CN114292504A - Graphene degradable lunch box and preparation method thereof - Google Patents
Graphene degradable lunch box and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 84
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- 238000002360 preparation method Methods 0.000 title claims abstract description 32
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- 239000004594 Masterbatch (MB) Substances 0.000 claims description 22
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 22
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- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 claims description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 3
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Abstract
The invention belongs to the technical field of graphene, and particularly relates to a novel graphene degradable lunch box and a preparation method thereof. Aiming at the problems of complex preparation process, high production cost and poor antibacterial performance of the existing PLA (polylactic acid) prepared lunch box, the invention provides the graphene degradable lunch box. The antibacterial lunch box disclosed by the invention has better antibacterial performance and longer antibacterial time, and meanwhile, the weight of the lunch box is greatly reduced. The preparation method of the lunch box is simple, has excellent performance and is suitable for industrial production.
Description
Technical Field
The invention belongs to the technical field of graphene, and particularly relates to a novel graphene degradable lunch box and a preparation method thereof.
Background
The disposable lunch box is a common consumer product, and the demand of the disposable lunch box is increasing due to the development of the domestic fast food industry. With the increasing environmental pollution and the continuous emphasis on the sanitary safety problem, the safety and environmental protection of the disposable lunch box are pushed to the wave tip of the air opening. The national authorities have restricted the use of disposable foamed plastic tableware to the national extent from 10/30.2000. Therefore, the degradable tableware is necessarily made of natural degradable high polymer materials instead of high polymer materials synthesized by taking petroleum as raw materials, and the degradable tableware has wide application scenes.
The degradable tableware is tableware which can generate biochemical reaction under the action of natural environment microorganism (bacteria, mould and algae) enzyme to cause the appearance to be mildewed to change to the internal quality, and finally form carbon dioxide and water. The existing disposable tableware is divided into the following three categories according to the source of raw materials, production process, degradation mode and recovery level: 1. biodegradation class: such as paper products (pulp-containing molded forms, cardboard coated forms), edible powder molded forms, vegetable fiber molded forms, etc.; 2. light/biodegradable materials: light/biodegradable plastics (non-foamed) type, such as photobiodegradable PP; 3. materials easy to recycle: such as polypropylene (PP), High Impact Polystyrene (HIPS), Biaxially Oriented Polystyrene (BOPS), natural inorganic mineral filled polypropylene composite products, and the like.
The application is widest, the yield is the largest, the two degradable plastics are PLA and PBAT, and the PLA can be applied to disposable lunch boxes, food and beverage outer packages and high value-added films in the field of food packaging; can also be applied to the field of biological medical treatment, and can be used for medical suture lines, drug controlled release carriers, orthopedic internal fixation materials, engineering stents, drug controlled release materials, ophthalmic materials and the like. However, at present, there are few PLA degradable lunch boxes produced, mainly due to the reasons that the processing technology is not as mature as general plastics, the process is complex, the cost is high, the selling price is high, the use stability is insufficient, and the product quality is poor.
Patent CN105440611A discloses a high-toughness polylactic acid film with antibacterial barrier property, which is prepared from polylactic acid, EVOH, polylactic acid-grafted glycidyl methacrylate, glycidyl methacrylate-grafted ethylene octene, eight-arm maleic anhydride, nano TiO2, an antioxidant and an ultraviolet resistant agent.
Patent CN102550456A discloses a method for preparing antibacterial polylactic acid master batch by using ultrafine antibacterial powders such as titanium dioxide, silver-loaded fluorite, etc., which improves the antibacterial performance of pure PLA tableware, but the adopted antibacterial powders have higher density, increase the weight of tableware products, and reduce the antibacterial rate to staphylococcus aureus.
Therefore, the existing composite polylactic acid antibacterial agent has poor antibacterial effect, complex preparation process, numerous raw materials and difficult industrial application, and further research is needed to apply the polylactic acid antibacterial agent to the field of degradable lunch boxes in order to widen the application range of polylactic acid.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the prior polylactic acid has the problems of complex preparation process, high production cost and poor antibacterial property when preparing the lunch box.
The technical scheme for solving the technical problems comprises the following steps: a preparation method of a graphene degradable lunch box is provided. The method comprises the following steps:
a. dissolving copper sulfate in deionized water to form a copper sulfate solution A;
b. keeping the temperature of polyvinyl alcohol and stirring to dissolve the polyvinyl alcohol in deionized water to form a polyvinyl alcohol solution B;
c. stirring the solution B in a magnetic stirrer, and dripping the solution A while stirring to dissolve copper ions in the solution B to obtain a solution C;
d. dissolving graphene oxide in deionized water, performing ultrasonic stirring to form a stably dispersed suspension, adding the solution C into the suspension, transferring the suspension into a long glass tube, sealing, freezing and then thawing, and repeating the steps for a plurality of times to form a graphene oxide/copper composite material;
e. washing, centrifuging, and freeze-drying to obtain the graphene oxide/copper composite antibacterial agent;
f. mixing the graphene oxide/copper composite antibacterial agent with polylactic acid to obtain composite antibacterial master batches;
g. uniformly mixing the composite antibacterial master batch with PLA, cutting and rolling after extrusion to obtain the graphene degradable sheet;
h. uniformly mixing starch, PLA and an auxiliary agent, cutting and rolling after extrusion to obtain a mixed degradable sheet;
i. placing the mixed degradable sheet prepared in the step h between the graphene degradable sheets prepared in the step g, heating and softening the three layers of sheets, performing compression molding, and preparing the graphene degradable lunch box after cutting.
Wherein in the step a, the concentration of the copper sulfate solution is 1-10 mg/ml.
In the step b, the temperature of the polyvinyl alcohol is 65-100 ℃.
Wherein in the step b, the concentration of the polyvinyl alcohol solution is 0.1-2 g/ml.
Wherein, in the step c, the polyvinyl alcohol plays a role in protection.
Wherein in the step c, the stirring time is 30-90 min.
In the step c, the volume ratio of the solution A to the solution B is 0.5-4: 2.5 to 9.
Wherein, in the step d, the concentration of the graphene oxide suspension is 20 mg/ml.
In the step d, the volume ratio of the graphene oxide suspension to the solution C is 1.5-4.5: 4 to 8.5.
Wherein in the step d, the freezing refers to freezing to-15 to-35 ℃ in a refrigerator, and the unfreezing refers to standing at room temperature until the temperature is 20-30 ℃.
Wherein, in the step d, the repetition times are 3-8 times.
In the step e, the temperature of the freeze drying is-20 to-30 ℃, and the freeze drying time is 8 to 12 hours.
In the step f, in the composite antibacterial master batch, the weight ratio of the graphene oxide composite antibacterial agent to the polylactic acid is 1-5: 95 to 99 parts.
In the step f, the ratio of the graphene oxide composite antibacterial agent to the polylactic acid matrix is 1-5: 95-99, adding the mixture into a hopper of a double-screw extruder, and performing extrusion granulation by the double-screw extruder to form the graphene composite polylactic acid composite antibacterial master batch.
In step g, the weight ratio of the composite antibacterial master batch to the PLA is as follows: 1-5: 95 to 99 parts.
In the step g, the extrusion is performed through a multi-channel control extrusion die head, and the extrusion temperature is 180-210 ℃.
In the step h, the weight ratio of the starch, the PLA and the auxiliary agent is as follows: 15-45: 40-75: 5 to 20.
Wherein, the auxiliary agent comprises: calcium carbonate, PBS and PBAT. The calcium carbonate is used for improving the temperature resistance and strength of the sheet and also serves as a nucleating agent; PBS, which is used for improving temperature resistance; PBAT, for toughening.
Further, the auxiliary agent is: the adhesive comprises, by weight, 25-50 parts of calcium carbonate, 25-50 parts of PBS and 25-50 parts of PBAT.
In the step h, the extrusion is performed through a multi-channel control extrusion die head, and the extrusion temperature is 180-210 ℃.
In the step i, the compression molding equipment is an air pressure thermoforming machine, and the molding temperature is 190-210 ℃.
The invention has the beneficial effects that:
in order to reduce the weight of the lunch box and achieve a good effect, the graphene oxide is adopted in the invention, the graphene oxide is firstly prepared into the antibacterial agent, and then the antibacterial agent is effectively combined with polylactic acid on the basis to improve the antibacterial property and the mechanical strength of the polylactic acid, so that the degradable lunch box with a three-layer structure is prepared. The degradable lunch box prepared by the invention is an ultra-low density lunch box, the weight of the lunch box is greatly reduced, and the degradable lunch box also has good antibacterial effect and higher stability. The method for preparing the graphene degradable lunch box is simple, has low requirements on raw materials and equipment, and is suitable for industrial production.
Detailed Description
The invention provides a preparation method of a graphene degradable lunch box, which comprises the steps of firstly preparing a graphene oxide/copper composite antibacterial agent, freezing and then thawing, repeating for 3-5 times, and enabling carboxyl on a graphene oxide sheet layer and hydroxyl on PVA to be combined to form an ester group, so that PVA wrapping nanoparticles is combined on the graphene oxide sheet layer by virtue of a chemical bond, and simultaneously graphene oxide can also form strong hydrogen bond combination with PVA, so that the stability of the composite antibacterial agent can be improved, and the antibacterial effect is more durable.
And then, mixing the graphene oxide/copper composite antibacterial agent with polylactic acid to obtain the composite antibacterial master batch. And mixing the composite antibacterial master batch with polylactic acid to obtain the graphene degradable sheet. According to the invention, the graphene oxide/copper composite antibacterial agent and the polylactic acid are mixed to prepare the master batch, and then the master batch and the polylactic acid are mixed again, and the polylactic acid is added twice, mainly because the dosage of the graphene is extremely low relative to that of the polylactic acid, the dosage is better controlled by adopting a step-by-step adding mode, and the mixing is more uniform.
The invention also adopts the mixed degradable sheet prepared by starch and PLA as the middle layer, and the manufacturing cost of the lunch box can be reduced by using the sheet without influencing other performances. In order to ensure the antibacterial performance of the lunch box, the sheet material containing graphene is used as the outermost layer sheet material.
The lunch box prepared from the graphene degradable sheet disclosed by the invention has excellent antibacterial performance and long antibacterial aging, and can guarantee food safety more effectively. Meanwhile, the anti-mildew effect is good, and the storage time of the lunch box can be prolonged. In addition, the graphene degradable lunch box provided by the invention has the advantages that the mechanical strength is obviously improved, the lowest thickness of the lunch box can be reduced, and the weight and the cost are reduced.
The graphene degradable lunch box disclosed by the invention adopts a mode that three layers from bottom to top are 'graphene degradable sheet + mixed degradable sheet + graphene degradable sheet', but the mode is not limited to the mode, and more layers of degradable sheets can be stacked. But it is always necessary to ensure that the outermost layer is the graphene degradable sheet to maintain good antibacterial performance. But in order to save cost, the graphene degradable lunch box prepared by using three layers of degradable sheets is preferred.
The graphene lunch box disclosed by the invention adopts a three-layer structure, and the innermost layer and the outermost layer are graphene oxide/copper composite antibacterial agent prepared graphene degradable sheets, so that the lunch box has excellent antibacterial performance. The main components of the middle layer are starch and PLA, and the mixed degradable sheet is prepared, so that the manufacturing cost of the lunch box can be reduced. Adopt such mode of "graphite alkene degradable sheet + mixed degradable sheet + graphite alkene degradable sheet" to guarantee that the cutlery box has enough intensity, reduces manufacturing cost and cutlery box weight and possess excellent antibacterial property, still can prolong the storage time. In addition, the lunch box is degradable and environment-friendly.
The graphene degradable lunch box prepared by the invention comprises: lunch boxes, cups or straws.
The following examples are intended to illustrate specific embodiments of the present invention without limiting the scope of the invention to the examples.
The reagents used in the examples and comparative examples are all common commercial products.
Embodiment 1 preparing graphene composite antibacterial lunch box by adopting method of the invention
The specific operation steps are as follows:
1. dissolving 60mg of copper sulfate in 15ml of deionized water to form a solution A;
2. stirring 5g of polyvinyl alcohol (PVA) at the temperature of 85 ℃ to uniformly disperse and dissolve the PVA in 30ml of deionized water to form a solution B;
3. stirring the solution B in a magnetic stirrer, dropwise adding the solution A while stirring to dissolve copper ions in the solution B, and stirring for 30min to finally form a solution C;
4. dissolving 200mg of graphene oxide in 10ml of deionized water, carrying out ultrasonic stirring to form a stably dispersed suspension, adding the solution C, transferring the mixed solution into a long glass tube, sealing, freezing at-20 ℃, thawing, and repeating for 3 times to form the graphene oxide/copper sulfate nanocrystal composite material;
5. finally, freeze-drying the product for 8 hours to form composite antibacterial agent powder;
6. putting 2% of the composite antibacterial agent and 98% of polylactic acid into a hopper of a double-screw extruder, setting the temperature of each zone of the screw at 180 ℃, 185 ℃, 190 ℃, 200 ℃, 210 ℃, 205 ℃, 200 ℃, 190 ℃ and 180 ℃, and setting the rotating speed of a main machine at 700 rpm;
7. and cooling and shaping the resin mixture extruded by the double-screw extruder through a cooling water tank, introducing the resin mixture into a granulator for cutting and granulation, and finally drying and screening the obtained resin master batch to obtain the graphene oxide composite antibacterial master batch.
8. The graphene composite antibacterial sheet comprises the following components in parts by weight: 95 parts of PLA and 5 parts of composite antibacterial master batch, and the raw materials are melted and uniformly mixed by an extruder and then extruded into the antibacterial sheet. The heating temperature is 210 ℃, the cooling temperature is 50 ℃, and the extrusion pressure is 0.6 Mpa.
9. The mixed degradable sheet material of starch and PLA comprises the following components in parts by weight: 45 parts of PLA, 15 parts of other auxiliary agents and 40 parts of corn starch subjected to coupling treatment, wherein the other auxiliary agents comprise the following components in parts by weight: 50 parts of calcium carbonate, 25 parts of PBS and 25 parts of PBAT. The raw materials are melted and mixed uniformly by an extruder and then extruded into the antibacterial sheet. The heating temperature is 210 ℃, the cooling temperature is 50 ℃, and the extrusion pressure is 0.6 Mpa.
10. A layer of starch and PLA mixed degradable sheet is placed between two layers of graphene composite antibacterial sheets. Heating and softening the three-layer sheet at 200 ℃, carrying out positive and negative pressure integrated compression molding through a pneumatic thermoforming machine, integrally molding the sheet into a lunch box, and cutting to obtain a novel graphene degradable lunch box finished product.
Embodiment 2 preparing graphene composite antibacterial lunch box by adopting the method
The difference from example 1 is that the PVA dissolution temperature is 90 ℃, the freezing and unfreezing cycles in step 4 are 4 times, the freeze-drying time in step 5 is 10 hours, the concentration of the copper sulfate solution is 5mg/ml, the concentration of the PVA solution is 0.20g/ml, the volume ratio of the two is 2.5: 3.5; when the graphene oxide composite antibacterial master batch is prepared, the weight ratio of the raw materials is 97% of polylactic acid master batch and 3% of graphene oxide composite antibacterial agent.
Embodiment 3 preparing graphene composite antibacterial lunch box by adopting the method
The difference from example 1 is that the PVA dissolution temperature is 90 ℃, the freezing and unfreezing cycles are 5 times in step 4, the freeze-drying time in step 5 is 12 hours, the concentration of the copper sulfate solution is 6mg/ml, the concentration of the PVA solution is 0.35g/ml, and the volume ratio of the two is 3: 4; when the graphene oxide composite antibacterial master batch is prepared, the weight ratio of the raw materials is 95% of polylactic acid master batch and 5% of graphene oxide composite antibacterial agent.
Comparative example 1 preparation of polylactic acid lunch box using pure PLA resin
The difference from the embodiment 1 is that the used raw material is pure PLA resin, and graphene oxide composite antibacterial master batch and starch are not added when the sheet is manufactured.
Comparative example 2 preparation of polylactic acid lunch box using pure PLA resin and starch
The difference from the embodiment 1 is that the used raw materials are pure PLA resin and starch, and the graphene oxide composite antibacterial master batch is not added when the sheet is manufactured.
Comparative example 3 preparation of graphene composite antibacterial lunch box without using parameters of the present invention
The difference from example 1 is that the dissolution temperature of PVA is 60 ℃, and the ratio of graphene oxide solution concentration to solution C is 0.6: 2, the freezing and unfreezing cycles are carried out for 2 times, and the freeze drying time is 6 h.
The technical effects are as follows:
the properties of the polylactic acid sheets and the lunch boxes prepared in examples and comparative examples were measured, and the measurement methods and the measurement results are shown in the following table.
TABLE 1 Properties of polylactic acid sheets prepared by different methods
The results of the embodiment and the comparative example show that the graphene oxide composite antibacterial master batch prepared by the method can effectively improve the antibacterial performance and the mechanical performance of the polylactic acid product, and the weight of the polylactic acid product is reduced by reducing the density of the sheet; the polylactic acid sheet and the lunch box (comparative example 2) prepared by adopting the pure PLA resin and the starch have little performance difference with the pure PLA material (comparative example 1), but the performance effect is far inferior to that of the lunch box (examples 1-3) prepared by adopting the method of the invention. When the antibacterial sheet is not prepared by adopting the parameters within the range of the invention (comparative example 3), the antibacterial effect is better than that of the polylactic acid sheet of comparative example 1 and comparative example 2, but the antibacterial effect is weaker than that of the graphene composite antibacterial sheet prepared by the invention (examples 1-3); in the aspect of antibacterial aging, the antibacterial performance of the polylactic acid sheet prepared by the invention is only slightly reduced after 72 hours of action, and the antibacterial effect of the 3 comparative examples is obviously reduced.
TABLE 2 mildew time of polylactic acid sheet lunch box prepared by different methods
As can be seen from the results of the examples and comparative examples, the polylactic acid lunch box made of pure PLA resin and starch (comparative example 2) has poor performance and shorter anti-mildew time compared with the polylactic acid lunch box made of pure PLA material (comparative example 1). When the antibacterial lunch box is not prepared by adopting the parameters in the range of the invention (comparative example 3), the effect is better than that of the lunch boxes prepared by the polylactic acid sheets in the comparative examples 1 and 2 in the aspect of effect, but the effect is much weaker than that of the graphene composite antibacterial lunch box prepared by the invention (examples 1-3). As the amount of the complex antibacterial agent used increases, the mildew time also increases.
Claims (10)
1. The preparation method of the graphene degradable lunch box is characterized by comprising the following steps:
a. dissolving copper sulfate in deionized water to form a copper sulfate solution A;
b. keeping the temperature of polyvinyl alcohol and stirring to dissolve the polyvinyl alcohol in deionized water to form a polyvinyl alcohol solution B;
c. stirring the solution B in a magnetic stirrer, and dripping the solution A while stirring to dissolve copper ions in the solution B to obtain a solution C;
d. dissolving graphene oxide in deionized water, performing ultrasonic stirring to form a stably dispersed suspension, adding the solution C into the suspension, transferring the suspension into a long glass tube, sealing, freezing and then thawing, and repeating the steps for a plurality of times to form a graphene oxide/copper composite material;
e. washing, centrifuging, and freeze-drying to obtain the graphene oxide/copper composite antibacterial agent;
f. mixing the graphene oxide/copper composite antibacterial agent with polylactic acid to obtain composite antibacterial master batches;
g. uniformly mixing the composite antibacterial master batch with PLA, cutting and rolling after extrusion to obtain the graphene degradable sheet;
h. uniformly mixing starch, PLA and an auxiliary agent, cutting and rolling after extrusion to obtain a mixed degradable sheet;
i. placing the mixed degradable sheet prepared in the step h between the graphene degradable sheets prepared in the step g, heating and softening the three layers of sheets, performing compression molding, and preparing the graphene degradable lunch box after cutting.
2. The preparation method of the graphene degradable meal box according to claim 1, wherein the preparation method comprises the following steps: at least one of the following is satisfied,
the concentration of the copper sulfate solution in the step a is 1-10 mg/ml; or
The temperature of the polyvinyl alcohol in the step b is 65-100 ℃; or
The concentration of the polyvinyl alcohol solution in the step b is 0.1-2 g/ml; or
The stirring time of the step c is 30-90 min; or
The volume ratio of the solution A to the solution B in the step c is 0.5-4: 2.5 to 9; or
The concentration of the graphene oxide suspension liquid in the step d is 20 mg/ml; or
The volume ratio of the graphene oxide suspension to the solution C in the step d is 1.5-4.5: 4-8.5; or
Step d, freezing to-15 to-35 ℃ in a refrigerator, and unfreezing to 20 to 30 ℃ at room temperature; or
And d, repeating the step d for 3-8 times.
3. The preparation method of the graphene degradable meal box according to claim 1, wherein the preparation method comprises the following steps: at least one of the following is satisfied,
the temperature of the freeze drying in the step e is-20 to-30 ℃, and the freeze drying time is 8 to 12 hours; or
In the composite antibacterial master batch obtained in the step f, the weight ratio of the graphene oxide composite antibacterial agent to the polylactic acid is 1-5: 95 to 99 parts.
4. The preparation method of the graphene degradable meal box according to claim 1, wherein the preparation method comprises the following steps: the weight ratio of the composite antibacterial master batch to the PLA in the step g is as follows: 1-5: 95 to 99 parts.
5. The preparation method of the graphene degradable meal box according to claim 1, wherein the preparation method comprises the following steps: and g, extruding through a multi-channel control extrusion die head, wherein the extrusion temperature is 180-210 ℃.
6. The preparation method of the graphene degradable meal box according to claim 1, wherein the preparation method comprises the following steps: in the step h, the weight ratio of the starch, the PLA and the auxiliary agent is as follows: 15-45: 40-75: 5 to 20.
7. The preparation method of the graphene degradable meal box according to claim 6, wherein the preparation method comprises the following steps: the auxiliary agent comprises: calcium carbonate, PBS and PBAT.
8. The preparation method of the graphene degradable meal box according to claim 7, wherein the preparation method comprises the following steps: the auxiliary agent is as follows: the adhesive comprises, by weight, 25-50 parts of calcium carbonate, 25-50 parts of PBS and 25-50 parts of PBAT.
9. The preparation method of the graphene degradable meal box according to claim 1, wherein the preparation method comprises the following steps: and in the step h, extruding is carried out through a multi-runner control extrusion die head, and the extrusion temperature is 180-210 ℃.
10. The preparation method of the graphene degradable meal box according to claim 1, wherein the preparation method comprises the following steps: and (i) the compression molding equipment is an air pressure thermoforming machine, and the molding temperature is 190-210 ℃.
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| CN106903952A (en) * | 2017-01-20 | 2017-06-30 | 山东农业大学 | A kind of polylactic acid/starch high-barrier composite membrane and preparation method thereof |
| CN113637232A (en) * | 2021-09-11 | 2021-11-12 | 深圳环能石墨烯科技有限公司 | Graphene oxide/nano-copper composite antibacterial agent, antibacterial master batch and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106903952A (en) * | 2017-01-20 | 2017-06-30 | 山东农业大学 | A kind of polylactic acid/starch high-barrier composite membrane and preparation method thereof |
| CN113637232A (en) * | 2021-09-11 | 2021-11-12 | 深圳环能石墨烯科技有限公司 | Graphene oxide/nano-copper composite antibacterial agent, antibacterial master batch and preparation method thereof |
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