CN108184898A - A kind of preparation method of inorganic complex antimicrobials - Google Patents
A kind of preparation method of inorganic complex antimicrobials Download PDFInfo
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- CN108184898A CN108184898A CN201810011750.7A CN201810011750A CN108184898A CN 108184898 A CN108184898 A CN 108184898A CN 201810011750 A CN201810011750 A CN 201810011750A CN 108184898 A CN108184898 A CN 108184898A
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/26—Phosphorus; Compounds thereof
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Abstract
The present invention relates to a kind of preparation methods of inorganic complex antimicrobials, include the following steps：1) zinc salt and water-soluble high-molecular compound are dissolved in organic solvent, are heated to flowing back, after under stirring condition, adding in deionized water thereto, persistently be stirred at reflux 2~5 hours；2) phosphoric acid zirconium powder is added in into the system after step 1) reaction, it is (0.01~100) to control the molar ratio of zirconium and zinc:1, continue 20~60min of stirring, rear rotary evaporation is evaporated all solvents and obtains the inorganic complex antimicrobials powder of zinc oxide and basic zirconium phosphate.The method of the present invention does not need to use in synthesis alkali as raw material (such as sodium hydroxide, potassium hydroxide, ammonium hydroxide), therefore basic zirconium phosphate load zinc oxide inorganic composite antimicrobial material can be prepared under conditions of heteroion is not introduced；This composite inorganic anti-biotic material can be effectively scattered in aqueous solution to prepare antimicrobial fluid and antimicrobial coating, all with good antibacterial effect.
Description
Technical field
Preparation method more particularly to a kind of preparation method of inorganic complex antimicrobials the present invention relates to a kind of antiseptic,
Belong to antiseptic technical field.
Background technology
Antiseptic is widely used in daily life and health care, and common antiseptic mainly includes machine
Anti-biotic material and inorganic antibacterial material, the former is since stability is poor thus the short-acting rate of antibacterial timeliness is low；Although the latter's antibacterial is imitated
Rate is higher, but has many limitations in practical applications, such as common silver ion or Nano silver grain anti-biotic material, potentially
Chemical toxicity makes it that can not use in many occasions.Silver-series antibacterial agent occupies leading position in inorganic antiseptic at present, in addition
The inorganic antiseptic with photocatalyst effect with titanium oxide and zinc oxide etc. for representative is also widely used.Inorganic particulate grain shape resists
The antibacterial effect of microbial inoculum and its dispersibility have great relationship, work as particle agglomeration, and specific surface area reduces, and antibacterial effect can subtract significantly
It is weak.Therefore the dispersibility for improving inorganic antibacterial particle is a kind of effective ways for improving anti-biotic material performance.
The dispersibility for improving antimicrobial particles can be by using the method for surfactant, but surfactant molecule
Loading can bring some negative effects, such as antibacterial effect to decline to antiseptic, complex process, cost raising etc..
Basic zirconium phosphate is a kind of with laminar structured inorganic material, and due to the characteristic of its layer structure, it has good
Ion adsorption capacity, therefore basic zirconium phosphate is particularly well suited as the carrier of antibacterial agent material, such as adsorbs silver ion with basic zirconium phosphate
Silver load basic zirconium phosphate anti-biotic material can be prepared, but does not have the report using basic zirconium phosphate load granular pattern inorganic antibacterial material also.
Due to the potential chemical toxicity of silver ion antimicrobial agent, it would be highly desirable to which we develop the inorganic composite antimicrobial material of New raxa, existing skill
There is following several, open substantive examination patent CN201610963746 in art using the method that basic zirconium phosphate prepares composite inorganic anti-biotic material
In refer to it is a kind of basic zirconium phosphate is first modified intercalation processing with amine molecule, then it is removed with zinc oxide, finally obtain
Adsorption aoxidizes the basic zirconium phosphate delamination material of zinc.But this method needs to carry out intercalation processing with amine molecule, and cannot be direct
Zinc oxide is carried on unmodified basic zirconium phosphate surface, the problem of basic zirconium phosphate of amine-modified mistake is due to its dissolubility and toxicity
Generally it cannot act as anti-biotic material.The system of Zinc oxide quantum dot antiseptic is disclosed involved in substantive examination patent CN201710218408
Standby, this invention is only by the use of single nanoscale zinc oxide as anti-biotic material.
Invention content
The present invention, using basic zirconium phosphate as deficiency existing for the composite antibacterial material of carrier, provides a kind of basic zirconium phosphate table for existing
The preparation method of the inorganic complex antimicrobials of face load zinc oxide.
The technical solution that the present invention solves above-mentioned technical problem is as follows：
A kind of preparation method of inorganic complex antimicrobials, includes the following steps：
1) zinc salt and water-soluble high-molecular compound are dissolved in organic solvent, are heated to flowing back, after stirring condition
Under, deionized water is added in thereto, be persistently stirred at reflux 2~5 hours, wherein control zinc salt and water-soluble high-molecular compound
Weight ratio is (0.1~100)：1, the weight ratio of deionized water and zinc salt is (1~1000)：1；
2) add in phosphoric acid zirconium powder into the system after step 1) reaction, control the molar ratio of zirconium and zinc for (0.01~
100)：1, continue 20~60mi of stirring n, rear rotary evaporation is evaporated all solvents and obtains the inorganic compounding of zinc oxide and basic zirconium phosphate
Anti-bacterial powders.
Further, the zinc salt is appointing in two water zinc acetates, zinc chloride, zinc sulfate, zinc nitrate, zinc bromide, zinc carbonate
Meaning is a kind of.
Further, the water-soluble high-molecular compound be polyvinylpyrrolidone, it is polyvinyl alcohol, polyethylene glycol, aqueous
Any one in polyurethane, aqueous polyacrylamide acid resin, gelatin.
Further, the organic solvent be isopropanol, it is propyl alcohol, methanol, ethyl alcohol, butanol, amylalcohol, ethylene glycol, butanediol, different
Any one in pentanediol.
The process mechanism of preparation method of the present invention is：
As shown in figure 4, water soluble polymer is by adsorbing zinc ion, after under the action of water into nuclear reaction, finally in phosphorus
Sour zirconium surface forms Zinc oxide nanoparticle.
The beneficial effects of the invention are as follows：
1) method of the invention does not need to use in synthesis alkali as raw material (such as sodium hydroxide, potassium hydroxide, ammonium hydroxide
Deng), therefore basic zirconium phosphate load zinc oxide inorganic composite antimicrobial material can be prepared under conditions of heteroion is not introduced；
2) this composite inorganic anti-biotic material can be effectively scattered in aqueous solution is applied with preparing antimicrobial fluid and antibacterial
Layer, all with good antibacterial effect.
Description of the drawings
Fig. 1 is the SEM image of raw material basic zirconium phosphate；
Fig. 2 is the TEM image of 1 gained Zinc oxide powder of comparative example；
Fig. 3 is the TEM image of 1 gained inorganic complex antimicrobials of embodiment；
In Fig. 3,1 is zinc oxide；2 be basic zirconium phosphate；
Fig. 4 is the process mechanism schematic diagram of preparation method of the present invention.
Specific embodiment
The principle of the present invention and feature are described below in conjunction with example, the given examples are served only to explain the present invention, and
It is non-to be used to limit the scope of the present invention.
The size of raw material basic zirconium phosphate used in the embodiment of the present invention is 200~300nm, with sheet knot
Structure, specific preparation method are as follows：In the hydrothermal reaction kettle (Teflon Godson) that volume is about 300ml, by 20.0g's
ZrOCl2.8H2O is mixed with the phosphoric acid of a concentration of 2.0mol/L of 200ml and is poured into wherein.Reaction kettle is positioned over 220 DEG C after closed
2h is reacted in baking oven, reaction kettle is taken out after room temperature is naturally cooled to, reaction product is washed with water three times, by being collected by centrifugation
Product, then by obtained sample at 80 DEG C it is dry for 24 hours, after be ground into fine powder, SEM image is as shown in Figure 1.
Embodiment 1：
Bis- water zinc acetates of 4.4g and 2g PVP are dissolved in 200ml isopropanols, are heated to flowing back, in the condition of stirring
Under, 10ml deionized waters are slowly added dropwise, after being persistently refluxed 3 hours, add in 1.6g phosphoric acid zirconium powders, after being stirred for 30min,
It is evaporated after all solvents using rotary evaporation and obtains zinc oxide basic zirconium phosphate inorganic complex antimicrobials white powder.Zinc oxide basic zirconium phosphate
The TEM image of inorganic complex antimicrobials is shown in Fig. 3.It can be seen that zinc oxide load and basic zirconium phosphate surface completely, forms inorganic compounding
Anti-biotic material.
Embodiment 2：
0.5g zinc sulfate and 5g PVP are dissolved in 200ml isoprenes, are heated to flowing back, under conditions of stirring,
500ml deionized waters are slowly added dropwise, after being persistently refluxed 2 hours, adds in 6.4g phosphoric acid zirconium powders, after being stirred for 20min, makes
Zinc oxide basic zirconium phosphate inorganic complex antimicrobials white powder is obtained after being evaporated all solvents with rotary evaporation.
Embodiment 3：
200g zinc bromides and 2g PVP are dissolved in 200ml ethylene glycol, are heated to flowing back, under conditions of stirring, is delayed
It is slow that 200ml deionized waters are added dropwise, after being persistently refluxed 5 hours, 2.6g phosphoric acid zirconium powders are added in, after being stirred for 60min, are used
Rotary evaporation obtains zinc oxide basic zirconium phosphate inorganic complex antimicrobials white powder after being evaporated all solvents.
Embodiment 4：
10g zinc carbonates and 1g PVP are dissolved in 200ml methanol, are heated to flowing back, under conditions of stirring, is slowly dripped
Add 2000ml deionized waters, after being persistently refluxed 3 hours, add in 1290g phosphoric acid zirconium powders, after being stirred for 30min, use rotation
Turn to obtain zinc oxide basic zirconium phosphate inorganic complex antimicrobials white powder after being evaporated all solvents.
Comparative example 1：
Bis- water zinc acetates of 4.4g and 2g polyvinylpyrrolidones (PVP) are dissolved in 200ml isopropanols, be heated at reflux to
After 70 DEG C, under conditions of stirring, 10ml deionized waters are slowly added dropwise, after being persistently refluxed 3 hours at 70 DEG C, use rotation
Turn to obtain zinc oxide white powder after being evaporated all solvents, TEM image is as shown in Figure 2.
In order to verify the antibacterial effect of inorganic complex antimicrobials obtained by the method for the present invention, we are by 1 gained nothing of embodiment
Machine complex antimicrobials, raw material basic zirconium phosphate, 1 gained Zinc oxide powder of comparative example are respectively with water according to weight ratio 1：50 be mixed to get it is molten
Liquid.
According to《Disinfection technology standard》(version in 2002) -2.1.11.3 product bactericidal properties, bacteriostasis property and stability are surveyed
Method for testing tests the bacteriostasis rate (Escherichia coli and staphylococcus aureus) of above-mentioned antiseptic respectively, and concrete outcome is as shown in table 1.
Note：According to standard：Bacteriostasis rate >=50~90%, product have bacteriostasis；Bacteriostasis rate >=90%, product have stronger suppression
Bacterium acts on.
1 fungistatic effect comparing result of table
| Inorganic complex antimicrobials | Basic zirconium phosphate | Zinc oxide | |
| Escherichia coli (%) | 99.1 | 0 | 72.2 |
| Staphylococcus aureus (%) | 92.7 | 0 | 51.2 |
Raw material basic zirconium phosphate is can be seen that from the data in table 1 and has no bacteriostasis antibiosis effect in itself, and zinc oxide is in this experiment item
Part and fungistatic effect under concentration are general, and present invention gained zinc oxide basic zirconium phosphate inorganic complex antimicrobials are with stronger antibacterial anti-
Bacterium acts on.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all the present invention spirit and
Within principle, any modification, equivalent replacement, improvement and so on should all be included in the protection scope of the present invention.
Claims (4)
1. a kind of preparation method of inorganic complex antimicrobials, which is characterized in that include the following steps：
1) zinc salt and water-soluble high-molecular compound are dissolved in organic solvent, are heated to flowing back, after under stirring condition, to
Deionized water is wherein added in, is persistently stirred at reflux 2~5 hours, wherein the weight of control zinc salt and water-soluble high-molecular compound
The ratio between be (0.1~100)：1, the weight ratio of deionized water and zinc salt is (1~1000)：1；
2) phosphoric acid zirconium powder is added in into the system after step 1) reaction, it is (0.01~100) to control the molar ratio of zirconium and zinc：1,
Continue 20~60mi of stirring n, rear rotary evaporation is evaporated all solvents and obtains the inorganic complex antimicrobials powder of zinc oxide and basic zirconium phosphate
End.
2. preparation method according to claim 1, which is characterized in that the zinc salt is two water zinc acetates, zinc chloride, sulfuric acid
Any one in zinc, zinc nitrate, zinc bromide, zinc carbonate.
3. preparation method according to claim 1, which is characterized in that the water-soluble high-molecular compound is polyethylene pyrrole
Any one in pyrrolidone, polyvinyl alcohol, polyethylene glycol, aqueous polyurethane, aqueous polyacrylamide acid resin, gelatin.
4. preparation method according to claim 1, which is characterized in that the organic solvent for isopropanol, propyl alcohol, methanol,
Any one in ethyl alcohol, butanol, amylalcohol, ethylene glycol, butanediol, isoprene.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112335681A (en) * | 2020-11-08 | 2021-02-09 | 上海聚治新材料科技有限公司 | Preparation method of layered unsaturated silver-zinc-copper loaded composite antibacterial and antiviral agent |
| CN112913856A (en) * | 2021-02-07 | 2021-06-08 | 上海润河纳米材料科技有限公司 | Anti-agglomeration slow-release inorganic antibacterial material and preparation method thereof |
| WO2021114539A1 (en) * | 2019-12-13 | 2021-06-17 | 佛山欧神诺陶瓷有限公司 | Antibacterial ceramic tile and preparation method therefor |
| CN112972367A (en) * | 2021-03-29 | 2021-06-18 | 烟台鲁量新材料科技有限公司 | Modified nano zinc oxide antibacterial gel and preparation method and application thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021114539A1 (en) * | 2019-12-13 | 2021-06-17 | 佛山欧神诺陶瓷有限公司 | Antibacterial ceramic tile and preparation method therefor |
| CN112335681A (en) * | 2020-11-08 | 2021-02-09 | 上海聚治新材料科技有限公司 | Preparation method of layered unsaturated silver-zinc-copper loaded composite antibacterial and antiviral agent |
| CN112335681B (en) * | 2020-11-08 | 2022-07-26 | 上海聚治新材料科技有限公司 | Preparation method of layered unsaturated load silver-zinc-copper composite antibacterial and antiviral agent |
| CN112913856A (en) * | 2021-02-07 | 2021-06-08 | 上海润河纳米材料科技有限公司 | Anti-agglomeration slow-release inorganic antibacterial material and preparation method thereof |
| CN112972367A (en) * | 2021-03-29 | 2021-06-18 | 烟台鲁量新材料科技有限公司 | Modified nano zinc oxide antibacterial gel and preparation method and application thereof |
| CN112972367B (en) * | 2021-03-29 | 2023-03-24 | 烟台鲁量新材料科技有限公司 | Modified nano zinc oxide antibacterial gel and preparation method and application thereof |
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