RU2451578C1 - Method of producing biocide inorganic zinc oxide-based composite nanoparticles - Google Patents

Abstract

FIELD: process engineering.

SUBSTANCE: invention may be used for producing antivirus and fungicidal woven and nonwoven disposable and reusable materials to be used in medical institutions. Silver nitrate is reduced by nitrogen-containing compound selected from the group including triethylamine, tributylamine, trioctylamine, monoethanolamine and diethanolamine in th presence of preformed nanoparticlesof zinc oxide and carboxylic acid selected from the group including myristic acid, stearic acid, palmitic acid and oleic acid. Obtained mix is blown by nitrogen, processed by ultrasound, heated and cured at 80-110°C for 1 h. Precipitate is filtered out to produce nanoparticles with zinc oxide-to-silver oxide ratio varying from 90/10 to 10/90.

EFFECT: minimum amount of reaction mix components low reaction temperature, simplified process.

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Description

The invention relates to the field of creating nanomaterials that can be used to create antiviral and fungicidal tissue and non-woven textile materials of single and multiple use for use in medical institutions.

The main requirements for antibacterial and fungicidal textile materials used in medical institutions are the combination of high biocidal and fungicidal activity with no toxicity to the human body, the ability not to lose their properties during sterilization and to preserve them for a long period of time.

A known method for the synthesis of ZnO / Ag nanoparticles [1], according to which ZnO / Ag nanoparticles were obtained from zinc and silver foil in an electrochemical bath in the presence of acetonitrile, tetrahydrofuran and tetraoctylammonium bromide, as a stabilizing agent. The disadvantages of this method include the need to use an expensive platinum cathode, as well as salts of the Quaternary ammonium base as a stabilizer.

The known method [2], which consists in photochemical synthesis. The sol of zinc oxide nanoparticles was obtained by hydrolysis of zinc acetate in the presence of sodium hydroxide at temperatures of 0-5 ° C. The resulting sol was mixed with silver nitrate, methylene blue and irradiated with visible light with a wavelength of 310-390 nm. The disadvantage of this synthetic scheme is the need to use a dye and a mercury lamp for irradiation.

The known method [3], which consists in a hydrothermal method of carrying out the reaction. Known amounts of sodium hydroxide, zinc nitrate and cetylammonium bromide were placed in an autoclave, a vigorous amount of an aqueous solution of silver nitrate was added with vigorous stirring, the autoclave was closed and kept at a temperature of 180 ° C for 24 hours. The silver content in the obtained nanoparticles ranged from 0 to 22%. The main disadvantage of this method is the use of sophisticated equipment operating at high pressure and temperature.

A known method of producing silver powder, including the precipitation of silver chloride at a temperature of 20-50 ° C at pH 1-5 from a solution of silver nitrate with a water-soluble chloride, processing a suspension of freshly precipitated silver chloride with an alkali metal hydroxide solution with a concentration in the reaction medium of 12-200 g / l, reduction of silver from solution with formalin at a temperature of 40-90 ° C and drying of the precipitate at a temperature of 70-120 ° C, which is then sieved through a sieve with a mesh size of 250 μm [4]. The disadvantages of the method include the use of a large amount of toxic formaldehyde, the need for its regeneration and a large number of effluents.

A known method [5] for producing nanostructured metal and bimetallic particles by reducing metal ions in a reverse micelle system, comprising preparing a reverse micellar dispersion of a reducing agent based on a solution of a surfactant in a non-polar solvent, using a substance from the group of flavonoids as a reducing agent, as a surface the active substance is sodium bis-2-ethylhexyl sulfosuccinate (RT aerosol), and the substance is used as a non-polar solvent and h groups of saturated hydrocarbons. The method allows to increase the lifetime and the rate of formation of the obtained nanostructured metal and bimetallic particles and to eliminate the need to create anaerobic conditions during their synthesis. The disadvantages of this method include the need to use relatively inaccessible surfactants and a reducing agent, as well as the difficulty in creating a micellar solution and the stability of the recovery process.

A known method for the synthesis of ZnO / Ag nanoparticles [6], which is a sol-gel process. ZnO sol is obtained from zinc acetate dissolved in a mixture of isopropyl alcohol and monoethanolamine. A silver sol is obtained from silver nitrate dissolved in a mixture consisting of ethyl alcohol and acetonitrile. Then the sols were mixed, left to ripen at room temperature for 3 days, the obtained nanoparticles contained 20, 12 and 5% (mol.) Silver. The specified method is adopted as a prototype, despite the fact that it is not without certain drawbacks - the need to use a significant amount of solvents and the duration of the process.

The technical result of the claimed invention is to obtain composite nanoparticles based on zinc oxide and silver.

The technical result is achieved due to the fact that the synthesis of composite nanoparticles is carried out in the presence of preformed zinc oxide nanoparticles in a nitrogen-containing compound, which simultaneously acts as a reducing agent and a reaction medium, from a precursor, which is a complex of silver nitrate with a nitrogen-containing compound selected from the series triethylamine, tributylamine , trioctylamine, monoethanolamine, diethanolamine, in the presence of a carboxylic acid selected from a number of myristic, stearic, palmitic acids new, oleic, in the temperature range of 80-110 ° C for 1 hour and the mass ratio of zinc oxide / silver in the final product from 90/10 to 10/90. The advantages of the invention are the minimum number of components of the reaction mixture, low reaction temperature, short duration and the absence of the need for complex equipment.

The invention can be illustrated by the following examples.

Example 1

30 ml of triethylamine, 0.9 g of zinc oxide, 0.15 g of silver nitrate, 0.21 g of myristic acid were placed in a glass reactor equipped with a heat-exchange jacket, inert gas fittings, a mechanical stirrer and a reflux condenser. The resulting mixture was sonicated, then heated and kept at a temperature of 80 ° C for 1 hour. Then, 5 ml of acetone was added to the reaction mixture, cooled to room temperature. The precipitated nanoparticle precipitate was filtered, washed with acetone and dried under vacuum. The composition of nanoparticles ZnO / Ag = 9/1 (wt.).

Example 2

It differs from Example 1 in that tributylamine was used as the active reaction medium, 0.7 g of zinc oxide, 0.3 g of silver nitrate, 0.78 g of stearic acid were taken and the reaction was carried out at a temperature of 110 ° C. The composition of the nanoparticles ZnO / Ag = 7/3 (wt.).

Example 3

It differs from Example 1 in that monoethanolamine was used as the active reaction medium, 0.5 g of zinc oxide, 0.75 g of silver nitrate, 1.3 g of oleic acid were taken and the reaction was carried out at a temperature of 110 ° C. The composition of the nanoparticles ZnO / Ag = 5/5 (wt.).

Example 4

It differs from Example 1 in that diethanolamine was used as the active reaction medium, 0.5 g of zinc oxide, 0.75 g of silver nitrate, 1.3 g of oleic acid were taken and the reaction was carried out at a temperature of 110 ° C. The composition of the ZnO / Ag nanoparticles is 5/5 (wt.).

Example 5

It differs from Example 1 in that triethylamine was used as the active reaction medium, 0.7 g of zinc oxide, 1.05 g of silver nitrate, 1.48 g of palmitic acid were taken and the reaction was carried out at a temperature of 90 ° C. The composition of the nanoparticles ZnO / Ag = 7/3 (wt.).

Example 6

It differs from Example 1 in that tributylamine was used as the active reaction medium, 0.1 g of zinc oxide, 1.35 g of silver nitrate, 1.89 g of myristic acid were taken and the reaction was carried out at a temperature of 85 ° C. The composition of the ZnO / Ag nanoparticles is 1/9 (wt.).

Sources of information taken into account

1. Shashikant Patole W M. Islam W R. C. Aiyer W Shailaja Mahamuni. Optical studies of ZnO / Ag nanojunctions // J Mater Sci (2006) V.41, pp.5602-5607.

2. V.V. Schvalagin, A.L. Stroyuk * and S.Ya. Kuchmii Photochemical synthesis of ZnO / Ag nanocomposites // Journal of Nanoparticle Research (2007) V.9, pp. 427-440.

3. Xiao-Yun Ye Zh Yu-Ming Zhou Zh Yan-Qing Sun Jing Chen Zh Zhi-Qiang Wang. Preparation and characterization of Ag / ZnO composites via a simple hydrothermal route // J Nanopart Res (2009) V.11, pp. 1159-1166.

4. Application for invention RU 2003113772 A dated 05/12/2003, IPC ⁷ B22F 1/00, 9/24, publ. 01/10/2005.

5. Patent RU No. 2147487 C1 of 07/01/1999, IPC ⁷ B22F 9/24, publ. 04/20/2000.

6. Mohammad Hossein Habibi, Reza Sheibani Preparation and characterization of nanocomposite ZnO-Ag thin film containing nano-sized Ag particles: influence of preheating, annealing temperature and silver content on characteristics // J Sol-Gel Sci Technol (2010) V.54 , pp. 195-202. (prototype).

Claims (1)

A method for producing biocidal inorganic composite nanoparticles based on zinc oxide and silver, which method consists in the fact that silver nitrate is reduced with a nitrogen-containing compound selected from the group consisting of triethylamine, tributylamine, trioctylamine, monoethanolamine and diethanolamine, in the presence of preformed zinc oxide and carboxylic acid nanoparticles, selected from the group consisting of myristic acid, stearic acid, palmitic acid and oleic acid, the resulting mixture is purged with nitrogen, processing melt by ultrasound, heat, incubated at a temperature of 80-110 ° C for 1 h and the precipitated precipitate is filtered to obtain nanoparticles in a mass ratio of zinc oxide / silver from 90/10 to 10/90.