CN113637232B - Graphene oxide/nano-copper composite antibacterial agent, antibacterial master batch and preparation method thereof - Google Patents
Graphene oxide/nano-copper composite antibacterial agent, antibacterial master batch and preparation method thereof Download PDFInfo
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
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- C08K3/042—Graphene or derivatives, e.g. graphene oxides
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/085—Copper
Abstract
The invention belongs to the technical field of graphene, and particularly relates to a graphene oxide/nano-copper composite antibacterial agent, an antibacterial master batch and a preparation method thereof. Aiming at the defects that the existing composite polylactic acid antibacterial agent has poor antibacterial effect and stability, or has complex preparation process, numerous raw materials and difficult industrial application, the invention provides a preparation method of a graphene oxide/nano-copper composite antibacterial agent. The preparation method of the antibacterial agent is simple to operate, and raw materials are easy to obtain; the prepared antibacterial agent has good antibacterial effect, low cost, higher stability and longer antibacterial time; meanwhile, the antibacterial agent can be effectively combined with polylactic acid, so that the antibacterial performance and the mechanical strength of the polylactic acid are improved, and the weight of the environment-friendly tableware is reduced.
Description
Technical Field
The invention belongs to the technical field of graphene, and particularly relates to a graphene oxide/nano-copper composite antibacterial agent, an antibacterial master batch and a preparation method thereof.
Background
With the development of the medical health industry in China and the pursuit of people for healthy life, the requirements of people on antibacterial products are continuously improved. Improving the antimicrobial properties of some consumer products by the addition of antimicrobial agents is a low cost and efficient way of production.
The antibacterial agents are various in types, and the nano antibacterial materials such as nano silver, nano copper and the like have the characteristics of quantum effect, small-size effect, large specific surface area and the like, and can effectively destroy common bacteria, viruses and other eukaryotic microorganisms such as staphylococcus aureus, pseudomonas aeruginosa, escherichia coli and the like. However, the nano antibacterial material is easy to have the defects of low load rate, short antibacterial aging and the like. Graphene is a two-dimensional material with a single-layer sheet structure formed by carbon atoms, the basic structural unit of the graphene is a benzene six-membered ring, the carbon atoms of the graphene form a hexagonal honeycomb planar structure by sp2 hybridization orbits, and the edge layered structure of the graphene can directly pierce the cell membrane of bacteria to enable the contents of the bacteria to leak and further cause the bacteria to die, so that the graphene has a certain killing effect on the bacteria. Meanwhile, the graphene can also load inorganic nanoparticles, so that the stability of the nanoparticles is improved.
Therefore, the graphene loaded nano antibacterial material can be adopted to prepare a novel antibacterial material. However, in the preparation and use processes, the nano antibacterial material is agglomerated to reduce the antibacterial effect, and meanwhile, the noble metals such as silver and the like can increase the manufacturing cost of the antibacterial agent; the graphene has a loading effect on the nanoparticles, but the loading rate is not high and the graphene is easy to fall off in the using process, so that the antibacterial effect of the antibacterial agent is lost.
On the other hand, in the aspect of combining the graphene composite antibacterial agent with the polymer, although some patents report that the antibacterial agent can be effectively combined with the polymer, the antibacterial effect is not good, and the addition amount of the antibacterial agent needs to be increased to achieve a relatively good antibacterial effect.
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 adopts superfine antibacterial powder such as titanium dioxide, silver-carrying fluorite to prepare antibiotic polylactic acid master batch, has improved the antibacterial property of pure PLA tableware, but the antibacterial powder density that adopts is great, has increased the weight of tableware product, and is only 65% to the antibacterial rate of staphylococcus aureus.
Therefore, the existing composite polylactic acid antibacterial agent has poor antibacterial effect, or has complex preparation process, numerous raw materials and difficult industrial application, and the development of a composite antibacterial agent with simple preparation process and good antibacterial effect is urgently needed.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the existing composite polylactic acid antibacterial agent has the defects of poor antibacterial effect, poor stability, complex preparation process, numerous raw materials and difficult industrial application.
The technical scheme for solving the technical problems comprises the following steps: provides a preparation method of a graphene oxide/nano-copper composite antibacterial agent. 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, dripping the solution A while stirring to dissolve copper ions in the solution B, protecting polyvinyl alcohol, and then adding glucose to reduce the copper ions into nano copper particles to finally form 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 the graphene oxide/nano copper composite material;
e. and washing, centrifuging, and freeze-drying to obtain the graphene oxide/nano-copper composite antibacterial agent.
In the preparation method of the graphene oxide/nano-copper composite antibacterial agent, the concentration of the copper sulfate solution in the step a is 3-5 mg/ml.
In the preparation method of the graphene oxide/nano-copper composite antibacterial agent, the temperature for heat preservation of the polyvinyl alcohol in the step b is 80-90 ℃.
In the preparation method of the graphene oxide/nano-copper composite antibacterial agent, the concentration of the polyvinyl alcohol solution in the step b is 0.1-2 g/ml.
In the preparation method of the graphene oxide/nano-copper composite antibacterial agent, the stirring time in the step c is 0.5-1 h.
In the preparation method of the graphene oxide/nano-copper composite antibacterial agent, the volume ratio of the solution A to the solution B in the step c is 0.5-3: 2.5-8.
In the preparation method of the graphene oxide/nano-copper composite antibacterial agent, the concentration of the graphene oxide suspension in the step d is 1-20 mg/ml.
In the preparation method of the graphene oxide/nano-copper composite antibacterial agent, the volume ratio of the graphene oxide suspension to the solution C in the step d is 1.5-3: 4-6.
In the preparation method of the graphene oxide/nano-copper composite antibacterial agent, in the step d, the step of freezing is to freeze the graphene oxide/nano-copper composite antibacterial agent in a refrigerator to-20 to-30 ℃, and the step of unfreezing is to place the graphene oxide/nano-copper composite antibacterial agent at room temperature to 25 to 30 ℃.
In the preparation method of the graphene oxide/nano-copper composite antibacterial agent, the repetition frequency in the step d is 3-5 times.
In the preparation method of the graphene oxide/nano-copper composite antibacterial agent, the freeze drying temperature in the step e is-20 to-30 ℃, and the freeze drying time is 4 to 12 hours.
The invention also provides the graphene oxide/nano-copper composite antibacterial agent directly prepared by the method.
The invention also provides the graphene oxide/nano-copper composite antibacterial master batch prepared from the graphene oxide/nano-copper composite antibacterial agent.
Specifically, the antibacterial master batch is prepared by compounding a graphene oxide/nano-copper composite antibacterial agent and polylactic acid.
In the graphene oxide/nano-copper composite antibacterial master batch, the weight ratio of the graphene oxide/nano-copper composite antibacterial agent to the polylactic acid is 95-99: 1 to 5.
The invention also provides a preparation method of the graphene oxide/nano-copper composite antibacterial master batch, which comprises the following steps: the ratio of the graphene oxide/nano-copper composite antibacterial agent to the polylactic acid matrix is 95-99: 1-5, 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 antibacterial master batch.
Wherein, in the method, the temperatures of the zones of the double-screw extruder are 175-.
The invention has the beneficial effects that:
the antibacterial agent is a graphene oxide/nano-copper composite antibacterial agent, and has the advantages of good antibacterial effect, low cost, higher stability and longer antibacterial time compared with other conventional antibacterial agents; meanwhile, the antibacterial agent can be effectively combined with polylactic acid, so that the antibacterial performance and the mechanical strength of the polylactic acid are improved, and meanwhile, the weight of the environment-friendly tableware can be greatly reduced due to the ultralow density of the graphene oxide composite antibacterial agent. The antibacterial agent and the master batch have simple preparation methods and easily obtained raw materials, and are suitable for industrial popularization and use.
Detailed Description
The invention provides a preparation method of a graphene oxide/nano-copper composite antibacterial agent, which is characterized in that glucose is used for reducing copper ions into nano-copper to prepare the composite antibacterial agent, glucose is used for reducing the copper ions into nano-copper, so that the copper glucose is the nano-copper, and meanwhile, polyvinyl alcohol is used for wrapping nano-particles during reduction, so that the load stability of the graphene oxide/nano-copper composite antibacterial agent is improved under the combined action.
According to the method, when the graphene oxide/nano-copper composite antibacterial agent is prepared, the mode of freezing and then thawing is adopted, and the mode is repeated for 3-5 times, so that carboxyl groups on graphene oxide sheet layers and hydroxyl groups on PVA are combined to form ester groups, the PVA wrapping nano-particles is combined on the graphene oxide sheet layers by virtue of chemical bonds, and meanwhile, the graphene oxide can form strong hydrogen bond combination with the PVA, so that the stability of the composite antibacterial agent can be improved, and the antibacterial effect is more durable.
The antibacterial rate of the antibacterial agent of the invention to various bacteria can reach more than 98%, and after 72 hours of action, the antibacterial effect shows only small attenuation, the antibacterial stability is strong, and the antibacterial time is long.
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.
Example 1 preparation of graphene oxide composite polylactic acid antibacterial sheet by the method of the present invention
The specific operation steps are as follows:
1. dissolving 60mg of copper sulfate in 20ml of deionized water to form a solution A;
2.5 g of polyvinyl alcohol (PVA) is kept at 80 ℃ and stirred to be dissolved 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, protecting PVA, adding 5ml of glucose to reduce the copper ions into nano copper particles, and stirring for 0.5h to finally form a solution C;
4. dissolving 200mg of graphene oxide in 20ml of deionized water, carrying out ultrasonic stirring to form a stably dispersed suspension, adding the solution C into the suspension, transferring the mixed solution into a long glass tube, sealing, freezing at-20 ℃, thawing, and repeating for 3 times to form the Cu/GO composite material;
5. finally, freeze-drying the product for 9 hours to form composite antibacterial agent powder;
6. putting 1.5% of the composite antibacterial agent and 98.5% of polylactic acid into a hopper of a double-screw extruder, setting the temperature of each zone of a screw at 180 ℃, 185 ℃, 190 ℃, 200 ℃, 210 ℃, 205 ℃, 200 ℃, 190 ℃, 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 polylactic acid antibacterial master batch.
8. Compounding graphene oxide and polylactic acid antibacterial master batches and polylactic acid resin according to the proportion of 1: 9, melting and mixing the mixture by an extruder, and then putting the mixture into an injection molding machine for injection molding to obtain the antibacterial sheet. The injection machine heating temperature is 210 deg.C, cooling temperature is 50 deg.C, and injection zone pressure is 0.6 Mpa.
Embodiment 2 preparation of graphene oxide composite polylactic acid antibacterial sheet by the method of the present invention
The difference from example 1 is that the PVA dissolution temperature is 85 ℃, 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 4mg/ml, the concentration of the PVA solution is 0.18g/ml, the volume ratio of the two is 2.5: 3.5; when the graphene oxide composite polylactic acid antibacterial master batch is prepared, the weight ratio of the raw materials is 98% of the polylactic acid master batch and 2% of the graphene oxide composite antibacterial agent.
Example 3 preparation of graphene oxide composite polylactic acid antibacterial sheet by the method of the present invention
The difference from example 1 is that the PVA dissolution temperature is 90 ℃, the freezing and unfreezing cycles are carried out for 5 times in step 4, the freeze-drying time in step 5 is 12 hours, the concentration of the copper sulfate solution is 5mg/ml, the concentration of the PVA solution is 0.32g/ml, and the volume ratio of the two is 3: 4; when the graphene oxide composite polylactic acid 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.
Comparative example 1 preparation of polylactic acid antibacterial sheet Using pure PLA resin
The difference from the embodiment 1 is that the used raw material is pure PLA resin, and the graphene oxide composite polylactic acid antibacterial master batch is not used.
Comparative example 2 preparation of polylactic acid antibacterial sheet Using titanium dioxide as antibacterial agent
The difference from example 1 is that 93.5% polylactic acid resin, 1.5% silver-loaded titanium dioxide as an antibacterial agent, and 5% surfactant were used as raw materials. The preparation method of the antibacterial master batch and the forming method of the sheet are the same.
Comparative example 3 preparation of graphene oxide composite polylactic acid antibacterial sheet without using the parameters of the present invention
The difference from example 1 is that the dissolution temperature of PVA is 75 ℃, and the ratio of graphene oxide solution concentration to solution C is 0.5: 2, the freezing and unfreezing cycles are carried out for 2 times, and the freeze drying time is 7 h.
The performances of the graphene oxide composite polylactic acid antibacterial sheets prepared in the examples and the comparative examples were measured, and the measurement methods and the measurement results are shown in table 1 below.
TABLE 1 Properties of graphene oxide composite polylactic acid antibacterial sheets prepared by different methods
The results of the examples and the comparative examples show that the graphene oxide composite polylactic acid antibacterial master batch prepared by the method can effectively improve the antibacterial performance and the mechanical performance of polylactic acid, and reduce the weight of a polylactic acid product (the weight reduction purpose is achieved by reducing the density of a composite sheet); although the polylactic acid product prepared by adopting the antibacterial agents such as the silver-loaded titanium dioxide (comparative example 2) has better antibacterial rate of escherichia coli and poorer performance in other antibacterial tests, the polylactic acid product prepared by the method is inferior to the polylactic acid product prepared by the method of the invention although the strength of the polylactic acid product is improved and the density is reduced. And when the polylactic acid sheet was not prepared using the parameters within the range of the present invention (comparative example 3), it was better than the polylactic acid sheet modified with the inorganic antibacterial agent (comparative example 1) in terms of antibacterial effect, but still weaker than the polylactic acid sheets prepared according to the present 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 3 comparative examples is obviously reduced.
Claims (3)
1. The preparation method of the graphene oxide/nano-copper composite antibacterial agent is characterized by comprising the following steps:
a. dissolving 60mg of copper sulfate in 20ml of deionized water to form a copper sulfate solution A;
b. 5g of polyvinyl alcohol is kept at 80 ℃ and stirred to be dissolved in 30ml of deionized water to form a polyvinyl alcohol solution B;
c. stirring the solution B in a magnetic stirrer, dropwise adding the solution A while stirring to dissolve copper ions in the solution B, protecting polyvinyl alcohol, adding 5ml of glucose to reduce the copper ions into nano copper particles, and stirring for 0.5h to finally form a solution C;
d. dissolving 200mg of graphene oxide in 20ml of deionized water, carrying out 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 at-20 ℃, then unfreezing, and repeating for 3 times to form the graphene oxide/nano copper composite material;
e. washing, centrifuging, and freeze-drying at the temperature of minus 20 to minus 30 ℃ for 9 hours to obtain the graphene oxide/nano-copper composite antibacterial agent; or
The PVA dissolution temperature is 85 ℃, the freezing and unfreezing circulation in the step d is 4 times, the freeze-drying time in the step e is 10 hours, the concentration of the copper sulfate solution is 4mg/ml, the concentration of the PVA solution is 0.18g/ml, and the volume ratio of the two is 2.5: 3.5; or
The PVA dissolving temperature is 90 ℃, the freezing and unfreezing circulation is carried out for 5 times in the step d, the freeze-drying time in the step e is 12 hours, the concentration of the copper sulfate solution is 5mg/ml, the concentration of the PVA solution is 0.32g/ml, and the volume ratio of the two is 3: 4.
2. the graphene oxide/nano-copper composite antibacterial master batch prepared from the graphene oxide/nano-copper composite antibacterial agent prepared by the method of claim 1.
3. The preparation method of the graphene oxide/nano-copper composite antibacterial masterbatch according to claim 2, characterized by comprising the following steps: the ratio of the graphene oxide/nano-copper composite antibacterial agent to the polylactic acid matrix is 95-99: 1-5, 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 antibacterial master batch.
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| CN114775019A (en) * | 2022-05-25 | 2022-07-22 | 西南医科大学附属医院 | Preparation method of medical metal implant surface antibacterial coating |
| CN117024811A (en) * | 2023-09-07 | 2023-11-10 | 广州华瑞环保新材料科技有限公司 | Degradable antibacterial plastic film and preparation method thereof |
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