CN111253622B - Preparation method of high-antibacterial-activity and yellowing-resistant antibacterial agent, plastic plate and storage cabinet - Google Patents
Preparation method of high-antibacterial-activity and yellowing-resistant antibacterial agent, plastic plate and storage cabinet Download PDFInfo
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Abstract
The invention relates to a preparation method of an antibacterial agent with high antibacterial activity and yellowing resistance, wherein the antibacterial agent for a door cabinet plate is modified silver-loaded graphene oxide modified by maleic anhydride, or/and a modified composite antibacterial agent formed by loading nano silver-metal oxide on graphene oxide and modifying by maleic anhydride, and the preparation method comprises the following steps: step 1, completely dissolving maleic anhydride in a DMF solvent, then continuously adding dimethylbenzene, and stirring to completely dissolve all components; step 2, adding the silver-loaded graphene oxide or/and the composite antibacterial agent into the solution obtained in the step 1, reacting for 5-6 hours at 40-50 ℃ under the stirring condition, and then performing suction filtration treatment to obtain antibacterial agent filter residue; and 3, fully washing the filter residue, and then drying in an oven at 86-90 ℃ to obtain the modified silver-loaded graphene oxide or/and modified composite antibacterial agent modified by maleic anhydride.
Description
Technical Field
The invention relates to the technical field of functional plastics, in particular to an antibacterial plastic and a door cabinet using the same.
Background
Along with the wider application range of the door cabinets, the plastic door cabinets are also raised. But the current plastic door cabinets have no antibacterial function. With the continuous pursuit of people for quality of life and health management, the demand of the antibacterial property of the door cabinet is increased. For example, door cabinets used in food factories, medical laboratories, hospitals, kindergartens, etc. have increasingly high demands for antibacterial properties of the door cabinets. In order to increase the antibacterial property of the door cabinet, one method is to directly paint antibacterial paint on the original door cabinet, but the antibacterial paint can change the style or the color tone of the original door cabinet, the antibacterial capability cannot be lasting, and the procedure of painting the antibacterial paint is added, so that time and labor are wasted.
In addition, the conventional antibacterial materials include inorganic antibacterial agents and organic antibacterial agents. However, the most widely used inorganic antibacterial agents are nano-silver antibacterial agents, and organic antibacterial agents such as quaternary ammonium salts and natural antibacterial extracts.
In order to solve the above problems, the prior art with publication number CN109517314A discloses a nano-antibacterial door cabinet sheet, which is prepared from the following components in parts by weight: 30-40 parts of ABS; 60-80 parts of HIPS; 1-5 parts of nano-silver antibacterial agent; 5-8 parts of a compatilizer; 2-5 parts of a lubricant; 3-6 parts of a heat preservation agent. The nano antibacterial door cabinet sheet material has the antibacterial property of more than 98 percent, can achieve the antibacterial effect for more than 10 years, and is suitable for door cabinets required by food factories, medical laboratories, hospitals, kindergartens and other places. The rise of nano silver antibacterial agents brings new opportunities for improving the living environment of human beings, and nano-scale substances have higher specific surface area and reaction activity, show stronger antibacterial effect, are not easy to generate tolerance and have good biocompatibility, and are commonly used antibacterial agents at present.
In addition, graphene, which is known to have a single-layer thickness of only 0.35nm, is the thinnest and lightest nanomaterial known in the world at present, has a huge specific surface area, shows excellent antibacterial performance, shows only weak cytotoxicity when acting on cells or organisms, and is a nanomaterial with both antibacterial property and good biocompatibility.
However, Graphene Oxide (GO) is a novel carbon material with excellent performance as a precursor of graphene, has a thickness of only about 1nm, a width of at most ten micrometers, a high specific surface area and rich oxygen-containing functional groups, and is a product in which partial double bonds on graphene are replaced by hydroxyl (-OH), Carboxyl (COOH) and epoxy (C-O-C). Therefore, many hydroxyl groups and epoxy groups are generated on the graphene oxide monolayer, and a large number of carboxyl groups and carbonyl groups are introduced at the edge of the monolayer.
It can be seen that when graphene oxide is compounded with polymer matrix resin, on one hand, due to the large specific surface area and strong van der waals force between sheets, the graphene oxide is very easy to agglomerate during application, and therefore, the dispersibility of the graphene oxide in the polymer matrix and the compatibility of the graphene oxide and the polymer are key factors for exerting the antibacterial ability and other special functions of the graphene oxide. On the other hand, the graphene oxide and the nano-silver antibacterial agent have both advantages and disadvantages and cannot achieve the optimal antibacterial effect. Therefore, the synergistic antibacterial performance of the graphene oxide and nano-silver antibacterial agent is fully exerted, and the development of the silver-loaded graphene composite antibacterial agent becomes a current research hotspot.
In conclusion, the surface of Graphene Oxide (GO) contains hydroxyl, carboxyl, carbonyl and epoxy, and the graphene oxide is easy to agglomerate when being compounded with polymer matrix resin, so that the comprehensive antibacterial performance of the graphene oxide and the nano-silver antibacterial agent is seriously influenced.
Disclosure of Invention
The invention provides an antibacterial agent which has good dispersibility, excellent mechanical property and excellent comprehensive antibacterial property and can not cause yellowing of a high polymer product in a processing process or a using process, and aims to solve the technical problems that the mechanical property and the antibacterial property of the high polymer product are influenced by poor dispersibility of the antibacterial agent in the prior art, or/and the mechanical property and the quality of the high polymer product are influenced by easy yellowing of the antibacterial agent in the processing process or the using process.
The invention is realized by the following technical scheme: the preparation method of the high antibacterial activity and yellowing resistance antibacterial agent for the door cabinet board comprises the following steps of:
step 1, completely dissolving maleic anhydride in a DMF solvent to obtain a maleic anhydride-DMF solution, then continuously adding xylene which is 3-4 times of the weight of the maleic anhydride into the maleic anhydride-DMF solution, and stirring to completely dissolve all components.
And 2, adding the silver-loaded graphene oxide or/and the composite antibacterial agent into the solution obtained in the step 1, reacting for 5-6 hours at 40-50 ℃ under the stirring condition, performing suction filtration treatment after the reaction is finished, and separating to obtain the modified silver-loaded graphene oxide or/and the modified composite antibacterial agent filter residue.
And 3, fully washing the filter residue by acetone, ethanol and deionized water solution in sequence, and then drying in an oven at 86-90 ℃ to obtain the modified silver-loaded graphene oxide modified by maleic anhydride or/and the modified composite antibacterial agent.
In a specific embodiment, before performing step 1, the method further comprises a step of loading nano silver on the graphene-like oxide to obtain the silver-loaded graphene oxide, or/and a step of loading and intercalating nano silver-metal oxide on the graphene-like oxide to obtain the composite antibacterial agent.
Preferably, the composite antibacterial agent is composed of 5-15 parts by weight of nano silver-metal oxide and 15-45 parts by weight of graphene oxide-like, wherein the nano silver-metal oxide is composed of the following components in parts by weight:
Ag-CuO45％-55％；
Ag-ZnO22％-35％；
Ag-TiO220％-25％。
preferably, the nano silver-metal oxide consists of 48 mass percent of Ag-CuO, 30 mass percent of Ag-ZnO and 22 mass percent of Ag-TiO2The composition of (1).
Preferably, the weight part ratio of the maleic anhydride to the graphene oxide-like substance is 1-3.
Preferably, the plastic sheet material uses the high antibacterial activity and yellowing-resistant antibacterial agent prepared by the preparation method.
Preferably, the storage cabinet is made of the plastic plate.
The invention has the beneficial technical effects that:
firstly, the surface of the graphene oxide-like material adopted by the invention mainly contains oxygen-containing groups of hydroxyl groups, so that the graphene oxide-like material can be subjected to esterification reaction with maleic anhydride.
In addition, the silver-loaded graphene oxide and the composite antibacterial agent are modified by maleic anhydride, the surface hydroxyl groups of the graphene oxide are converted into ester groups, and the compatibility and the dispersibility of the silver-loaded graphene oxide and the composite antibacterial agent with matrix resin and powdered rubber are improved, so that the antibacterial agent system disclosed by the invention is easy to disperse uniformly, the synergistic antibacterial effect and the comprehensive antibacterial performance of the graphene oxide-silver source antibacterial component are effectively improved, and the antibacterial performance is excellent.
And secondly, the graphene-like oxide is used as a carrier of the silver-source antibacterial component, the silver-source antibacterial component is loaded and adsorbed on the graphene-like oxide through hybridization intercalation and chemical hydrogen bond effects of the silver-source antibacterial component to form a composite antibacterial agent between layers, on one hand, the nano particles of the silver-source antibacterial component grow on the surface of the graphene-like oxide to promote the comprehensive antibacterial performance of the graphene-like oxide and the graphene-like oxide, so that the efficient synergistic bactericidal effect is realized, on the other hand, the antibacterial performance is realized and prolonged through slow release, and the composite antibacterial agent has the advantages of high efficiency, no toxicity and environmental protection. Meanwhile, the silver-loaded zirconium phosphate antibacterial agent and the composite antibacterial agent are not easy to hydrolyze, and the antibacterial agent does not have yellowing phenomenon in the process of processing a high polymer product or using the high polymer product, and has high antibacterial activity and yellowing resistance.
Finally, the graphene adopted by the invention has a lubricating effect and is cooperated with the reinforcing effect of the silver source antibacterial component on the matrix resin system, so that the impact strength and the tensile strength of the polymer product are improved.
Detailed Description
The processing additive comprises one or more of a compatilizer, an antioxidant, a toughening agent, a coupling agent, an antistatic agent, an ultraviolet absorbent, a stabilizer, a lubricant and a dispersing agent, and the processing additive which is conventionally used in the technical field is suitable for the processing additive and can be selectively added by a person skilled in the art according to needs. Such as: the coupling agent can be selected from silane coupling agent such as KH560 or KH550, the dispersant can be white oil, calcium stearate, zinc stearate and silicone powder, the antioxidant can be selected from hindered phenol antioxidant, the toughening agent can be selected from one or more of POE-g-GMA, EMA-g-GMA and methyl acrylate-butadiene-styrene terpolymer, the lubricant can be one or more of E wax, OP wax and PE wax, and the compatilizer can be selected from maleic anhydride modified ethylene-vinyl acetate copolymer and maleic anhydride grafted polypropylene.
Ag-CuO, Ag-ZnO or Ag-TiO of the present invention2Can be prepared according to the prior art or purchased from commercial products. The graphene oxide-like material is prepared from graphene oxide by the conventional method, and is prepared by adding manganese sulfate and hydrogen peroxide into the graphene oxide under the condition of an acid solution, performing radiation treatment under the condition of ultraviolet light with the wavelength of 185nm, and performing suction filtration and drying.
Example 1
The preparation process of the modified silver-loaded graphene oxide of this embodiment is as follows:
and S1, loading 5 parts of nano silver on 15 parts of graphene oxide to obtain the silver-loaded graphene oxide. The operation of the step is the same as that of the existing method that nano silver is loaded on graphene oxide.
And step S2, completely dissolving maleic anhydride in a DMF solvent to obtain a maleic anhydride-DMF solution, then continuously adding xylene which is 3-4 times of the weight of the maleic anhydride into the maleic anhydride-DMF solution, and stirring to completely dissolve all components.
In this step, the ratio of the parts by weight of maleic anhydride to the graphene oxide-like compound is 1 to 3, and more preferably 1.5.
And S3, adding the silver-loaded graphene oxide into the solution obtained in the step S2, reacting for 5-6 hours at 40-50 ℃ under the stirring condition, performing suction filtration treatment after the reaction is finished, and separating to obtain the modified silver-loaded graphene oxide filter residue.
And step S4, fully washing the modified silver-loaded graphene oxide filter residue by acetone, ethanol and deionized water solution in sequence, and then drying in an oven at 86-90 ℃ to obtain the modified silver-loaded graphene oxide modified by maleic anhydride.
The method has the technical effects that the silver-loaded graphene oxide is modified by maleic anhydride, and the surface hydroxyl groups of the silver-loaded graphene oxide are converted into ester groups, so that the compatibility and the dispersibility of the silver-loaded graphene oxide, matrix resin (ABS, HIPS or PP) and powder rubber are improved.
Example 2
The modified composite antibacterial agent comprises the following components in parts by weight: 15 parts of graphene oxide-like, 5 parts of nano silver-metal oxide, wherein: the nano silver-metal oxide comprises the following components in percentage by mass: 45% of Ag-CuO, 35% of Ag-ZnO and 20% of Ag-TiO2. Wherein the surface of the graphene oxide-like material mainly contains oxygen-containing groups of hydroxyl groups.
The nano silver-metal oxide composite antibacterial agent of the present example was prepared by the following steps:
and step S1, dissolving the graphene oxide in deionized water, and performing ultrasonic dispersion treatment to form a suspension solution.
And step S2, adding the nano silver-metal oxide into the suspension solution obtained in the step 1, continuing ultrasonic treatment, carrying out suction filtration and drying treatment to obtain the composite antibacterial agent.
And step S3, completely dissolving maleic anhydride in a DMF solvent to obtain a maleic anhydride-DMF solution, then continuously adding xylene which is 3-4 times of the weight of the maleic anhydride into the maleic anhydride-DMF solution, and stirring to completely dissolve all components.
Wherein, the weight portion ratio of the maleic anhydride to the similar graphene oxide can be 1-3. However, in this example, the ratio of the weight parts of maleic anhydride to the graphene oxide-like compound was 1.5.
And S4, adding the compound antibacterial agent into the solution obtained in the step S3, carrying out suction filtration treatment after the reaction is finished at 40-50 ℃ under the stirring condition and 5-6, and separating to obtain the modified compound antibacterial agent filter residue.
And step S5, fully washing the modified composite antibacterial agent filter residue by acetone, ethanol and deionized water solution in sequence, and then drying in an oven at 86-90 ℃ to obtain the modified composite antibacterial agent modified by maleic anhydride.
In the embodiment, graphene-like oxide is used as a carrier, the graphene-like oxide is loaded and adsorbed on the graphene-like oxide through the hybridization intercalation effect and the chemical hydrogen bond effect of silver source antibacterial components to form a composite antibacterial agent between layers, the composite antibacterial agent is modified by maleic anhydride, and the surface hydroxyl groups of the graphene-like oxide are converted into ester groups.
Example 3
The nano silver-metal oxide composite antibacterial agent comprises the following components in parts by weight: 45 parts of graphene oxide-like, and 12 parts of nano silver-metal oxide, wherein: the nano silver-metal oxide comprises the following components in percentage by mass: 53 percent of Ag-CuO, 22 percent of Ag-ZnO and 25 percent of Ag-TiO2. Wherein the surface of the graphene oxide-like material mainly contains oxygen-containing groups of hydroxyl groups. Otherwise, the same procedure as in example 2 was followed to prepare the nano silver-metal oxide composite antibacterial agent of example 2.
Example 4
The nano silver-metal oxide composite antibacterial agent comprises the following components in parts by weight: 30 parts of graphene oxide-like, 8 parts of nano silver-metal oxide, wherein: the nano silver-metal oxide comprises the following components in percentage by mass: 48% of Ag-CuO, 30% of Ag-ZnO and 22% of Ag-TiO2. Wherein the surface of the graphene oxide-like material mainly contains oxygen-containing groups of hydroxyl groups. Otherwise, the same procedure as in example 2 was followed to prepare the nano silver-metal oxide composite antibacterial agent of example 2.
Example 5
The antibacterial plastic comprises the following components in parts by weight: 70 parts of HIPS, 0.5 part of silver-loaded zirconium phosphate, 1 part of powdered rubber, 0.5 part of coupling agent, 0.5 part of compatilizer, 0.5 part of lubricant and 0.5 part of dispersant.
The antibacterial plastic is prepared by the following steps:
(1) carrying out surface coupling coating treatment on the silver-loaded zirconium phosphate for later use;
(2) putting the compatilizer, the lubricant and the dispersant into a mixer for mixing for 1-5 minutes, and then putting the silver-loaded zirconium phosphate, the ABS and the HIPS into the mixer for mixing for at least 3 minutes;
(3) and setting the temperature to be 180-235 ℃, injecting the blend into a mold through an injection molding machine, and cooling to 65-85 ℃ in the mold to form to obtain the antibacterial door cabinet plate.
The antibacterial cabinet or the antibacterial door cabinet can be manufactured by adopting the antibacterial door cabinet plate in the embodiment.
Example 6
The antibacterial plastic comprises the following components in parts by weight: 100 parts of HIPS, 5 parts of the modified composite antibacterial agent prepared in example 2, 5 parts of powdered rubber, 0.5 part of compatilizer and 0.5 part of lubricant. Then, the antibacterial door cabinet plate is prepared according to the method steps of the embodiment 5.
The antibacterial cabinet or the antibacterial door cabinet can be manufactured by adopting the antibacterial door cabinet plate in the embodiment.
Example 7
The antibacterial plastic comprises the following components in parts by weight: 85 parts of HIPS, 5 parts of powdered rubber, 4 parts of the modified composite antibacterial agent prepared in example 3, 0.5 part of compatilizer and 0.5 part of lubricant. Then, the antibacterial door cabinet plate is prepared according to the method steps of the embodiment 5.
The antibacterial cabinet or the antibacterial door cabinet can be manufactured by adopting the antibacterial door cabinet plate in the embodiment.
Example 8
The antibacterial plastic comprises the following components in parts by weight: 90 parts of HIPS, 5 parts of powdered rubber, 1.5 parts of modified silver-loaded graphene oxide prepared in example 1, 2.5 parts of modified composite antibacterial agent prepared in example 4, 0.5 part of compatilizer and 0.5 part of lubricant. Then, the antibacterial door cabinet plate is prepared according to the method steps of the embodiment 5.
The antibacterial cabinet or the antibacterial door cabinet can be manufactured by adopting the antibacterial door cabinet plate in the embodiment.
Example 9
The antibacterial plastic comprises the following components in parts by weight: 90 parts of HIPS, 5 parts of powdered rubber, 4 parts of the modified silver-loaded graphene oxide prepared in example 1, 0.5 part of a compatilizer and 0.5 part of a lubricant. Then, the antibacterial door cabinet plate is prepared according to the method steps of the embodiment 5.
The antibacterial cabinet or the antibacterial door cabinet can be manufactured by adopting the antibacterial door cabinet plate in the embodiment.
Comparative example 1
In this embodiment, nano silver is loaded on graphene oxide to obtain silver-loaded graphene oxide. The plastic of the embodiment comprises the following components in parts by weight: 90 parts of HIPS, 5 parts of powdered rubber, 4 parts of silver-loaded graphene oxide, 0.5 part of compatilizer and 0.5 part of lubricant. A comparative panel was then prepared according to the method steps of example 5.
COMPARATIVE EXAMPLE 2 (blank COMPARATIVE EXAMPLE)
The plastic of the embodiment comprises the following components in parts by weight: 90 parts of HIPS, 5 parts of powdered rubber, 0.5 part of compatilizer and 0.5 part of lubricant. A comparative panel was then prepared according to the method steps of example 5.
And (3) performance testing:
1. test methods and standards: tensile strength GB/T1040-2006, impact strength GB/T1843-2008.
2. And (3) testing antibacterial performance: according to "ISO 22196: 2011 measurement of antimicrobial activity on plastics and other non-porous surfaces.
The results are shown in the following table:
table 1 attached mechanical properties test results
The test results show that the graphene is modified by maleic anhydride, so that the surface hydroxyl groups of the silver-loaded graphene oxide and the graphene oxide in the composite antibacterial agent are converted into ester groups, the compatibility and the dispersibility of the silver-loaded graphene oxide and the composite antibacterial agent and a matrix resin system are improved, the antibacterial agent system is easy to disperse uniformly, the modified antibacterial agent has a lubricating effect on the polymer system, a reinforcing effect on the matrix resin system and an effect of improving the impact strength and the tensile strength of a polymer product, and the comprehensive antibacterial performance of the graphene oxide-silver source antibacterial component is effectively exerted.
In addition, the organic antibacterial agent is easy to have a yellowing phenomenon in the processing process, the inorganic antibacterial agent has the defects of easy hydrolysis and short effective period, and part of the inorganic antibacterial agent is easy to have a yellowing phenomenon.
TABLE 2 attached test results for E.coli
TABLE 3 attached Table 3 detection results of Staphylococcus aureus
The test results show that the dispersibility of the antibacterial agent in a polymer system is an important factor influencing the antibacterial performance of the antibacterial agent, and the modified silver-loaded graphene oxide and the modified composite antibacterial agent modified by maleic anhydride are easy to disperse uniformly in the polymer system, so that the synergistic antibacterial effect and the comprehensive antibacterial performance of the graphene oxide-silver source antibacterial component are effectively improved, and the antibacterial performance is excellent.
The test results also show that the antibacterial activity of the antibacterial agent prepared by compounding 1.5 parts of modified silver-loaded graphene oxide and 2.5 parts of modified composite antibacterial agent is optimal, wherein the modified composite antibacterial agent is prepared by mixing 30 parts of graphene oxide, 48% of Ag-CuO, 30% of Ag-ZnO and 22% of Ag-TiO28 parts of nano silver-metal oxide.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (1)
1. The utility model provides a high antibacterial activity and antibiotic door cabinet panel that resists yellowing, antibiotic door cabinet panel adopts antibiotic plastics to make its characterized in that: the paint comprises the following components in parts by weight: 90 parts of HIPS (high impact polystyrene), 5 parts of powdered rubber, 1.5 parts of modified silver-loaded graphene oxide, 2.5 parts of modified composite antibacterial agent, 0.5 part of compatilizer and 0.5 part of lubricant, wherein:
the preparation process of the modified silver-loaded graphene oxide is as follows:
s1, loading 5 parts of nano silver on 15 parts of graphene oxide to obtain silver-loaded graphene oxide;
step S2, completely dissolving maleic anhydride in a DMF solvent to obtain a maleic anhydride-DMF solution, continuously adding xylene which is 3-4 times of the weight of the maleic anhydride into the maleic anhydride-DMF solution, and stirring to completely dissolve all components, wherein the weight part ratio of the maleic anhydride to the graphene oxide is 1-3;
step S3, adding the silver-loaded graphene oxide into the solution obtained in the step S2, reacting for 5-6 hours at 40-50 ℃ under the stirring condition, performing suction filtration after the reaction is finished, and separating to obtain modified silver-loaded graphene oxide filter residues;
step S4, fully washing the modified silver-loaded graphene oxide filter residue by acetone, ethanol and deionized water solution in sequence, and then drying in a drying oven at 86-90 ℃ to obtain modified silver-loaded graphene oxide modified by maleic anhydride;
the modified composite antibacterial agent comprises the following components in parts by weight: 30 parts of graphene oxide-like, 8 parts of nano silver-metal oxide, wherein: the nano silver-metal oxide comprises the following components in percentage by mass: 48% of Ag-CuO, 30% of Ag-ZnO and 22% of Ag-TiO2Wherein the surface of the graphene oxide-like material mainly contains oxygen-containing groups of hydroxyl,
the nano silver-metal oxide composite antibacterial agent is prepared by the following steps:
step 1, dissolving graphene oxide-like in deionized water, and performing ultrasonic dispersion treatment to form a suspension solution;
step 2, adding nano silver-metal oxide into the suspension solution obtained in the step 1, continuing ultrasonic treatment, carrying out suction filtration and drying treatment to obtain a composite antibacterial agent;
step 3, completely dissolving maleic anhydride in a DMF solvent to obtain a maleic anhydride-DMF solution, then continuously adding xylene which is 3-4 times of the weight of the maleic anhydride into the maleic anhydride-DMF solution, and stirring to completely dissolve all the components, wherein the weight part ratio of the maleic anhydride to the graphene oxide is 1.5;
step 4, adding the composite antibacterial agent into the solution obtained in the step 3, carrying out suction filtration treatment after reaction at 40-50 ℃ under the stirring condition and reaction at 5-6, and separating to obtain modified composite antibacterial agent filter residue;
step 5, fully washing the filter residue of the modified composite antibacterial agent by acetone, ethanol and deionized water solution in sequence, and then drying in an oven at 86-90 ℃ to obtain the modified composite antibacterial agent modified by maleic anhydride;
the antibacterial plastic is prepared by the following steps:
step 1, carrying out surface coupling coating treatment on modified silver-loaded graphene oxide and a modified composite antibacterial agent for later use;
step 2, putting the compatilizer, the lubricant and the dispersing agent into a mixer to mix for 1-5 minutes, and then putting the modified silver-loaded graphene oxide, the modified composite antibacterial agent, the ABS, the HIPS and the powdered rubber into the mixer to mix for at least 3 minutes;
step 3, setting the temperature to be 180-235 ℃, injecting the blend into a mold through an injection molding machine, and cooling to 65-85 ℃ in the mold to form to obtain the antibacterial plastic;
the tensile strength of the antibacterial plastic is 44.5MPa, and the impact strength is 16.1KJ/m2(ii) a The antibacterial plastic has an antibacterial activity value of 5.8 on escherichia coli and an antibacterial activity value of 4.9 on staphylococcus aureus.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015165287A1 (en) * | 2014-04-28 | 2015-11-05 | 宁波墨西科技有限公司 | Graphene composite powder material and preparation method therefor |
| CN106928413A (en) * | 2017-03-26 | 2017-07-07 | 天津工业大学 | A kind of method of styrene maleic anhydride copolymer graft modification Graphene |
| CN107474427A (en) * | 2017-08-14 | 2017-12-15 | 江苏苏沃尚新材料科技有限公司 | A kind of graphene oxide antibiotic complex pvc material and preparation method thereof |
| CN108588883A (en) * | 2018-05-02 | 2018-09-28 | 广州市泽福医疗科技有限公司 | graphene fiber and preparation method and product |
| CN109517314A (en) * | 2018-10-23 | 2019-03-26 | 厦门富桂通科技有限公司 | A kind of nano-antibacterial door cabinet board material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105218815B (en) * | 2015-09-15 | 2017-05-10 | 沈阳航空航天大学 | Preparation method for maleic anhydride modified graphene oxide/bismaleimide nanometer composite material |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015165287A1 (en) * | 2014-04-28 | 2015-11-05 | 宁波墨西科技有限公司 | Graphene composite powder material and preparation method therefor |
| CN106928413A (en) * | 2017-03-26 | 2017-07-07 | 天津工业大学 | A kind of method of styrene maleic anhydride copolymer graft modification Graphene |
| CN107474427A (en) * | 2017-08-14 | 2017-12-15 | 江苏苏沃尚新材料科技有限公司 | A kind of graphene oxide antibiotic complex pvc material and preparation method thereof |
| CN108588883A (en) * | 2018-05-02 | 2018-09-28 | 广州市泽福医疗科技有限公司 | graphene fiber and preparation method and product |
| CN109517314A (en) * | 2018-10-23 | 2019-03-26 | 厦门富桂通科技有限公司 | A kind of nano-antibacterial door cabinet board material |
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Denomination of invention: A Preparation Method of High Antibacterial Activity and Yellowing Resistance Antibacterial Agent for Plastic Sheet and Storage Cabinet Effective date of registration: 20230926 Granted publication date: 20220218 Pledgee: Bank of China Limited Xiamen Haicang sub branch Pledgor: Dehong cabinet Intelligent Technology (Xiamen) Co.,Ltd. Registration number: Y2023980058904 |
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