CN104472537A - Eggshell-type antibacterial microspheres and preparation method thereof - Google Patents
Eggshell-type antibacterial microspheres and preparation method thereof Download PDFInfo
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- CN104472537A CN104472537A CN201410631003.5A CN201410631003A CN104472537A CN 104472537 A CN104472537 A CN 104472537A CN 201410631003 A CN201410631003 A CN 201410631003A CN 104472537 A CN104472537 A CN 104472537A
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- microballoon
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Abstract
The invention discloses eggshell-type antibacterial microspheres and a preparation method thereof. According to the preparation method, melamine resin (MF) microspheres are taken as cores; the surface of the MF microspheres is coated with antibacterial metal ions via complexation so as to form shell layers by using active groups on the surface of the MF microspheres such as hydroxyl groups and amino groups, and obtain the eggshell-type antibacterial microspheres. Particle size of the eggshell-type antibacterial microspheres ranges from 1 to 3mum; particle size is uniform; stability is high; antibacterial performance is excellent; and the eggshell-type antibacterial microspheres can be used for antibacterial fabric, household electrical appliance, plastic film products, ceramics, and building coating.
Description
Technical field
The present invention relates to antibacterial microballoon of a kind of eggshell type and preparation method thereof, belong to anti-biotic material field.
Technical background
Anti-biotic material can be continual and steady kill malignant bacteria, fungi and virus, suppress the various diseases that it causes, as etiologies such as tuberculosis, pneumonia, bird flus, be the focus that modern society pays close attention to, be widely used in fields such as household electrical appliance, plastic membrane product, ceramic, building coatings; Antibacterial agent is the core of these anti-biotic materials, and it is a kind of material that can suppress microbial growth or kill germ, comprises organic antibacterial agent, inorganic antiseptic, polymer antibacterial agent and complex antimicrobials four class.Wherein organic antibacterial agent mainly contains the refinement product of the natural extract such as shitosan, chitin and juniper, argy wormwood, aloe etc., these organic antibacterial agents have the advantages such as sterilization speed is fast, antibacterial efficacy good, colour stable, but its heat resistance is poor, easily separate out in a solvent, drug resistance can be produced after using a period of time, and catabolite is often with toxic; Inorganic antiseptic mainly contains containing metal ion (Cu
2+, Ag
+, Zn
2+deng) zeolite, active carbon, silica gel and phosphate and ZnO, MgO and so on oxidation photocatalyst two class, these inorganic metal antibacterial agent good heat resistances, has a broad antifungal spectrum, effective antibacterial phase is long, toxicity is low, but its cost is high, antimycotic and mould effect is poor.Polymer antibacterial agent is by the monomer direct polymerization of the low molecule antibacterial antiplaque agent active groups such as quaternary amines, pyridine, guanidine class, halogenated amine or the organic antibacterial agent that obtained by inorganic metal ion, the group modified common modification of organic anti-bacterial, these polymer antibacterial agent stable performances, bactericidal effect be good, non-volatile, be easy to processing and storage, safety non-toxic and can not infiltrate human or animal's epidermis, but biocompatibility is bad, not easily degrade, production process is complicated, be difficult to selection synthesis material, causes daily life to use less.Complex antimicrobials refers to the general designation of the class high-performance antibiosis agent that the various combination that first three plants antibacterial agent obtains, but its production cost is high, preparation complicated.
The invention provides a kind of antibacterial agent and preparation method thereof, its thinking is: with brand-new for the melamine resin microballoon of undried process for mother bulb matrix, utilize the surface active groups such as its amino, hydroxyl, the multiple metal ion with anti-microbial property of complexing, then adjust cloudy complex ion kind, prepare the antibacterial microballoon of eggshell type that antibacterial components is shell, compared to conventional antimicrobial agent, this antibacterial agent had the following advantages: (1), at antibacterial microballoon outer surface complexing metal, makes antibacterial metal ion availability high; (2) there is the feature such as high molecular light weight, stable, convenient preparation; (3) antibacterial metal ion and macromolecule matrix have stronger chemical complexing effect, add the kind that can adjust cloudy complex ion easily, significantly improve the stability of antibacterial agent, ensure that antibacterial ion not easily decomposes in subsequent applications process; (4) macromolecule matrix can the multiple metal ion with anti-microbial property of complexing, and different combinations uses under can facilitating multiple condition and do not reduce its antibacterial effect, and preparation process is simply efficient, and cost is low, has good actual application prospect.
Summary of the invention
The object of the invention is to provide antibacterial microballoon of a kind of eggshell type single dispersing and preparation method thereof, concrete technical scheme is:
The melamine resin microballoon of brand-new for undried process is dispersed in water, add the antibacterial metal ions solution of metering, the pH value of adjustment mixed liquor is 2.5-4.5, complex reaction 0.1-2h under 40-80 DEG C of condition, adds concentration at more than 0.1M containing specific cloudy complex ion (non-NO after separation
3 -) solution, under 40-80 DEG C of condition, react 0.1-2h, microballoon be separated after through washing, be drying to obtain the antibacterial microballoon of eggshell type.
In above-mentioned steps, to select with brand-new for the melamine resin microballoon of undried process as matrix mother bulb, mainly now the activity group content of microballoon is relatively high, there is the ability belonging to ion compared with high chromium allioy, as through super-dry process, then these active groups can react reduction reactivity each other, and microsphere volume can be shunk and be become fine and close simultaneously, and subsequent metal ion complexation reaction difficulty increases.
In above-mentioned steps, antibacterial ion solution is Cu
2+, Ag
+, Zn
2+in one or several mixture, concentration is 0.1-0.6M, and now the amount of microballoon is 0.5-5%; The relative scale of metal ion need not be particularly limited to, and can require adjustment according to anti-microbial property, cost, stability etc.; Although select this three metal ion species to be because Cu
2+and Zn
2+anti-microbial property is more weak, but there is higher chemical stability and Heat stability is good, not easy to change, low price, safety are high; And Ag
+there is antimicrobial spectrum and relative high safety widely, but easy to change, cost is high, the combination of these metal ions then can be played respective feature, obtain anti-microbial property is stablized, not easy to change, economy is good antibacterial agent.
Mixed liquor pH value is regulated to be 2.5-4.5 in above-mentioned steps, complex reaction 0.1-2h under 40-80 DEG C of condition; This is because the complexing of metal ion and the pH value of solution closely related, too lowly will cause MF microspheres swell until lose spherical structure, too high, likely cause complexing of metal ion amount very few, affect anti-microbial property.The temperature and time of complex reaction is relevant with the relative amount of pH value and metal ion, and pH value lower temperature is lower, the time is shorter, otherwise temperature is higher, the time is longer, Ag
+the more complexation temperature of the content lower time is shorter, otherwise temperature is higher, the time is longer.Experiment finds, when pH value is within the scope of 2.5-4.5, under 40-80 DEG C of condition, complex reaction 0.1-2h effect is better.
Add in above-mentioned steps containing specific cloudy complex ion (non-NO
3 -) solution, under 40-80 DEG C of condition, react 0.1-2h; Adding cloudy complex ion is stability and dissolution rate in order to regulate antibacterial metal ions, improves the heat endurance of antibacterial agent and antibacterial timeliness.Experiment finds, cloudy complex ion is Cl
-, SO
4 2--, SCN
-, AC
-in one or several mixture all can, ratio need not be particularly limited to, concentration more than 0.1M both can, now, reaction condition is that to react 0.1-2h effect under 40-80 DEG C of condition better.
The antibacterial microballoon of eggshell type prepared by the present invention can find out microsphere surface relative smooth by SEM (SEM), some is protruding slightly, and the MF microspherulite diameter of complexing metal ion is homogeneous, good dispersion.Also illustrate that metal ion is on the particle diameter of MF microballoon and the impact of dispersion nothing.The XRD figure spectral representation complexing of microballoon Ag
+, Cu
2+, Zn
2+mF microballoon there is not new diffraction maximum, Ag is described
+, Cu
2+, Zn
2+be highly dispersed at MF microsphere surface with amorphous state.Thermogravimetric (TG) and differential thermal analysis (DTA) interpretation of result show that the antibacterial microballoon of eggshell type has excellent heat endurance.Escherichia coli are placed on and staphylococcus aureus strains is coated with on uniform medium respectively by making bacteria inhibition tablet containing the antibacterial agent of microballoon, after 24h, the antibacterial agent bacterial strain killed around print forms a transparent circle, and testing result is that microballoon suppresses circle radius 0.5mm to Escherichia coli; Staphylococcus aureus suppresses radius 0.7mm, has remarkable antibiotic property.
To sum up tell, technology tool provided by the invention be simple efficient, cost is low, metal ion combined and instant, availability advantages of higher, gained antibacterial agent has that light weight, anti-microbial property are excellent, the feature such as have good stability, and has good actual application prospect.
Below in conjunction with drawings and Examples, the present invention is further described.
Figure mono-eggshell type antibacterial microballoon SEM picture
Figure bis-eggshell type antibacterial microballoon XRD result
The antibacterial microballoon TG of figure tri-eggshell type and DTA result
Figure tetra-eggshell type antibacterial microballoon anti-microbial property test result
Embodiment
In order to better the present invention is described, attached embodiment is as follows.It is emphasized that embodiment and do not mean that scope of the present invention is limited in the condition that embodiment describes, the object of embodiment sets forth content of the present invention and feasibility thereof further.
Embodiment 1:
Be dispersed in water by the melamine resin microballoon of brand-new for undried process, add 0.1M liquor argenti nitratis ophthalmicus, the pH value of adjustment mixed liquor is 2.5, complex reaction 0.1h under 40 DEG C of conditions, adds concentration at 0.1M containing Cl after separation
-cloudy complex ion solution, reacts 1h under 40 DEG C of conditions, through washing, being drying to obtain the antibacterial microballoon of complex silver eggshell type after microballoon is separated.
Embodiment 2:
Be dispersed in water by the melamine resin microballoon of brand-new for undried process, add 0.2M copper nitrate solution, the pH value of adjustment mixed liquor is 3, complex reaction 0.5h under 40 DEG C of conditions.Concentration is added at 0.1M containing SO after separation
4 2-cloudy complex ion solution, reacts 0.5h under 40 DEG C of conditions, through washing, being drying to obtain the antibacterial microballoon of complex copper eggshell type after microballoon is separated.
Embodiment 3:
Be dispersed in water by the melamine resin microballoon of brand-new for undried process, add 0.3M zinc nitrate solution, the pH value of adjustment mixed liquor is 3.5, stirring reaction 1h under 50 DEG C of conditions.Concentration is added at 0.2M containing SO after separation
4 2-cloudy complex ion solution, reacts 1h under 50 DEG C of conditions, through washing, being drying to obtain the antibacterial microballoon of complexing zinc eggshell type after microballoon is separated.
Embodiment 5:
Be dispersed in water by the melamine resin microballoon of brand-new for undried process, add the mixed solution of 0.4M zinc nitrate and copper nitrate, the pH value of adjustment mixed liquor is 4.0, stirring reaction 1.5h under 60 DEG C of conditions.Concentration is added at 0.3M containing SO after separation
4 2-and Cl
-cloudy complex ion solution, reacts 1.5h under 60 DEG C of conditions, through washing, being drying to obtain complexing zinc, the antibacterial microballoon of copper eggshell type after microballoon is separated.
Embodiment 6:
Be dispersed in water by the melamine resin microballoon of brand-new for undried process, add the mixed solution of 0.5M zinc nitrate and silver nitrate, the pH value of adjustment mixed liquor is 4.0, stirring reaction 2h under 70 DEG C of conditions.Concentration is added at 0.4M containing SCN after separation
-and Cl
-cloudy complex ion solution, reacts 2h under 80 DEG C of conditions, through washing, being drying to obtain complexing zinc, the antibacterial microballoon of copper eggshell type after microballoon is separated.
Embodiment 7:
Be dispersed in water by the melamine resin microballoon of brand-new for undried process, add the mixed solution of 0.6M silver nitrate and copper nitrate, the pH value of adjustment mixed liquor is 4.5, stirring reaction 2h under 80 DEG C of conditions.Concentration is added at 0.4M containing AC after separation
-and Cl
-cloudy complex ion solution, reacts 2h under 80 DEG C of conditions, through washing, being drying to obtain complex silver, the antibacterial microballoon of zinc eggshell type after microballoon is separated.
Embodiment 8:
Be dispersed in water by the melamine resin microballoon of brand-new for undried process, add 0.6M zinc nitrate, the mixed solution of silver nitrate and copper nitrate, the pH value of adjustment mixed liquor is 4.5, stirring reaction 2h under 80 DEG C of conditions.Concentration is added at 0.4M containing AC after separation
-and SCN
-cloudy complex ion solution, reacts 2h under 80 DEG C of conditions, through washing, being drying to obtain complex silver, the antibacterial microballoon of zinc eggshell type after microballoon is separated.
Claims (6)
1. antibacterial microballoon of eggshell type and preparation method thereof, is characterized in that this antibacterial microballoon, is prepared by following steps for mother bulb with melamine resin (MF) microballoon:
The melamine resin microballoon of brand-new for undried process is dispersed in water, add the antibacterial metal ions solution of metering, the pH value of adjustment mixed liquor is 2.5-4.5, and complex reaction 0.1-2h under 40-80 DEG C of condition, adds after separation containing specific cloudy complex ion (non-NO
3 -) solution, under 40-80 DEG C of condition, react 0.1-2h, microballoon be separated after through washing, be drying to obtain the antibacterial microballoon of eggshell type.
2. antibacterial microballoon of one according to claim 1 and preparation method thereof, it is characterized in that microballoon is the melamine resin microballoon of brand-new for undried process, microballoon consumption is 0.5-5%.
3. antibacterial metal ions solution according to claim 1 is Cu
2+, Ag
+, Zn
2+in one or several mixed solution.
4. antibacterial metal ions solution concentration according to claim 1 is between 0.1-0.6M.
5. according to claim 1 is Cl containing cloudy complex ion in the solution of specific cloudy complex ion
-, SO
4 2+, SCN
-, AC
-in one or several mixture, its concentration is at more than 0.1M.
6. antibacterial eggshell type microballoon of the one according to claim 1 and 2 ~ 6 and preparation method thereof, is characterized in that described antibacterial microballoon can be used for the fields such as antibacterial fabric, household electrical appliance, plastic membrane product, ceramic, building coating.
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US6291632B1 (en) * | 1998-12-10 | 2001-09-18 | Grantec Inc. | Microspheres of melamine |
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