqueous solution under a negative pressure condition, then alkalization, heat treatment and coupling are carried out, so that an antibacterial filler of ZnO uniform powder can be obtained, and finally the antibacterial filler is mixed with PLA and PBAT to obtain the PLA/PBAT material with high antibacterial property, so that the antibacterial efficiency of the material can be improved, and the reduction of the mechanical property of the material caused by directly filling nano ZnO can be avoided.
The prior art CN111286178A discloses an antibacterial degradable blown film material, the raw materials for preparing the material include matrix resin, stabilizer, degradation additive, coupling agent, compatible modifier, antibacterial agent and auxiliary agent, the matrix resin includes at least one of PLA, PBS, PHA or PBAT, the adopted antibacterial agent is modified lignocellulose, modified chitosan or matrine, the material not only can meet the requirement of the blowing process, but also has good antibacterial function, and the mechanical property and stability of the material can be enhanced by adding components such as nano silicon dioxide, nano titanium dioxide and nano cerium oxide, and the material can assist in bacteriostasis.
The existing biodegradable tableware such as meal boxes and the like pay attention to certain aspects of improving the biodegradation rate, mechanical property, antibacterial property, heat resistance and the like of materials, and the problem that meal soup and the like overflow due to the fact that the meal boxes are easily punctured by loaded hard objects during extrusion is not solved. Aiming at the problems that the biodegradable lunch box provided by the prior art cannot simultaneously meet the requirements of degradability, mechanical property, antibacterial property, puncture resistance and the like, the invention provides the biodegradable lunch box which has high biodegradation rate, good mechanical property, excellent antibacterial property and puncture resistance.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide biodegradable tableware with excellent biodegradability, mechanical property, antibacterial property and puncture resistance.
In one aspect of the present invention, there is provided an antibacterial biodegradable tableware comprising the following raw materials
The components are as follows:
40-70 parts of starch
20-30 parts of PLA
PBAT 5-15 parts
10-15 parts of plant fiber
10-15 parts of compatilizer
1-3 parts of chain extender
10-15 parts of an antibacterial agent.
The starch used in the invention is selected from one or more of corn starch, wheat starch, sweet potato starch, cassava starch, potato starch and the like, the natural starch has rich resources, low cost and high degradation rate, but the molecules of the starch contain a large amount of hydroxyl groups, so that the starch has strong hydrophilicity and poor compatibility with biodegradable resin, and the modified starch of the starch is preferably used, and specifically, the modified starch is obtained by mixing the starch and glycerol according to the mass ratio of 2-5:1, adding maleic anhydride accounting for 2-5% of the mass of the starch into the mixture, fully mixing, and extruding and granulating by a double-screw extruder.
The weight average molecular weight of the polylactic acid used in the present invention is 10 to 30X 104g/mol, such as 4032D, 3052D, etc., which are commonly used.
The number average molecular weight of PBAT used in the present invention is 2 to 5X 104g/mol, such as the commonly used commercial brands Ecoflex-F-blend-C1200, TH-801T, etc.
The plant fiber used in the invention is selected from one or more of straw fiber, cotton fiber, hemp fiber, bamboo fiber, wood pulp fiber and the like, preferably the plant fiber is modified by a coupling agent, the coupling agent comprises one or more of silane coupling agent, titanate coupling agent and aluminate coupling agent, for example, an ethanol solution containing 3-5% by weight of gamma-aminopropyltriethoxysilane coupling agent is sprayed on the surface of the straw fiber, and the straw fiber is dried for standby.
The compatilizer used in the invention is a hydroxyl-terminated polylactic acid oligomer and an epoxy-containing vinyl polymer, wherein the hydroxyl-terminated polylactic acid oligomer can further improve the compatibility between the modified starch and the polylactic acid, and the hydroxyl-terminated polylactic acid oligomer and the chain extender in the component carry out in-situ chain extension reaction to obtain high-molecular-weight polylactic acid which can be well mixed with the starch to improve the mechanical property of the blend; the epoxy group in the vinyl polymer containing the epoxy group can react with the tail end of the PBAT, and the vinyl polymer has good compatibility with the polylactic acid, so that the compatibility between the polylactic acid and the PBAT can be solved, and the biodegradable packaging bag is favorable for improving the mechanical property and the puncture resistance of the biodegradable packaging bag; further, the molecular weight of the above-mentioned hydroxyl-terminated polylactic acid oligomer is 400-1200, the epoxy value of the epoxy-containing vinyl polymer is between 0.20 and 0.80mmol/g, the selection of the epoxy value in this range is advantageous for improving the compatibility between the polylactic acid and the PBAT, and the specific epoxy-containing vinyl polymer can be selected from epoxy-containing vinyl polymers containing copolymerized units of polyacrylate and/or polymethacrylate; wherein the weight ratio of the hydroxyl-terminated lactic acid oligomer to the epoxy-containing vinyl polymer is 3-5: 1.
The chain extender added in the invention has enough reaction activity on one hand, can improve the molecular weight and increase the melt viscosity; on the other hand, the addition of the chain extender can improve the compatibility among different polymer materials and improve the mechanical property of the materials. The specific chain extender can be one or more selected from a bisoxazoline chain extender, an isocyanate chain extender with the functionality of more than 2 and an epoxy chain extender, the specific bisoxazoline chain extender is one or more selected from 2, 2 '-bis (4-methyl-2-oxazoline), 2' -bis (4-butyl-2-oxazoline), 2 '- (1, 3-phenylene) -bisoxazoline, 2' - (1, 4-phenylene) -bisoxazoline and the like, the isocyanate chain extender is one or more selected from hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate and the like, preferably the bisoxazoline chain extender and the isocyanate chain extender are used together, and the bisoxazoline chain extender and the isocyanate chain extender show different activities on carboxyl and hydroxyl, the two chain extenders are used together, so that the chain extender can simultaneously have higher reactivity on hydroxyl and/or carboxyl in the polymer, and the effect of fully improving the interface compatibility of the two is achieved, thereby being beneficial to improving the mechanical property and the puncture resistance of the degradable lunch box; wherein the mass ratio of the bisoxazoline chain extender to the diisocyanate chain extender is 1-4: 4-1.
The antibacterial agent used in the invention is a composite antibacterial agent of carbon nano tube-carboxymethyl chitosan-silver, wherein the introduction amount of nano silver is about 5-15% of the total weight of the composite antibacterial agent; the composite contains two antibacterial active substances, namely carboxymethyl chitosan and silver, and has excellent antibacterial property on staphylococcus aureus, escherichia coli and the like, and the carbon nano tube has a large specific surface area and abundant cavity structures, so that the carbon nano tube has strong adsorption capacity, has excellent strength, can improve the strength and puncture resistance of the degradable plastic bag, can play a good slow-release role, and improves the antibacterial property of the degradable lunch box; specifically, the acyl chloride carbon nano tube can be prepared by carrying out acyl chloride reaction on a carboxylated multi-walled carbon nano tube, then the acyl chloride carbon nano tube is reacted with carboxymethyl chitosan to obtain a covalent grafted carbon nano tube-carboxymethyl chitosan compound, wherein the grafting amount of the carboxymethyl chitosan is 36% -50%, finally the carbon nano tube-carboxymethyl chitosan compound is added into deionized water, the ultrasonic dispersion is uniform, and AgNO with a certain concentration is slowly added3The solution is fully stirred and then reduced to prepare the carbon nano tube-carboxymethyl chitosan-silver composite antibacterial agent.
In addition, on the premise of not violating the basic concept of the present invention, other biodegradable resins commonly used in the field can be added, specifically, one or more of poly (butylene terephthalate-succinate) (PBST), poly (butylene adipate-succinate) (PBSA), poly (propylene carbonate) (PPC), poly (hydroxy fatty acid ester) (PHA), poly (butylene succinate) (PBS) and the like, and the addition amount is 2-10 parts;
the invention can also add and use the additive variety commonly used in the field, its addition amount is between 5-30, include inorganic filler, coupling agent, lubricant, anti-oxidant, opening agent, antistatic agent, etc. component specifically; the inorganic filler is selected from one or more of talcum powder, calcium carbonate, diatomite, kaolin, nano silicon dioxide and the like, the coupling agent is one or more of titanate coupling agent, silane coupling agent and aluminate coupling agent, the lubricant is selected from one or more of N, N-ethylene bis-stearamide, calcium stearate, aluminum stearate, white oil, polyethylene wax, paraffin or monoglyceride, the antioxidant is selected from hindered phenol antioxidants, phosphite antioxidants and phosphate antioxidants, and the opening agent is selected from one or more of oleamide, erucamide and the like.
In another technical scheme of the invention, the invention also provides a preparation method of the antibacterial biodegradable tableware, which comprises the following steps:
(1) carrying out modification treatment on starch to prepare modified starch for later use;
(2) performing vacuum drying treatment on PLA, PBAT and modified starch for later use;
(3) adding the dried raw materials in the step (2) into a high-speed stirrer, sequentially adding a compatilizer, a chain extender and an antibacterial agent, uniformly mixing, adding the mixture into a double-screw extruder from a main material port, adding the plant fibers through a side feeding port, and performing melt extrusion granulation to prepare granules;
(4) and (4) adding the granules prepared in the step (3) into an injection mold, performing hot press molding, demolding and drying to obtain the biodegradable lunch box.
Further, the starch modification step in the step (1) is specifically as follows: mixing starch and glycerol according to the mass ratio of 2-5:1, adding maleic anhydride accounting for 2-5% of the mass of the starch into the mixture, fully mixing, and extruding and granulating by a double-screw extruder to obtain the modified starch.
The drying temperature in the step (2) is 40-60 ℃, and the drying time is 2-6 h;
the temperature of each section of the double-screw extruder in the step (3) is controlled to be 200 ℃ plus 120 ℃, and the temperature of the injection in the step (4) is controlled to be 200 ℃ plus 120 ℃.
Further, the biodegradable tableware body of the present invention includes meal boxes, meal plates, meal bowls, meal cups, meal forks, meal spoons, etc.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention takes starch as a main raw material, biodegradable high polymers PLA and PBAT are added, the degradation rate and the mechanical property of the degradable lunch box are well balanced, the mechanical property of plastic can be further improved by adding plant fibers, the compatibility between the starch and the polymers can be improved by specifically modifying the starch, the end hydroxyl polylactic acid oligomer and the epoxy vinyl polymer which are compatilizers are further matched for use, the compatibility between the modified starch and the polylactic acid can be further improved by the end hydroxyl polylactic acid oligomer, and the in-situ chain extension reaction is carried out on the end hydroxyl polylactic acid oligomer and the chain extender in the component to obtain the high molecular weight polylactic acid which can be well mixed with the starch, so that the mechanical property of a blend is improved; the epoxy group in the vinyl polymer containing the epoxy group can react with the tail end of the PBAT, and the vinyl polymer has good compatibility with the polylactic acid, so that the compatibility between the polylactic acid and the PBAT can be solved, and the mechanical property and the puncture resistance of the biodegradable tableware, particularly the lunch box, can be improved.
2. The chain extender selected by the invention has sufficient reaction activity, can improve the molecular weight, improve the compatibility between different polymer materials and improve the mechanical property and the puncture resistance of the materials, particularly, the bisoxazoline chain extender and the isocyanate chain extender are selected to be used together, show different activities to carboxyl and hydroxyl, and can fully improve the interface compatibility of the two, thereby being beneficial to improving the mechanical property and the puncture resistance of degradable tableware, particularly lunch boxes.
3. The invention selects the carbon nano tube-carboxymethyl chitosan-silver compound as the antibacterial agent, the compound simultaneously contains two antibacterial active substances of carboxymethyl chitosan and silver, the compound has excellent antibacterial property to staphylococcus aureus, escherichia coli and the like, the carbon nano tube has excellent strength and can improve the mechanical strength and the puncture resistance of the degradable plastic bag, and the carbon nano tube has good adsorption effect to silver due to the abundant cavity structure on the carbon nano tube, so that the invention can play a good antibacterial slow-release role and ensure the effective antibacterial performance of the degradable tableware, particularly the lunch box.
Detailed Description
The present invention will be described in further detail with reference to the following specific examples. The procedures, conditions, experimental methods and the like for carrying out the present invention are general knowledge and common general knowledge in the art, except for the contents specifically mentioned below, and the present invention is not particularly limited to the contents. The protection of the present invention is not limited to the following examples. Variations and advantages that may occur to those skilled in the art may be incorporated into the invention without departing from the spirit and scope of the inventive concept, and the scope of the appended claims is intended to be protected.
1. Sources of main raw materials
Polylactic acid 4032D, supplied by NatureWorks, usa;
PBAT Ecoflex-F-blend-C1200, supplied by BASF corporation, Germany;
an epoxy group-containing vinyl polymer selected from Reseda GP-301, manufactured by Toyo Synthesis;
the hydroxyl-terminated lactic acid oligomer is prepared according to the method disclosed in the prior art CN201010128741. X.
The modified corn starch is prepared by the following method: the method comprises the following steps of (1) uniformly mixing commercial corn starch and glycerol, adding maleic anhydride, uniformly mixing, and performing double-screw melt extrusion to prepare modified starch; wherein the mass ratio of the starch to the glycerol is 4:1, and the addition amount of the maleic anhydride is 4% of the starch.
The preparation process of the carbon nano tube-carboxymethyl chitosan-silver compound comprises the following steps: firstly, carrying out acyl chlorination reaction on a carboxylated carbon nanotube and oxalyl chloride to obtain an acyl chlorinated carbon nanotube, then adding carboxymethyl chitosan for reaction to obtain a covalently grafted carbon nanotube-carboxymethyl chitosan compound, wherein the grafting amount of the carboxymethyl chitosan is about 45 percent, finally adding the carbon nanotube-carboxymethyl chitosan compound into deionized water, carrying out ultrasonic dispersion uniformly, and slowly adding AgNO with the concentration of 8g/L3The solution is fully stirred and reduced to prepare the carbon nano tube-carboxymethyl chitosan-silver composite antibacterial agent, wherein the load capacity of the nano silver is about 12 percent of the total weight of the composite antibacterial agent, the grafting amount of the carboxymethyl chitosan and the nano silverThe load amount of (a) is calculated by the difference of the thermal weight loss curves.
The carboxymethyl chitosan-silver complex is prepared as follows: adding carboxymethyl chitosan into deionized water, performing ultrasonic dispersion uniformly, and adding AgNO with mass concentration of 8g/L3Stirring the solution at constant temperature to enable the solution to be fully fused and reacted, slowly dripping sodium hydroxide solution into the mixed solution, adjusting the pH value to be alkaline, changing the solution into golden brown after reacting for a period of time, dialyzing the reacted mixed solution to remove unreduced silver ions and the like, and performing a vacuum freeze-drying method to obtain the carboxymethyl chitosan-silver compound, wherein the load capacity of nano silver is about 12 percent of the total weight of the compound.
The pretreatment steps of the straw fiber are as follows: spraying a gamma-aminopropyl triethoxysilane ethanol solution with the mass concentration of 3% onto the surface of the straw fiber for pretreatment and later use.
The other test materials were obtained by conventional commercial purchase.
2. Performance testing
(1) And (3) testing mechanical properties: the test was carried out according to the method of GB/T1040.1-2006.
(2) And (3) testing the degradation performance: testing by soil burying method to obtain the weight (M) of the degradable lunch box dried to constant weight1) Burying the sample in a container filled with soil, degrading for a period of time, taking out the buried sample, cleaning, and drying to constant weight (M)2) And calculating the degradation rate according to a calculation formula: degradation rate (M)1-M2)/M1×100％。
(3) And (3) testing antibacterial performance: antibacterial performance tests were carried out with reference to GB/T31402-2015.
(4) And (3) puncture resistance testing: the test was carried out according to the standard GB/T37841-2019.
3. Detailed description of the preferred embodiments
Example 1: an antibacterial biodegradable lunch box is prepared from the following raw materials in parts by weight: 20 parts of PLA, 10 parts of PBAT, 50 parts of modified corn starch, 10 parts of pretreated straw fiber, 8 parts of hydroxyl-terminated lactic acid oligomer, 0.6 part of 2, 2' - (1, 3-phenylene) -bisoxazoline, 0.8 part of diphenylmethane diisocyanate and 10 parts of carbon nanotube-carboxymethyl chitosan-silver compound.
The preparation method of the biodegradable lunch box comprises the following steps:
(1) carrying out modification treatment on starch to prepare modified starch for later use;
(2) performing vacuum drying treatment on PLA, PBAT and modified starch for later use;
(3) adding the dried raw materials in the step (2) into a high-speed stirrer, sequentially adding a hydroxyl-terminated lactic acid oligomer, an epoxy-containing vinyl polymer GP-301, 2' - (1, 3-phenylene) -bisoxazoline, diphenylmethane diisocyanate and a carbon nanotube-carboxymethyl chitosan-silver compound, uniformly mixing, adding a mixed material into a double-screw extruder from a main material port, adding pretreated straw fibers through a side feeding port, and performing melt extrusion granulation to prepare granules;
(4) and (4) adding the granules prepared in the step (3) into an injection mold, performing hot press molding, demolding and drying to obtain the biodegradable lunch box.
Embodiment 2 an antibacterial biodegradable lunch box is prepared from the following raw materials in parts by weight: 25 parts of PLA, 15 parts of PBAT, 70 parts of modified corn starch, 12 parts of pretreated straw fiber, 9 parts of hydroxyl-terminated lactic acid oligomer, GP-3013 parts of vinyl polymer containing epoxy groups, 1 part of 2, 2' - (1, 3-phenylene) -bisoxazoline, 1 part of diphenylmethane diisocyanate and 12 parts of carbon nanotube-carboxymethyl chitosan-silver compound.
The specific preparation procedure was the same as in example 1.
Embodiment 3 an antibacterial biodegradable lunch box is prepared from the following raw materials in parts by weight: 30 parts of PLA, 15 parts of PBAT, 60 parts of modified corn starch, 15 parts of pretreated straw fiber, 12 parts of hydroxyl-terminated lactic acid oligomer, GP-3013 parts of vinyl polymer containing epoxy groups, 1.2 parts of 2, 2' - (1, 3-phenylene) -bisoxazoline, 1.5 parts of diphenylmethane diisocyanate and 15 parts of carbon nanotube-carboxymethyl chitosan-silver compound.
The specific preparation procedure was the same as in example 1.
Embodiment 4 an antibacterial biodegradable lunch box is prepared from the following raw materials in parts by weight: 25 parts of PLA, 15 parts of PBAT, 70 parts of modified corn starch, 12 parts of pretreated straw fiber, 9 parts of hydroxyl-terminated lactic acid oligomer, GP-3013 parts of vinyl polymer containing epoxy groups, 2, 2' - (1, 3-phenylene) -bisoxazoline and 12 parts of carbon nanotube-carboxymethyl chitosan-silver compound.
The specific preparation procedure was the same as in example 1.
Comparative example 1 an antibacterial biodegradable lunch box is made from the following raw materials in parts by weight: 20 parts of PLA, 10 parts of PBAT, 50 parts of corn starch, 10 parts of pretreated straw fiber, 10 parts of epoxy-containing vinyl polymer GP-301, 0.6 part of 2, 2' - (1, 3-phenylene) -bisoxazoline, 0.8 part of diphenylmethane diisocyanate and 10 parts of carbon nanotube-carboxymethyl chitosan-silver compound.
The relevant preparation procedure was as in example 1.
Comparative example 2 an antibacterial biodegradable lunch box is made from the following raw materials in parts by weight: 25 parts of PLA, 15 parts of PBAT, 70 parts of corn starch, 12 parts of pretreated straw fiber, 12 parts of vinyl polymer GP-30112 parts containing epoxy groups, 2, 2' - (1, 3-phenylene) -bisoxazoline and 12 parts of carbon nanotube-carboxymethyl chitosan-silver compound.
The relevant preparation procedure was as in example 1.
Comparative example 3 an antibacterial biodegradable lunch box is made from the following raw materials in parts by weight: 30 parts of PLA, 15 parts of PBAT, 60 parts of modified corn starch, 15 parts of pretreated straw fiber, 15 parts of hydroxyl-terminated lactic acid oligomer, 1.2 parts of 2, 2' - (1, 3-phenylene) -bisoxazoline, 1.5 parts of diphenylmethane diisocyanate and 15 parts of carboxymethyl chitosan-silver compound.
The relevant preparation procedure was as in example 1.
Table 1 shows different properties of the antibacterial, biodegradable lunch box prepared in examples 1-4 and comparative examples 1-3, with different compositions and amounts.
TABLE 1
As can be seen from table 1, the present invention specifically provides a lunch box having excellent mechanical properties, antibacterial properties, puncture resistance, and at the same time, being rapidly biodegradable.
Although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the true spirit and scope of the present invention.
Claims (8)
1. An antibacterial biodegradable tableware, characterized in that: comprises the following components in parts by weight: 40-70 parts of starch, 20-30 parts of PLA (polylactic acid), 5-15 parts of PBAT (poly (butylene adipate-co-terephthalate)), 10-15 parts of plant fiber, 10-15 parts of compatilizer, 1-3 parts of chain extender and 10-15 parts of antibacterial agent;
wherein the compatilizer is a hydroxyl-terminated polylactic acid oligomer and an epoxy-containing vinyl polymer, the weight ratio of the hydroxyl-terminated polylactic acid oligomer to the epoxy-containing vinyl polymer is 3-5:1, the molecular weight of the hydroxyl-terminated polylactic acid oligomer is 400-1200, and the epoxy value of the epoxy-containing vinyl polymer is 0.20-0.80 mmol/g;
the antibacterial agent is a composite antibacterial agent of carbon nano tube-carboxymethyl chitosan-silver;
the starch is modified starch;
the chain extender is a mixture of a bisoxazoline chain extender and an isocyanate chain extender, and the mass ratio of the bisoxazoline chain extender to the isocyanate chain extender is 1-4: 4-1;
the preparation method of the carbon nano tube-carboxymethyl chitosan-silver composite antibacterial agent comprises the following steps: performing acyl chlorination reaction on a carboxylated multi-walled carbon nanotube to prepare an acyl chlorinated carbon nanotube, then reacting the acyl chlorinated carbon nanotube with carboxymethyl chitosan to obtain a covalent grafted carbon nanotube-carboxymethyl chitosan compound, finally adding the compound into deionized water, performing ultrasonic dispersion uniformly, and slowly adding AgNO3The solution is prepared by fully stirring and reducingA composite antibacterial agent of carbon nano tube-carboxymethyl chitosan-silver.
2. Antibacterial biodegradable tableware according to claim 1 characterized in that: the starch is selected from one or more of corn starch, wheat starch, sweet potato starch, cassava starch and potato starch.
3. Antibacterial biodegradable tableware according to claim 2 characterized in that: the starch is modified starch, and is prepared by mixing starch and glycerol according to the mass ratio of 2-5:1, then adding maleic anhydride accounting for 2-5% of the mass of the starch, fully mixing, and then extruding and granulating through a double-screw extruder.
4. Antibacterial biodegradable tableware according to any one of claims 1 to 3 characterized in that: the plant fiber is selected from one or more of straw fiber, cotton fiber, hemp fiber, bamboo fiber and wood pulp fiber, wherein
The plant fiber is modified by a coupling agent, wherein the coupling agent comprises one or more of a silane coupling agent, a titanate coupling agent and an aluminate coupling agent.
5. Antibacterial biodegradable tableware according to claim 1 characterized in that: the weight average molecular weight of the polylactic acid is 10-30 multiplied by 104g/mol。
6. Antibacterial biodegradable tableware according to claim 1 characterized in that: the number average molecular weight of the PBAT is 2-5 x 104g/mol。
7. The method for preparing antibacterial biodegradable tableware according to any one of claims 1 to 6, wherein: the method comprises the following steps:
(1) carrying out modification treatment on starch to prepare modified starch for later use;
(2) performing vacuum drying treatment on PLA, PBAT and modified starch for later use;
(3) melting, extruding and granulating the dried raw materials and the rest component raw materials in the step (2) by a double-screw extruder to prepare granules;
(4) and (4) adding the granules prepared in the step (3) into an injection mold, performing hot-press molding, demolding and drying to obtain the antibacterial biodegradable tableware.
8. The method of claim 7, wherein: the specific melt extrusion step in the step (3) is as follows: adding the dried raw materials obtained in the step (2) into a high-speed stirrer, sequentially adding a compatilizer, a chain extender and an antibacterial agent, uniformly mixing, adding the mixture into a double-screw extruder from a main material port, adding the plant fibers through a side feeding port, and performing melt extrusion to prepare granules.
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| US11820882B2 (en) * | 2021-06-22 | 2023-11-21 | China Yunhong Holdings Co., Ltd. | Method for preparing low-cost fully-biodegradable plant fiber starch tableware |
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| US11820882B2 (en) * | 2021-06-22 | 2023-11-21 | China Yunhong Holdings Co., Ltd. | Method for preparing low-cost fully-biodegradable plant fiber starch tableware |
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