CN102132706A

CN102132706A - Four-component compound antibacterial powder

Info

Publication number: CN102132706A
Application number: CN2010102788001A
Authority: CN
Inventors: 王黔平; 吴卫华; 范金岭; 黄转红; 郭治; 崔海滨
Original assignee: Hebei United University
Current assignee: Hebei United University
Priority date: 2010-09-13
Filing date: 2010-09-13
Publication date: 2011-07-27
Anticipated expiration: 2030-09-13
Also published as: CN102132706B

Abstract

The invention relates to a method for preparing a four-component compound antibacterial powder on which silver, zinc and copper ions are absorbed by a titanium sol carrier, by ultrasonically heating. The method comprises the following steps: uniformly mixing butyl titanate in ethanol under a certain condition and then adding glacial acetic acid, thereby acquiring a solution A; adding distilled water into ethanol, and then stirring while adding in nitric acid for adjusting PH value till the PH value reaches 2-3, thereby acquiring a solution B; dipping the solution B into the solution A at a certain speed; reacting for 20-30 minutes under an ultrasonic condition and then acquiring a titanium solution; drop-wise adding AgNO3, Zn(NO3)2 and Cu(NO3)2 solutions into the titanium solution, wherein the ion addition is 5:100 (the mole ratio of metal ion to butyl titanate) and the mole ratio of silver ion to zinc ion to copper ion is 1:2:1; then performing ultrasonic dispersion for 10-20 minutes, thereby acquiring the compound titanium sol absorbing silver, zinc and copper ions; and lastly drying, grinding and burning the compound titanium sol, thereby acquiring the required antibacterial powder. A study shows that the antibacterial agent has excellent property and the problems that the silver system antibacterial agent is high in cost, the color of antibacterial material is easily changed and the function is single are solved.

Description

A kind of four component composite antibiosis powders

Technical field:

The present invention relates to the technology of preparing of powder, relate in particular to a kind of ultrasonic method that adds four component composite antibiosis powders of hot preparation titanium sol vehicle absorption silver, zinc, copper ion that adopts.

Background technology:

Along with the raising of people's living standard, the antibiotic property of commodity, medical supplies, environmental supplies, packaging for foodstuff, water treatment facilities etc. there has been higher requirement, the material with sterilization and antimicrobial effect more and more is subjected to people's attention and attention.

In recent years, inorganic antiseptic is with its safety, persistence, antibiotic property, broad spectrum activity, warm tolerance with should not produce characteristics such as drug resistance and obtain extensive studies, development and application.According to the difference of antibiotic mechanism, the research of inorganic antiseptic at present mainly is divided into TiO ₂System and silver are two big classes.TiO ₂The photocatalysis antibacterial agent utilizes the ultraviolet light in sunshine, the fluorescent lamp to make excitaton source and have antibacterial action, and have purify air, dispose of sewage, from photocatalytic effects such as cleanings, it is compound that yet it exists light induced electron-hole commute, dependence to light is stronger, generally only can play a role under UV-irradiation, this just makes its range of application be subjected to certain limitation.Simultaneously, be in the antibiotic ion at silver, except that the advantage that has broad-spectrum antibacterial property, germicidal efficiency height, is difficult for developing immunity to drugs, also there is Ag ⁺Antibacterial agent easily is converted into Ag ₂O makes problems such as product variable color, cost height.

At present, seen and utilize infusion process on metallic substrates, to prepare silver-colored doped Ti O ₂Coating, employing photoreduction legal system are equipped with the TiO that silver mixes ₂Laminated film, the synergy of two kinds of antibacterial agents of performance can effectively be killed the relevant reports of Escherichia coli and bacillus subtilis etc. under fluorescent lamp irradiation.The present invention adopts under the condition of ultrasonic heating, and four component composite antibiosis powders of preparation titanium sol vehicle absorption silver, zinc, copper ion are intended to Ag ⁺, Zn ²⁺, Cu ²⁺Sterilization, bacteriostasis and TiO ₂Collaborative being combined with each other of two kinds of antibiotic self-cleanings effect, both can improve TiO by doped metal ion ₂Germicidal efficiency, can solve the cost height of single silver-series antibacterial agent and the problem of variable color again.

Summary of the invention:

The present invention under the condition of ultrasonic heating, is a carrier with titanium colloidal sol first, absorption silver, zinc, copper ion, and preparation possesses four component composite antibiosis powders antibiotic, two kinds of effects of automatically cleaning.Characteristics of the present invention are:

1. solved the high problem of cost of silver-series antibacterial agent.

2. by adopting ultrasonic heating method, optimized synthesis condition, made the antibacterial agent particle diameter little and even, anti-microbial property improves.

3. with Ag ⁺, Zn ²⁺, Cu ²⁺Sterilization, bacteriostasis and TiO ₂Collaborative being combined with each other of two kinds of antibiotic self-cleanings effect, solved the monistic problem of present anti-biotic material effect.

Its preparation method is as follows:

1. the preparation of titanium colloidal sol;

With 8mL butyl titanate (Ti (OBu) ₄) under 50 ℃ of stirrings, be added drop-wise in the 20mL ethanol and mix, add the 2mL glacial acetic acid again and obtain solution A.Distilled water with 60mL ethanol and 2mL under agitation adds nitre acid for adjusting pH value to 2～3 then, obtains solution B.The speed of solution B with 50～60 of per minutes is added drop-wise in the solution A, stirs and adjusting pH value to 2～3, after reaction temperature is 40～60 ℃ of reaction time 20～30min under the ultrasound condition, can obtain flaxen transparent titanium colloidal sol.

2. ion adds in titanium colloidal sol;

In colloidal sol, drip the AgNO of 0.3mol/L ₃, Zn (NO ₃) ₂And Cu (NO ₃) ₂Solution, ion addition are 5: 100 (mol ratio of metal ion and butyl titanate), and the mol ratio of silver, zinc, copper ion is 1: 2: 1, and ultrasonic then dispersion 10～20min can make the composite titanium colloidal sol that adsorbs the silver zinc copper ion.

3. dry, calcining, washing, dry antibacterial test.

Place drying box dry the composite titanium colloidal sol for preparing, 100 ℃ of baking temperatures obtain loose xerogel, grind to be placed in the crucible and calcine, and 450 ℃ of insulation 30～60min promptly get required antibacterial agent.

The four component composite antibiosis powder SEM collection of illustrative plates that Fig. 1 makes for the different heating mode.As seen from Figure 1, the antibiotic composite granule that the magnetic agitation heating makes obviously is cotton-shaped distribution, particle size is inhomogeneous, and there is particle agglomeration, and the antibiotic composite granule that the mode that adopts the ultrasonic heating makes, particle is flakes and distributes, its particle is less, and it is more even to distribute, and the degree of particle agglomeration obviously reduces, and this is because ultrasonic has heating function on the one hand, also has peptizaiton on the other hand, its peptizaiton makes intergranular active force reduce, and the reunion degree reduces, and grain graininess also correspondingly reduces simultaneously.

Fig. 2 is titanium colloidal sol adsorbs silver zinc copper ion gained under different adsorption conditionses four component composite granule inhibition zones test.As shown in Figure 2, its antibiotic property is best with the ultrasonic heating, and heating using microwave is taken second place, and agitating heating is the poorest.The analysis reason is: though the three has heating function, reach the effect that promotes titanium colloidal sol adion, it adds thermal effect and different to dispersibility.Just add thermal effect, heating using microwave is best, because heating using microwave is from inside to outside to heat, the instantaneous temperature of its generation is higher, can make ion be adsorbed on the colloid apace, and effect is relatively good, also can produce bigger agglomeration simultaneously but temperature is high, thereby reduces the antibiotic property of powder; With regard to dispersibility, ultrasonic is best.From the powder that makes, the powder dispersity that the ultrasonic heating makes is fabulous, and this has just improved the surface-active of powder.So in general, the antibiotic property of the powder that ultrasonic heating makes is best, and agitating heating add thermal effect and dispersiveness all bad, so antibiotic property is the poorest.

Description of drawings:

The four component composite antibiosis powder SEM collection of illustrative plates that Fig. 1 different heating mode makes.

The four component composite granule inhibition zones test that makes under the different adsorption conditionses of Fig. 2

Embodiment:

Embodiment 1

Embodiment 2

In colloidal sol, drip the AgNO of 0.3mol/L ₃, Zn (NO ₃) ₂And Cu (NO ₃) ₂Solution, ion addition are 5: 100 (mol ratio of metal ion and butyl titanate), and the mol ratio of silver, zinc, copper ion is 1: 2: 1, and ultrasonic then dispersion 10～20min can make the composite titanium colloidal sol that adsorbs the silver zinc copper ion.To prepare composite titanium colloidal sol then and place drying box dry, 100 ℃ of baking temperatures obtain loose xerogel, grind to be placed in the crucible and calcine, and 450 ℃ of insulation 30～60min promptly get required antimicrobial powder.

Claims

1. one kind is adopted the ultrasonic method that adds four component composite antibiosis powders of hot preparation titanium sol vehicle absorption silver, zinc, copper ion; It is characterized in that by adopting ultrasonic heating method, with Ag ⁺, Zn ²⁺, Cu ²⁺Sterilization, bacteriostasis and TiO ₂Collaborative being combined with each other of two kinds of antibiotic self-cleanings effect, solved the high problem of cost of present anti-biotic material effect unicity and silver-series antibacterial agent, optimized synthesis condition, make the antibacterial agent particle diameter little and even, the anti-microbial property raising;

Concrete preparation method is:

1. with 8mL butyl titanate (Ti (OBu) ₄) under 50 ℃ of stirrings, be added drop-wise in the 20mL ethanol and mix, add the 2mL glacial acetic acid again and obtain solution A; Distilled water with 60mL ethanol and 2mL under agitation adds nitre acid for adjusting pH value to 2～3 then, obtains solution B; The speed of solution B with 50～60 of per minutes is added drop-wise in the solution A, stirs and adjusting pH value to 2～3, after reaction temperature is 40～60 ℃ of reaction time 20～30min under the ultrasound condition, can obtain flaxen transparent titanium colloidal sol;

2. in colloidal sol, drip the AgNO of 0.3mol/L ₃, Zn (NO ₃) ₂And Cu (NO ₃) ₂Solution, ion addition are 5: 100 (mol ratio of metal ion and butyl titanate), and the mol ratio of silver, zinc, copper ion is 1: 2: 1, and ultrasonic then dispersion 10～20min can make the composite titanium colloidal sol that adsorbs the silver zinc copper ion;

3. the composite titanium colloidal sol for preparing is placed drying box dry, 100 ℃ of baking temperatures obtain loose xerogel, grind to be placed in the crucible and calcine, and 450 ℃ of insulation 30～60min promptly get required antimicrobial powder.