CN112831068B - Preparation method of novel antibacterial composite material - Google Patents

Preparation method of novel antibacterial composite material Download PDF

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CN112831068B
CN112831068B CN202110231163.0A CN202110231163A CN112831068B CN 112831068 B CN112831068 B CN 112831068B CN 202110231163 A CN202110231163 A CN 202110231163A CN 112831068 B CN112831068 B CN 112831068B
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composite material
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CN112831068A (en
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吴成华
洪德腾
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Ningbo Fuerda Smartech Co Ltd
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Abstract

The invention belongs to the technical field of composite materials, and particularly relates to a preparation method of a novel antibacterial composite material. The method comprises the steps of antibacterial agent preparation, antibacterial master batch preparation, antibacterial composite material molding and the like, improves the types and microstructures of the antibacterial agents added into the plastic products, combines the preparation method of antibacterial master batch granulation, and innovates related processes in the preparation process so as to ensure that the antibacterial performance and the mechanical performance of the final finished antibacterial products meet the requirements, and various used raw materials and the preparation process are environment-friendly and safe.

Description

Preparation method of novel antibacterial composite material
Technical Field
The invention belongs to the technical field of composite materials, and particularly relates to a preparation method of a novel antibacterial composite material applicable to automotive interiors or plastic panels.
Background
The antibacterial material is a novel functional material with the function of killing or inhibiting microorganisms, and has extremely wide application in the fields of medical treatment, household articles, household appliances, food packaging, livestock breeding industry and the like. The antibacterial principle is that a composite material is formed by adding a proper antibacterial agent into a common material, and the continuously released antibacterial agent permeates into cell membranes and cell nucleuses of microorganisms such as bacteria and the like to destroy amino acids and synthesis systems in bacterial proteins and influence cell genetic material replication, so that the antibacterial material plays a role in inhibiting or killing the bacteria.
Compared with the common material, the number of bacteria on the product made of the antibacterial material is reduced by more than 90 percent compared with the common product. The antibacterial composite material also has certain application in real life, and one of the application precedent of the modern antibacterial composite material is that the German army in the second war adopts quaternary ammonium salt to treat military uniforms so as to reduce the incidence rate of diseases and wound infection.
Currently, commonly used antimicrobial agents include:
organic antibacterial agents, including quaternary ammonium salts, phenol ethers, benzophenones, biguanides, pyrroles, and the like, for example: furan, thiophene, pyrrole, guanidine, biguanide, and the like. The organic antibacterial agent has the advantages of strong bactericidal power, good immediate effect and the like, but has the disadvantages of poor toxicity safety, high drug resistance risk and the like. In addition, because most organic antimicrobial agents have poor high temperature resistance, the application is mainly surface bonding, i.e., the antimicrobial agent is attached to the surface of the material by surface treatment.
Second, natural antibacterial agents, which are mainly extracts from natural substances, are the first antibacterial agents used by people, for example: is prepared from chitosan, propolis, chitin, and horse radish (allyl thiocyanic acid). The natural antibacterial agent is mainly extracted from animals and plants, and has limited sources; in addition, the antibacterial function is limited, the long-acting effect cannot be achieved, the heat resistance is poor, and carbonization and decomposition are started at 150-180 ℃; after the antibacterial agent is used, peculiar smell or discoloration is often generated on foods and articles, and the application range is greatly limited.
And the inorganic antibacterial agent generally contains metal ions such as Ag, Zn, Cu and the like loaded on inorganic carriers such as zeolite, phosphate and the like to generate the function of slowly releasing antibacterial metal ions, so that the inorganic antibacterial agent has excellent antibacterial long-acting property. The sterilization mechanism of the inorganic antibacterial agent is that when metal ions with positive charges contact with the cell membrane of bacteria, coulomb attraction is generated between the metal ions and the cell membrane with negative charges so that the metal ions are firmly combined with the cell membrane, and the metal ions penetrate through the cell membrane to enter the bacteria and react with amino, sulfydryl and the like on the protein of the bacteria to destroy the protein structure, so that the bacteria die or lose activity.
For the antibacterial product, the actual antibacterial effect is mainly influenced by two factors; one is that the added antibacterial material has the antibacterial effect, including the aspects of antibacterial mechanism, processing difficulty degree, long-acting property and the like, and is most important for antibacterial products; and secondly, the influence on the comprehensive performance of the finished product in the preparation process of the antibacterial product comprises the influence on the performance of the base material and the performance exertion of the antibacterial material. In contrast, the former is more important for antibacterial products because the antibacterial function of the antibacterial material is closely related to the actual antibacterial effect of the finally prepared antibacterial product.
For example, chinese invention patent CN109749250A discloses an antibacterial masterbatch, a preparation method and an application thereof, and an antibacterial material. In the patent, in order to solve the defects of the existing antibacterial material in the aspects of antibacterial performance, stability, continuity and the like, the antibacterial master batch has the advantages of high-efficiency and stable antibacterial performance, good antibacterial continuity and the like through the reasonable proportion of the chlorophenol antibacterial agent, the dispersing agent and the carrier resin in the component content.
For another example, chinese patent CN103910996A discloses an antibacterial masterbatch, a nano antibacterial super tough plastic with the antibacterial masterbatch, and preparation and application thereof. In the patent, in order to solve the problems of basic performance (such as toughness, fracture resistance) and antibacterial property of the material, 1-40 wt% of inorganic nano antibacterial agent and 60-99 wt% of carrier resin are blended and extruded to prepare the antibacterial material, and the inorganic nano antibacterial agent is nano powder of grafted polymer antibacterial agent; so that the basic performances of the material such as toughness and the like and the antibacterial property can meet the requirements.
The existing antibacterial agent is mainly applied to a specific composite material, and the preparation process of the composite material is improved, so that the prepared antibacterial product can have better antibacterial property on the premise of meeting the basic performance requirements of the material. In addition, there are other patents directed to the improvement of the antibacterial masterbatch, or the application of the improved antibacterial agent to specific composite materials, in order to significantly improve the antibacterial performance of the prepared antibacterial product.
For example, chinese invention patent CN101255254A discloses an antibacterial polypropylene pipe, an antibacterial composite masterbatch thereof, and methods for manufacturing the same. In this patent, to solve the problem of insufficient antibacterial effect and persistence, TiO is added2Coated silver-loaded SiO2The antibacterial polypropylene pipe is prepared from the antibacterial particles (prepared according to the method of CN 1663390A) by a conventional melt extrusion process, the antibacterial rate of the pipe reaches over 99 percent, and the antibacterial durability is improved to about 50 years.
For another example, chinese patent CN106221014A discloses a nano-copper antibacterial plastic master batch. In the patent, in order to solve the defects of the prior antibacterial agent in aspects of stability, cost, antibacterial range and the like, the antibacterial effect can be effectively improved and the mechanical performance of an antibacterial product is not influenced by adding the antibacterial agent by improving the components and the content of the antibacterial master batch.
For example, chinese patent CN103571055A discloses an antibacterial plastic masterbatch, a preparation method thereof, and an antibacterial plastic. In the patent, in order to solve the problem of compatibility of the antibacterial agent and the plastic, the components and the content of the antibacterial master batch are also improved, so that the prepared antibacterial master batch has good universality and long-term antibacterial effect, and the mechanical property of the plastic is not influenced by the addition of the antibacterial master batch.
Although the above patent solves the technical problem to be solved more or less by improving the manufacturing process of the plastic product or improving the composition of the antibacterial master batch, there is still a great room for improvement based on the specificity of the application scenario of the composite material.
In addition, aiming at the special requirements of the plastic composite material for the antibacterial material, the antibacterial effect of the antibacterial product is improved correspondingly according to the special requirements in the subsequent preparation of the plastic composite material and the antibacterial property of the antibacterial agent in the finally prepared antibacterial product.
Disclosure of Invention
Therefore, the invention aims to provide a novel preparation method of an antibacterial composite material, which improves the types and microstructures of the antibiotics added into plastic products, combines the preparation method of antibacterial masterbatch granulation, and innovates related processes in the preparation process to ensure that the antibacterial performance and the mechanical performance of the final finished antibacterial products meet the requirements. In addition, various raw materials used by the antibacterial composite material and the manufacturing process are environment-friendly and safe, and have no adverse effect.
In order to achieve the purpose, the invention adopts the scheme that:
a method for preparing a novel antimicrobial composite material, comprising:
the preparation method of the antibacterial agent comprises the following steps: adding TiO into the mixture2With Zn (NO)3)2Respectively adding the mixture into a NaOH solution,stirring at 75-95 deg.C for 10-20h, cooling to room temperature, centrifuging to obtain precipitate, washing, and drying to obtain TiO2-ZnO complexes as TiO2-ZnO composite antibacterial agent.
The preparation method of the antibacterial master batch comprises the following steps: preparing raw materials according to parts by mass, including: 20-40 parts of an antibacterial agent, 0.05-10 parts of a coupling agent, 0.1-10 parts of a dispersing agent and the balance of resin; mixing the coupling agent and the antibacterial agent, uniformly stirring, adding the resin and the dispersing agent, and uniformly stirring to obtain a master batch original shape; and adding the master batch into a double-screw extruder, extruding and granulating, drying and cutting to obtain the antibacterial master batch.
The molding step of the antibacterial composite material comprises the following steps: preparing raw materials according to parts by mass, including: 1-10 parts of antibacterial master batch, 0.05-10 parts of coupling agent, 0.1-10 parts of dispersing agent, 0.1-5 parts of antioxidant, 0.1-5 parts of lubricant and the balance of resin; stirring and uniformly mixing the raw materials at a high speed, adding the mixture into a grinding machine for grinding, and controlling the grain diameter of the ground discharge material to be 500-1000 mu m to obtain the original shape of the composite material; and (3) adding the composite material into a double-screw extruder as it is, and performing melt extrusion granulation at the temperature of 170-260 ℃ in each extrusion section to obtain the antibacterial composite material.
The antibacterial composite material prepared by the method is prepared by nano TiO2The nano TiO compound and nano ZnO act synergistically from different mechanism angles and are matched with the particle characteristics under the nano scale, so that the nano TiO can be effectively improved2The overall antimicrobial properties and antimicrobial durability of the ZnO composite.
According to the preparation method of the novel antibacterial composite material, the step of preparing the antibacterial agent further comprises the step of preparing an additional antibacterial agent, wherein the additional antibacterial agent is nano Ga2O3。
The Ga is2O3The preparation method comprises the following steps: ga is mixed with3+Ga (NO) at a concentration of 0.01mol/L3)3Aqueous solution and 0.1-1mmol/L CH3Placing COONa aqueous solution in a hydrothermal reaction kettle, adjusting the pH value to 8-10, carrying out hydrothermal reaction at the temperature of 200 ℃ for 10-20h, cooling, filtering and washing to obtain GaOOH; roasting GaOOH at 550-700 ℃ for 2-5h, and then annealing for 3-5h to obtain nano Ga as an additional antibacterial agent2O3。
The method for preparing the novel antibacterial composite material according to any one of the above, wherein the additional antibacterial agent is nano Ga2O3With TiO2-ZnO composite antibacterial agent as the source of the antibacterial agent, both of which are as follows 1: 2-1: 5 as an antibacterial agent after being mixed in the proportion range, and is used in the subsequent preparation of the antibacterial master batch.
By using nano Ga with lower concentration requirement2O3As an additional antibacterial agent, with the aforementioned nano TiO2The combined action of the ZnO composite antibacterial agent can effectively improve the antibacterial performance of the antibacterial product.
A process for the preparation of a novel antibacterial composite material according to any one of the preceding claims, said Ga2O3The preparation method comprises the following steps: ga is mixed with3+Ga (NO) at a concentration of 0.01mol/L3)3Aqueous solution with 0.05mmol/L CH3COONa aqueous solution is prepared by the following steps of 1: 1, placing the mixture into a hydrothermal reaction kettle, adjusting the pH value to 9, carrying out hydrothermal reaction at 180 ℃ for 15h, cooling, filtering and washing to obtain GaOOH; roasting GaOOH at 600 deg.C for 3h, and then roasting for 5h to obtain Ga as additional antibacterial agent2O3。
A process for the preparation of a novel antibacterial composite material according to any one of the preceding claims, said Ga2O3With TiO2-ZnO is present as 1: 4 mixing the raw materials to be used as the raw material of the antibacterial agent during the preparation of the antibacterial master batch. The mixed antibacterial agent prepared according to the proportion has the optimal antibacterial performance and can also take the cost and the process complexity into consideration.
According to the preparation method of any one of the novel antibacterial composite materials, the step of uniformly stirring the antibacterial agent and the resin comprises the following steps: and adding the master batch raw sample into a vibration mill, setting the vibration frequency at 1000-1500r/min for 2-5h to obtain the dispersed master batch raw sample and applying the master batch raw sample to the subsequent step of forming the antibacterial composite material. Through carrying out extra vibration mill to the master batch former state and handling, can be so that the granularity of the master batch raw materials after handling more even to can avoid the reunion effect of nanometer antibacterial agent, promote the dispersibility of antibacterial agent in antibiotic master batch or antibiotic goods, in order to increase antibacterial effect.
According to any one of the preparation methods of the novel antibacterial composite material, in the step of preparing the antibacterial master batch, the ratio of the raw materials is as follows: 20-30 parts of antibacterial agent, 0.1-5 parts of coupling agent, 0.1-5 parts of dispersing agent and the balance of resin.
According to any one of the preparation methods of the novel antibacterial composite material, in the step of preparing the antibacterial master batch, the raw materials are in the following ratio: 20-25 parts of antibacterial agent, 0.1-1 part of coupling agent, 0.1-1 part of dispersing agent and the balance of resin.
According to any one of the preparation methods of the novel antibacterial composite material, in the step of forming the antibacterial composite material, the raw materials are mixed in proportion as follows: 1-5 parts of antibacterial master batch, 0.1-5 parts of coupling agent, 0.1-5 parts of dispersing agent, 0.1-5 parts of antioxidant, 0.1-5 parts of lubricant and the balance of resin.
According to any one of the preparation methods of the novel antibacterial composite material, in the step of forming the antibacterial composite material, the raw materials are mixed in proportion as follows: 3-4 parts of antibacterial master batch, 0.1-1 part of coupling agent, 0.1-1 part of dispersing agent, 0.1-1 part of antioxidant, 0.1-1 part of lubricant and the balance of resin.
According to any one of the preparation methods of the novel antibacterial composite material, the grinding discharge particle size is 500-700 mu m.
According to any one of the preparation methods of the novel antibacterial composite material, the temperature of each extrusion section is as follows: 200 ℃ and 260 ℃.
According to any one of the above preparation methods of the novel antibacterial composite material, the resin is PP, PC, PE, ABS or a combination thereof.
The preparation method of the novel antibacterial composite material provided by the invention has the advantages that through a plurality of improvements in the preparation process of the antibacterial composite material, the overall mechanical property of the antibacterial composite material meets the basic requirements of various use scenes, and the antibacterial composite material also has excellent antibacterial performance. In particular, the preparation method of the invention prepares nano-scale TiO2-ZnO composite antibacterial agent and Ga2O3The antibacterial agent is prepared by matching with an antibacterial master batch method, and the antibacterial master batch is ground and dispersed in a vibration mill treatment mode in the preparation process of the antibacterial master batch, so that the discharge granularity is ensuredMeanwhile, the dispersion uniformity of the related antibacterial agent in the resin can be improved, and the antibacterial performance of the whole antibacterial product is finally improved.
In particular nano Ga2O3Due to the introduction of the antibacterial agent, the antibacterial composite material prepared by the invention can have excellent antibacterial performance under the conditions of initial time and lower antibacterial concentration, which is not possessed by the existing antibacterial material.
Drawings
FIG. 1 shows the further preparation of nano Ga from samples according to different synthesis conditions shown in Table 22O3The antibacterial effect of (1) is shown by mixing nano Ga2O3Preparing 20mg/L solution and acting on Escherichia coli 8099, and observing sterilization rate (%) data at different times to draw a time-sterilization rate curve; the abscissa is time (unit: h) and the ordinate is the sterilization rate, expressed in percent (%).
Detailed Description
In order that those skilled in the art will better understand the invention and thus more clearly define the scope of the invention as claimed, it is described in detail below with respect to certain specific embodiments thereof. It should be noted that the following is only a few embodiments of the present invention, and the specific direct description of the related structures is only for the convenience of understanding the present invention, and the specific features do not of course directly limit the scope of the present invention. Such alterations and modifications as are made obvious by those skilled in the art and guided by the teachings herein are intended to be within the scope of the invention as claimed.
A preparation method of a novel antibacterial composite material comprises the following steps:
the preparation method of the antibacterial agent comprises the following steps: adding TiO into the mixture2With Zn (NO)3)2Respectively adding the mixture into NaOH solution, stirring at 75-95 ℃ for reaction for 10-20h, cooling to room temperature after the reaction is finished, centrifugally separating to obtain precipitate, washing and drying to obtain nano TiO2-ZnO complexes as TiO2-ZnO composite antibacterial agent.
The preparation method of the antibacterial master batch comprises the following steps: preparing raw materials according to parts by mass, including: 20-40 parts of an antibacterial agent, 0.05-10 parts of a coupling agent, 0.1-10 parts of a dispersing agent and the balance of resin; mixing the coupling agent and the antibacterial agent, uniformly stirring, adding the resin and the dispersing agent, and uniformly stirring to obtain a master batch original shape; and adding the master batch into a double-screw extruder, performing extrusion granulation, drying and cutting to obtain the antibacterial master batch.
The molding step of the antibacterial composite material comprises the following steps: preparing raw materials according to parts by mass, including: 1-10 parts of antibacterial master batch, 0.05-10 parts of coupling agent, 0.1-10 parts of dispersing agent, 0.1-5 parts of antioxidant, 0.1-5 parts of lubricant and the balance of resin; stirring and uniformly mixing the raw materials at a high speed, adding the mixture into a grinding machine for grinding, and controlling the grain diameter of the ground discharge material to be 500-1000 mu m to obtain the original shape of the composite material; and (3) adding the composite material into a double-screw extruder as it is, and performing melt extrusion granulation at the temperature of 170-260 ℃ in each extrusion section to obtain the antibacterial composite material.
In certain embodiments, the step of preparing the antimicrobial agent further comprises the step of preparing an additional antimicrobial agent, the additional antimicrobial agent being nano-Ga2O3。Ga2O3The preparation method comprises the following steps:
ga is mixed with3+Ga (NO) at a concentration of 0.01mol/L3)3Aqueous solution and 0.1-1mmol/L CH3Placing COONa aqueous solution in a hydrothermal reaction kettle, adjusting the pH value to 8-10, carrying out hydrothermal reaction at the temperature of 200 ℃ for 10-20h, cooling, filtering and washing to obtain GaOOH; roasting GaOOH at 550-700 ℃ for 2-5h, and then annealing for 3-5h to obtain Ga as an additional antibacterial agent2O3。
The additional antibacterial agent is nano Ga2O3With TiO2-ZnO composite antibacterial agent as the source of the antibacterial agent, both of which are as follows 1: 2-1: 5 as an antibacterial agent after being mixed in the proportion range, and is applied to the subsequent preparation of the antibacterial master batch.
In other embodiments, the Ga is2O3The preparation method specifically comprises the following steps: ga is mixed with3+Ga (NO) at a concentration of 0.01mol/L3)3Aqueous solution with 0.05mmol/L CH3COONa aqueous solution is prepared by the following steps of 1: 1 is placed in a hydrothermal reaction kettle in a volume ratioAdjusting the pH value to 9, carrying out hydrothermal reaction at 180 ℃ for 15h, cooling, filtering and washing to obtain GaOOH; roasting GaOOH at 600 deg.C for 3h, and then roasting for 5h to obtain Ga as additional antibacterial agent2O3。
Preferably, the Ga is2O3With TiO2-ZnO is present as 1: 4 mixing the raw materials to be used as the raw material of the antibacterial agent during the preparation of the antibacterial master batch.
In other embodiments, the step of agitating the antimicrobial agent with the resin comprises: adding the master batch raw sample into a vibration mill, setting the vibration frequency at 1000-1500r/min for 2-5h to obtain a dispersed master batch raw sample and applying the raw sample to the subsequent step of forming the antibacterial composite material; namely, the vibration mill mode replaces the common high-speed stirring and uniform mixing. Of course, it is also feasible to add a vibration mill to disperse after the conventional high-speed stirring and mixing.
In some preferred embodiments, the ratio of the raw materials in the step of preparing the antibacterial masterbatch is preferably: 20-30 parts of antibacterial agent, 0.1-5 parts of coupling agent, 0.1-5 parts of dispersing agent and the balance of resin. More preferably, the mixture ratio of the raw materials is as follows: 20-25 parts of antibacterial agent, 0.1-1 part of coupling agent, 0.1-1 part of dispersing agent and the balance of resin.
In other preferred embodiments, the ratio of the raw materials in the step of forming the antibacterial composite material is as follows: 1-5 parts of antibacterial master batch, 0.1-5 parts of coupling agent, 0.1-5 parts of dispersing agent, 0.1-5 parts of antioxidant, 0.1-5 parts of lubricant and the balance of resin. More preferably, the mixture ratio of the raw materials is as follows: 3-4 parts of antibacterial master batch, 0.1-1 part of coupling agent, 0.1-1 part of dispersing agent, 0.1-1 part of antioxidant, 0.1-1 part of lubricant and the balance of resin.
In other preferred embodiments, the grinding discharge particle size is 500-700um, and the temperature of each extrusion section is: 200 ℃ and 260 ℃, and the resin is PP, PC, PE, ABS or the combination thereof.
1. Preparation of antibacterial agents
1.1 nanometer TiO2-ZnO Complex preparation
Weighing 500mg TiO2、3g Zn(NO3)2·6H2O, added to 25mL of 5mol/LHeating to 80 ℃ in NaOH solution, stirring for reaction for 12 hours, cooling to room temperature after the reaction is finished, centrifugally separating for 3-5min at a speed of 5000r/min to obtain precipitate, washing and drying to obtain nano TiO2-ZnO complex for subsequent use as one of the antimicrobial agent sources.
1.2 nanometer TiO2Antibacterial test of-ZnO complexes
Detecting the prepared nano TiO by adopting a paper diffusion method2-ZnO Complex, commercially available Nano TiO2The test results of the samples with respect to the bacteriostatic effect on Escherichia coli 8099 compared with the blank control are shown in Table 1.
TABLE 1 results of antibacterial tests
Figure BDA0002958207460000071
The test method of the paper diffusion method comprises the following steps: firstly, washing lawn on 8099 inclined plane of Escherichia coli growing for more than 48h at room temperature with 5mL phosphate buffer solution, diluting to 10%5～106A bacterial suspension/mL. And adding the bacterial suspension into a bacterial culture dish, adding 20mL of agar culture medium, uniformly mixing, taking a filter paper sheet with the diameter of 6mm, soaking the antibacterial agent with the concentration of 1mg/mL, placing the filter paper sheet on a culture medium platform, culturing at constant temperature for more than 48h, and measuring the size of a bacteriostatic zone.
As can be seen from Table 1, nano TiO is commercially available2And the nano TiO prepared by the invention2the-ZnO compound has certain inhibiting effect on escherichia coli 8099, but the nano TiO prepared by the invention has antibacterial effect2the-ZnO complexes are significantly better.
The reasons for this may include:
the nano TiO prepared by the invention2-ZnO composite compared to nano TiO alone2Or nano ZnO, are significantly better, which may benefit from nano-sized TiO2The ZnO compound has smaller size, so that the surface area of the ZnO compound is increased, and the adsorbability of the material and the contact surface of chemical reaction are increased, thereby improving the antibacterial performance; on the other hand, distributed on the surface of ZnOOf TiO 22And TiO solid-dissolved in ZnO lattice2The photocatalytic capacity of ZnO is improved, so that the ZnO has stronger antibacterial capacity; zn2+After the ions are slowly released, the ions can be combined with cell membrane proteins of bacteria and damage the structures of the cell membrane proteins, and enzymes of an electron transfer system of the bacteria can be damaged and react with DNA (deoxyribonucleic acid) to play an antibacterial role.
In addition, the TiO attached to the surface of ZnO in the invention2The ultrafine particles have specific photocatalytic activity, and after the ultrafine particles can absorb near ultraviolet light with the wavelength of less than 387.3nm, electrons in a valence band can be excited to a conduction band to form high-activity electrons with negative charges, and positive holes are generated on the valence band. The highly active electrons and holes generated in this process can cause the catalytic reaction of the surrounding water molecules with oxygen molecules to generate OH (hydroxyl radical) and O (oxygen atom), and because of their strong oxidizing ability, the highly active electrons and holes can destroy the activity of the microbial cell wall or intracellular protein, or oxidize and decompose it to play an antibacterial role. At the same time, TiO2In the process, the catalyst is only used as a catalyst and is theoretically consumed, so that the durability of the antibacterial can be effectively improved.
The two are synergistic from different mechanism angles, and the characteristics of particles under the nanometer scale are matched, so that the nano TiO can be effectively improved2The overall antimicrobial properties and antimicrobial durability of the ZnO composite.
1.2Ga2O3Preparation of
Ga is mixed with3+Ga (NO) at a concentration of 0.01mol/L3)3Aqueous solution and 0.1-1mmol/L CH3Placing COONa aqueous solution in a hydrothermal reaction kettle, adjusting the pH value to 8-10, carrying out hydrothermal reaction at the temperature of 200 ℃ for 10-20h, cooling, filtering and washing to obtain GaOOH; roasting GaOOH at 550-700 ℃ for 2-5h, and then annealing for 3-5h to obtain nano Ga as an additional antibacterial agent2O3；
Ga2O3The material is mainly applied to semiconductor materials, and the quality requirements of the material and an antibacterial agent can be obviously different from those of the semiconductor material used as a wide forbidden band. For Ga in order to examine different preparation conditions2O3As an antimicrobial agentAnd (3) selecting parameters with large influence on the quality, such as raw material concentration, proportion, pH and the like, to test and examine the influence on the quality. The synthesis conditions for the different gaoohs are shown in table 2.
TABLE 2GaOOH Synthesis Condition testing
Numbering CH3COONa concentration V Ga(NO3)3：VCH3COONa pH
Sample 1 0.2 1：1 8
Sample 2 0.4 2：1 8
Sample 3 0.6 1：1 9
Sample No. 4 0.6 2：1 9
Sample No. 5 0.8 1：1 10
Sample No. 6 1.0 2：1 10
Wherein Ga (NO)3)3The concentration of the aqueous solution was fixed at 0.01mol/L, CH3The concentration of the COONa aqueous solution was measured by the parameters listed in the above table, and the volume ratio V was determinedGa(NO3)3：VCH3COONa. Reacting an aqueous solution of Ga (NO3)3 with CH3Volume ratio of COONa aqueous solution.
Ga obtained as above2O3The antibacterial agent is prepared into a solution with the same concentration, and the bactericidal effect of the antibacterial agent on escherichia coli 8099 is examined so as to determine the nano Ga prepared under the synthesis condition of the sample 42O3The bactericidal effect was optimized, and the bactericidal rate of each sample was plotted against time as shown in fig. 1.
Fig. 1 shows the bactericidal rate-time curves for the above samples at the same concentrations, from which it can be seen that: 1. the sterilization rate of each sample is increased along with the increase of time, and the samples tend to be stable after about 1.5-2 h; 2. the best synthesis conditions of the sample 4 were determined by combining the synthesis conditions and the sterilization rate results, and the synthesis conditions were determined to be the nano Ga of the present invention2O3Conditions for synthesis of the antibacterial agent.
Nano Ga obtained according to conditions of sample 42O3Only about 15mg/L of the solution is needed to kill over 90 percent of the Escherichia coli 8099. Compared with common ZnO and TiO2The sterilization rate of LD50 is 500mg/L, the nano Ga prepared by the invention2O3The sterilization rate is obviously improved.
1.3 preparation of Mixed antibacterial Agents
With nano TiO2-ZnO and nano Ga2O3Respectively as a composite antibacterial agent and an additional antibacterial agent, compared with the traditional method that only TiO is adopted2ZnO as an antibacterial agent, and Ga is added in the invention2O3As an antibacterial agent to improve the overall antibacterial performance of the material.
The mixed antibacterial agent of the present invention is preferably prepared by mixing 1: 2-1: 5 (mass ratio), i.e. in the conventional TiO2Ga is added into the-ZnO antibacterial agent in a proportion of 16.7-50 wt%2O3Thereby obtaining the mixed antibacterial agent and being applied to the subsequent preparation of the antibacterial master batch.
The Escherichia coli 8099 is still used as a target strain, and the antibacterial performance of the mixed antibacterial agent with different proportions is tested; the antibacterial effect of each sample was measured by the bacteriostatic loop method, and is shown in table 3.
TABLE 3 antibacterial Properties of the mixed antibacterial agents at different mixing ratios
Ga2O3：TiO2-ZnO Zone of inhibition/mm Ga2O3：TiO2-ZnO Zone of inhibition/mm
1：1 47 1：5 39
1：2 47 1：6 34
1：3 46 1：8 29
1：4 43 1：10 18
From the test results shown in Table 3, it is understood that nano Ga2O3The addition amount of (A) is increased to have a positive effect on the antibacterial performance, but considering factors such as cost, process complexity and the like, the Ga is preferably used2O3With TiO2-ZnO is present as 1: 4 used as raw material of antibacterial agent in preparation of antibacterial master batch after being mixed, namely Ga2O3Accounting for 20wt percent.
Meanwhile, the mixed antibacterial agent can be applied to the subsequent antibacterial master batch preparation after being mixed, or two antibacterial agents with corresponding mass can be respectively added into the antibacterial master batch preparation, and tests show that the two modes have no obvious substantial influence on the final effect.
2. Preparation of antibacterial masterbatch
The raw materials are prepared according to the parts by weight, and comprise 20-40 parts of an antibacterial agent, 0.05-10 parts of a coupling agent, 0.1-10 parts of a dispersing agent and 50-90 parts of resin, and the percentage of each component is ensured to meet 100%. The coupling agent is aminopropyltriethoxysilane (KH550), glycidoxypropyltrimethoxysilane (KH560) or methacryloxypropyltrimethoxysilane (KH 570). And (3) mixing the coupling agent and the antibacterial agent, uniformly stirring, adding the resin and the dispersing agent, and uniformly stirring at a high speed to obtain the master batch. And finally, adding the master batch into a double-screw extruder, performing extrusion granulation, drying and cutting to obtain the antibacterial master batch.
The dispersion degree of the antibacterial agent in the antibacterial master batch is closely related to the antibacterial performance of the antibacterial master batch and the overall antibacterial performance of the antibacterial product. Therefore, in order to improve the dispersion uniformity of the antibacterial agent in the antibacterial master batch and avoid the influence of co-agglomeration on the antibacterial performance, a vibration mill dispersion processing mode is introduced in the preparation process of the antibacterial master batch.
Namely, the step of uniformly stirring the antibacterial agent and the resin comprises the following steps: adding the master batch raw sample into a vibration mill, setting the vibration frequency at 1000-1500r/min for 2-5h to obtain a dispersed master batch raw sample and applying the master batch raw sample to the subsequent step of forming the antibacterial composite material, thereby solving the problem of agglomeration of nano antibacterial agent particles and adjusting the nano antibacterial agent (comprising nano Ga)2O3With nano TiO2-ZnO complex) to make it more uniformly dispersed.
3. The molding step of the antibacterial composite material comprises the following steps:
the raw materials are prepared according to the parts by weight, and comprise 1-10 parts of antibacterial master batch, 0.05-10 parts of coupling agent, 0.1-10 parts of dispersing agent and the balance of resin. In order to ensure the antibacterial performance of the final finished product, the raw materials are stirred at a high speed and mixed uniformly, and then are added into a grinding machine for grinding, and the grain diameter of the ground discharge is controlled to be 500-1000 mu m, so that the original shape of the composite material is obtained. And finally, adding the composite material into a double-screw extruder as it is, and performing melt extrusion granulation, wherein the temperature of each extrusion section is 200-.
4. Antimicrobial dispersion treatment
In order to examine the influence of vibration mill treatment on the finished antibacterial product in the preparation process of the antibacterial master batch, the antibacterial product is respectively manufactured according to two test tests of vibration mill treatment and non-vibration mill treatment, and the antibacterial test and the mechanical property test of the antibacterial product are carried out. PP was used as the resin in the experiments.
The 24-hour antibacterial ratio of each antibacterial product obtained by measuring the bacterial strain of Escherichia coli 8099 is shown in Table 4.
TABLE 424 hours antibacterial Rate
Sample (I) Antibacterial ratio/%)
Antimicrobial article with vibratory mill treatment 99.1
Vibration-free mill treated antimicrobial articles 100
The mechanical properties of the two samples were measured separately and the results are shown in table 5.
TABLE 5 mechanics performance table of antibacterial products
Figure BDA0002958207460000101
Wherein, the tensile strength (MPa) and the elongation at break/% are tested according to GB/T1040.1-2018, the notch impact strength (J/m2) is tested according to GB/T1843-2008, the flexural modulus is tested according to GB/T9341-2008, and the heat distortion temperature is tested according to GB/T1634.1-2019.
As can be seen from the results of the mechanical property tests in Table 5, the mechanical property of the antibacterial product prepared by the invention is improved compared with that of the common material. In addition, for the antibacterial product prepared by the invention, the antibacterial rate of the final product is measured according to QB/T2591-2003, and test results show that the antibacterial rate of the antibacterial product prepared by the invention is more than 99 percent, and the basic requirements of various application scenes on antibacterial materials are met.

Claims (8)

1. A preparation method of a novel antibacterial composite material is characterized by comprising the following steps:
the preparation method of the antibacterial agent comprises the following steps: adding TiO into the mixture2With Zn (NO)3)2Respectively adding the mixture into NaOH solution, stirring at 75-95 ℃ for reaction for 10-20h, cooling to room temperature after the reaction is finished, centrifugally separating to obtain precipitate, washing and drying to obtain nano TiO2-ZnO complexes as TiO2-ZnO complex antimicrobial agent;
the preparation method of the antibacterial master batch comprises the following steps: preparing raw materials according to parts by mass, including: 20-40 parts of an antibacterial agent, 0.05-10 parts of a coupling agent, 0.1-10 parts of a dispersing agent and the balance of resin; mixing the coupling agent and the antibacterial agent, uniformly stirring, adding the resin and the dispersing agent, and uniformly stirring to obtain a master batch original shape; adding the master batch into a double-screw extruder, performing extrusion granulation, drying and cutting to obtain antibacterial master batch;
the molding step of the antibacterial composite material comprises the following steps: preparing raw materials according to parts by mass, including: 1-10 parts of antibacterial master batch, 0.05-10 parts of coupling agent, 0.1-10 parts of dispersing agent, 0.1-5 parts of antioxidant, 0.1-5 parts of lubricant and the balance of resin; stirring and uniformly mixing the raw materials at a high speed, adding the mixture into a grinding machine for grinding, and controlling the grain diameter of the ground discharge material to be 500-1000 mu m to obtain the original shape of the composite material; adding the composite material into a double-screw extruder in the original state, and performing melt extrusion granulation, wherein the temperature of each extrusion section is 170-260 ℃, so as to obtain the antibacterial composite material;
the step of preparing the antibacterial agent further comprises the step of preparing an additional antibacterial agent, wherein the additional antibacterial agent is nano Ga2O3(ii) a The Ga is2O3The preparation method comprises the following steps: ga is mixed with3+Ga (NO) at a concentration of 0.01mol/L3)3Aqueous solution with 0.05mmol/L CH3COONa aqueous solution is prepared by the following steps of 1: 1, placing the mixture in a hydrothermal reaction kettle, adjusting the pH value to be pH =9, carrying out hydrothermal reaction at 180 ℃ for 15 hours, cooling, filtering and washing to obtain GaOOH; roasting GaOOH at 600 deg.C for 3h, and then roasting for 5h to obtain Ga as additional antibacterial agent2O3；
The additional antibacterial agent is nano Ga2O3With TiO2-ZnO composite antibacterial agent as the source of antibacterial agent, both of which are as follows 1: 2-1: 4, and mixing the mixture as an antibacterial agent to prepare the antibacterial master batch.
2. The method of preparing a novel antimicrobial composite material according to claim 1, wherein the Ga is2O3With TiO2-ZnO is present as 1: 4 mixing the raw materials to be used as the raw material of the antibacterial agent during the preparation of the antibacterial master batch.
3. The preparation method of the novel antibacterial composite material as claimed in claim 1 or 2, wherein the step of uniformly stirring and mixing the antibacterial agent and the resin comprises the following steps: and adding the master batch raw sample into a vibration mill, setting the vibration frequency at 1000-1500r/min for 2-5h to obtain the dispersed master batch raw sample and applying the master batch raw sample to the subsequent step of forming the antibacterial composite material.
4. The preparation method of the novel antibacterial composite material according to claim 1 or 2, wherein in the step of preparing the antibacterial master batch, the mixture ratio of the raw materials is as follows: 20-30 parts of antibacterial agent, 0.1-5 parts of coupling agent, 0.1-5 parts of dispersing agent and the balance of resin.
5. The preparation method of the novel antibacterial composite material according to claim 4, wherein in the step of preparing the antibacterial master batch, the raw materials are in the following ratio: 20-25 parts of antibacterial agent, 0.1-1 part of coupling agent, 0.1-1 part of dispersing agent and the balance of resin.
6. The preparation method of the novel antibacterial composite material as claimed in claim 3, wherein in the step of forming the antibacterial composite material, the mixture ratio of the raw materials is as follows: 1-5 parts of antibacterial master batch, 0.1-5 parts of coupling agent, 0.1-5 parts of dispersing agent, 0.1-5 parts of antioxidant, 0.1-5 parts of lubricant and the balance of resin.
7. The preparation method of the novel antibacterial composite material as claimed in claim 6, wherein in the step of forming the antibacterial composite material, the mixture ratio of the raw materials is as follows: 3-4 parts of antibacterial master batch, 0.1-1 part of coupling agent, 0.1-1 part of dispersing agent, 0.1-1 part of antioxidant, 0.1-1 part of lubricant and the balance of resin.
8. The method for preparing the novel antibacterial composite material as claimed in claim 3, wherein the grinding discharge particle size is 500-700 μm, and the temperature of each extrusion section is as follows: 200 ℃ and 260 ℃.
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