CN104308180A - Preparation method of organic-system high-concentration nano silver sol - Google Patents
Preparation method of organic-system high-concentration nano silver sol Download PDFInfo
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- CN104308180A CN104308180A CN201410549598.XA CN201410549598A CN104308180A CN 104308180 A CN104308180 A CN 104308180A CN 201410549598 A CN201410549598 A CN 201410549598A CN 104308180 A CN104308180 A CN 104308180A
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Abstract
The invention relates to a preparation method of an organic-system high-concentration nano silver sol. The preparation method comprises the following steps of dissolving a protective agent PVP (Poly Vinyl Pyrrolidone) and a reducing agent into an organic solvent at a room temperature so as to obtain a solution A, wherein the mass ratio of the PVP, the reducing agent and the organic solvent in the solution A is 1:(0.025-2.0):(2.6-7.5); dissolving a silver source into de-ionized water or an organic solvent so as to obtain a solution B with the silver salt concentration of 12wt%-46wt%; under the condition of stirring, dropwise adding the solution B into the solution A so as to obtain a mixed solution, wherein the mass ratio of the solution A to the solution B is 1:(0.5-2.6); and reacting at a temperature ranging from the room temperature to 80 DEG C for 2-9 hours, thereby obtaining the high-concentration nano silver sol. The silver content of the nano silver sol can be up to 10wt%, the nano silver sol can be conveniently and directly applied without further concentration and purification, is not related to aftertreatment processes such as centrifugation, ultrafiltration, drying and redispersion, and is less in energy consumption and easy for large-scale application and downstream product application.
Description
Technical field
The present invention relates to the preparation method of organic system highly concentrated nano silver sol, be specially in organic solvent system, prepared the method for highly concentrated nano silver sol by liquid-phase reduction one step, belong to nano-functional material preparation field.
Background technology
As a member in nano material family, Nano Silver shows the characteristics such as excellent optics, electronics, magnetic and heat, obtains extensive approval in fields such as electronics industry, anti-biotic material and organic catalysis.Therefore the preparation research tool carrying out Nano Silver is of great significance.At present in the main preparation methods of Nano Silver solution phase chemical reduction with simple to operate, equipment investment cost is low and be easy to enlarged experiment and be widely used.
Although the data preparing Nano Silver about solution phase chemical reduction is a lot, but from the paper delivered at present and disclosed patent, the research of nano silver colloidal sol should mostly be theoretical basis research, and the emphasis that people pay close attention to still is confined to the pattern of nano-Ag particles and the regulation and control etc. of granularity.In addition, in view of the thermodynamic phase that nano silver colloidal sol itself has, solution phase chemical reduction is generally applicable to the nano silver colloidal sol synthesis of extremely rare (below 0.5wt%), and the raising of concentration often can only obtain the precipitated product of Argent grain.In recent years, although there is a small amount of research and development group to start research emphasis to move to how to improve in the concentration of nano silver colloidal sol, so that next step directly applies in the production of downstream product, thus can remove from centrifugation and the loaded down with trivial details last handling process such as dispersion are again carried out to particle sediment.But still there is many weak points for how developing the technical elements such as nano silver colloidal sol and easy raising Nano Silver concentration being applicable to variety classes solvent in people.Chinese patent [CN1583332A] discloses a kind of nano silver colloidal sol and preparation method thereof.Silver nitrate aqueous solution is added in the mixed solution of dispersion protective agent colloid and reducing agent, thus carry out redox reaction.Although the method technique is simple, efficiency is high, only can obtain concentration in aqueous phase system be up to 1wt% nano silver colloidal sol by the method, is difficult to meet the requirement of application to different solvents system and higher concentration.Chinese patent [CN1803351A] discloses a kind of preparation method of inorganic carried nanometer silver sol.Dispersant is added in the mineral powder aqueous solution; then silver nitrate and protective agent are added in above-mentioned inorganic matter aqueous dispersion; under the condition stirred, be added in the reducing agent aqueous solution of freezing mistake at 0 ~ 8 DEG C, in aqueous phase system, obtain the nano silver colloidal sol that silver content reaches as high as 3wt%.
Although aqueous phase system has the advantage of environmental protection, but due to a lot of take Nano Silver as the downstream product of raw material be all prepare in organic system (as: oil phase nano-silver antibacterial paint etc.), according to the similar principle mixed, to be directly that the nano silver colloidal sol that medium prepares is used in required organic system with organic solvent, the process of can save purification, disperseing again, meets the requirement of energy-saving consumption-reducing in production process.Chinese patent [CN101220506A] discloses a kind of method at ethylene glycol middle and high concentration mass-synthesis of silver nano-wire.Under the protection of inactive gas; in reflux, oil bath is heated to 100 ~ 200 DEG C and obtains the organic phase nano silver colloidal sol of silver content between 2 ~ 4wt%; but the method complex process, condition are harsh, energy consumption is comparatively large, is not easy to amplification scale and scale up test.
As far as we know, all 5wt% is not reached by the concentration of the preparation-obtained nano silver colloidal sol of distinct methods at present.But in applications such as electronics and medicine, Nano Silver solubility is higher, and the impurity that the pure Nano Silver adding necessary amounts is brought into is fewer, the electronics of products obtained therefrom and the performance such as antibacterial higher.Therefore, the raising of Nano Silver solubility has conclusive effect to the performance promoting downstream product further.
Summary of the invention
The object of the invention is to for the deficiency in current highly concentrated nano silver sol preparation and application, there is provided simple, mild condition, energy-saving consumption-reducing, organic phase highly concentrated nano silver sol with low cost and preparation method thereof so that meet the needs in downstream product application.
The object of the invention is to be achieved through the following technical solutions:
On the basis ensureing nano silver colloidal sol dynamic stabilization, improve the concentration of nano silver colloidal sol, to reach the object promoting downstream product performance as far as possible.Compared with prior art, adopting liquid phase reduction one step to obtain the kinetically metastable highly concentrated nano silver sol of concentration between 5wt% ~ 10wt% is the highly concentrated nano silver sol that application is generally acknowledged.By protective agent PVP ((poly (vinyl pyrolidone); PVP)) and reducing agent dissolve successively in organic solvent; then the solution containing silver-colored source is dropwise added; after stirring; react a period of time at a certain temperature, obtain the highly concentrated nano silver sol in different organic system.
Concrete steps are as follows:
(1) at room temperature, be dissolved in organic solvent by protective agent PVP and reducing agent, preparation obtains PVP, and reducing agent and organic solvent mass ratio are the solution A of 1:0.025 ~ 2.0:2.6 ~ 7.5; Be dissolved in silver-colored source in deionized water or organic solvent, preparation obtains the solution B that silver salt concentrations is 12wt% ~ 46wt%;
(2) under the condition stirred, solution B dropwise added in solution A, be configured to solution A and B mass ratio is the mixed solution of 1:0.5 ~ 2.6, then reaction 2 ~ 9h at room temperature ~ 80 DEG C, namely obtains highly concentrated nano silver sol.
The model of the protective agent PVP that the present invention is used is respectively PVP-K15, and molecular weight is about 10, and 000; PVP-K30, molecular weight is about 25, and 000 ~ 40,000; PVP-K90, molecular weight is about 360, and 000.
The present invention's organic solvent used be saturated or unsaturated, have 1 ~ 2 hydroxy functional group, the fatty alcohol of C1 ~ C8, aromatic alcohol, amine, acid amides or sulfoxide type solvents, as: ethanol, normal propyl alcohol, n-hexyl alcohol, cyclohexanol, ethylene glycol, diethylene glycol, phenmethylol, dimethyl formamide (dimethylformamide, DMF), dimethylacetylamide (dimethylacetamide, DMAC) one or more, in monoethanolamine, isopropylamine, triethylamine, dimethyl sulfoxide (DMSO) (dimethyl sulfoxide, DMSO).
The present invention's reducing agent used is one or more in resorcinol, hydroquinones etc., sodium borohydride, hydrazine hydrate, glyoxal and ascorbic acid.
The present invention silver-colored source used is inorganic acid silver (as: silver nitrate) or organic acid silver (as: silver acetate, silver citrate etc.)
Silver content in the present invention in gained highly concentrated nano silver sol is 5wt% ~ 10wt%, and the average grain diameter of particle is 40 ~ 80nm.
Excellent results of the present invention is:
(1) silver content of involved in the present invention nano silver colloidal sol up to 10wt%, can be convenient to direct application, purifies without the need to concentrated further.
(2) the present invention directly prepares highly concentrated nano silver sol by one-step method, preparation method is simple, without the need to stringent process conditions and equipment, equipment cost is low, do not relate to centrifugal, ultrafiltration, the last handling process such as oven dry, again dispersion, energy resource consumption is few, is easy to the application of amplification scale and downstream product.
(3) involved in the present invention highly concentrated nano silver sol comprises multiple organic solvent system, can meet the demand in different application field.
(4) method adopted in the present invention, does not relate to the process conditions that high temperature, backflow, inert gas shielding etc. are harsh, is easy to enlarged experiment and large-scale production.
Accompanying drawing explanation
The X-ray diffraction spectrogram of the Nano Silver that Fig. 1 obtains for the embodiment of the present invention 1.
The uv-visible absorption spectroscopy figure of the Nano Silver that Fig. 2 obtains for the embodiment of the present invention 2.
Fig. 3 is the transmission electron microscope photo of the embodiment of the present invention 3 gained nano-Ag particles.
Fig. 4 is the particle size distribution figure of the embodiment of the present invention 4 nano-Ag particles.
Fig. 5 is the transmission electron microscope photo of the embodiment of the present invention 5 nano-Ag particles.
Fig. 6 is the particle size distribution figure of the embodiment of the present invention 6 gained nano-Ag particles.
Detailed description of the invention
The following examples further illustrate of the present invention, instead of limit the scope of the invention.
Embodiment 1
(1) at room temperature, be dissolved in 5ml DMF successively by 1.00g PVP-K90 and 1.20g resorcinol, preparation obtains solution A; By 1.70g AgNO
3be dissolved in 2.00ml water, preparation obtains solution B;
(2) under the condition stirred, solution B dropwise added in solution A, after dropwising, stirred at ambient temperature reaction 3h, is warming up to 60 DEG C of reaction 2h, then is warming up to 80 DEG C of continuation reaction 2h.Final that silver concentration is 10wt %, average grain diameter is the field gray highly concentrated nano silver sol of 75nm, and calculate through weighing, reaction yield is 98%.
X-ray diffraction spectrogram result shows, product is in 2 θ=38.1 °, 44.3 °, 64.4 °, 77.5 ° and 81.5 ° of places have diffraction maximum to occur, respectively corresponding silver-colored (111), (200), (220), (311) and (222) crystal face, illustrate that what obtain is the pure nanocrystalline silver of face-centered cubic, as shown in Figure 1.
Embodiment 2
(1) at room temperature, be dissolved in 3ml DMAC successively by 0.40g PVP-K30 and 0.65g hydroquinones, preparation obtains solution A; By 1.00g AgNO
3be dissolved in 2ml normal propyl alcohol, preparation obtains solution B;
(2) under the condition stirred, solution B dropwise added in solution A, after dropwising, stirred at ambient temperature reaction 3h, is warming up to 80 DEG C of reaction 6h.Final that silver concentration is 9wt%, average grain diameter is the khaki highly concentrated nano silver sol of 51nm.As shown in Figure 2, the maximum absorption wavelength of colloidal sol is 440nm to its ultraviolet visible light abosrption spectrogram result.
Embodiment 3
(1) at room temperature, be that 10% hydrazine hydrate is dissolved in 4ml ethylene glycol successively by 0.75g PVP-K30 and 0.70ml concentration, preparation obtains solution A; By 1.30g AgNO
3be dissolved in 3.50ml DMSO, preparation obtains solution B;
(2) under the condition stirred, solution B is dropwise added in solution A, after dropwising, be warming up to 80 DEG C of reaction 4h.Final silver concentration is the khaki highly concentrated nano silver sol of 8wt%.The display of its transmission electron microscope results prepares nano-Ag particles and mostly is triangular plate or class triangular plate, is 67nm, as shown in Figure 3 through statistical average particle diameter.
Embodiment 4
(1) at room temperature, be dissolved in the mixed solvent of 3ml diethylene glycol and 1ml phenmethylol successively by 0.75g PVP-K30 and 0.70ml glyoxal, preparation obtains solution A; By 1.11AgNO
3be dissolved in 3.50ml n-hexyl alcohol, preparation obtains solution B;
(2) under the condition stirred, solution B is dropwise added in solution A, after dropwising, be warming up to 80 DEG C of reaction 2h.Final silver concentration is the khaki highly concentrated nano silver sol of 7wt%.As shown in Figure 4, through the software statistics of particle size analyzer, average grain diameter is 45nm to the nano-Ag particles granularity distribution result prepared.
Embodiment 5
(1) at room temperature, the boron sodium cyanide solution being 10% by 0.20g PVP-K30 and 0.05ml concentration is dissolved in the mixed solvent of 0.25ml monoethanolamine and 0.75ml ethanol successively, and preparation obtains solution A; Be dissolved in by 0.42g silver acetate in 2.88ml triethylamine, preparation obtains solution B;
(2) under the condition stirred, solution B is dropwise added in solution A, after dropwising, be warming up to 40 DEG C of reaction 4h.The final highly concentrated nano silver sol obtaining silver concentration and be about 6wt%, transmission electron microscope results display prepares nano-Ag particles, and calculating its average grain diameter is 62nm, as shown in Figure 5.
Embodiment 6
(1) at room temperature, it is in the mixed solvent of 1% acetic acid that 0.50g PVP-K15 and 0.05g ascorbic acid are dissolved in 0.20ml monoethanolamine, 0.80ml cyclohexanol and 0.30ml concentration successively, and preparation obtains solution A; 1.20g silver citrate is dissolved in 1 of 2.00ml, in 2 propane diamine, preparation obtains solution B;
(2) under the condition stirred, solution B is dropwise added in solution A, after dropwising, under room temperature, continue reaction 4h.Final silver concentration is the highly concentrated nano silver sol of 5wt%.As shown in Figure 6, through the software statistics of particle size analyzer, average grain diameter is 42nm to the nano-Ag particles granularity distribution result prepared.
Claims (8)
1. the preparation method of organic system highly concentrated nano silver sol, is characterized in that concrete steps are as follows:
(1) at room temperature, be dissolved in organic solvent by protective agent PVP and reducing agent, preparation obtains PVP, and reducing agent and organic solvent mass ratio are the solution A of 1:0.025 ~ 2.0:2.6 ~ 7.5; Be dissolved in silver-colored source in deionized water or organic solvent, preparation obtains the solution B that silver salt concentrations is 12wt% ~ 46wt%;
(2) under the condition stirred, solution B dropwise added in solution A, be configured to solution A and B mass ratio is the mixed solution of 1:0.5 ~ 2.6, then reaction 2 ~ 9h at room temperature ~ 80 DEG C, namely obtains highly concentrated nano silver sol.
2. the method for claim 1, it is characterized in that the model of described protective agent PVP is respectively PVP-K15, molecular weight is about 10, and 000; PVP-K30, molecular weight is about 25, and 000 ~ 40,000; PVP-K90, molecular weight is about 360, and 000.
3. the method for claim 1, it is characterized in that described organic solvent be saturated or unsaturated, have 1 ~ 2 hydroxy functional group, the fatty alcohol of C1 ~ C8, aromatic alcohol, amine, acid amides or sulfoxide type solvents.
4. method as claimed in claim 3, is characterized in that described organic solvent is: one or more in ethanol, normal propyl alcohol, n-hexyl alcohol, cyclohexanol, ethylene glycol, diethylene glycol, phenmethylol, dimethyl formamide, dimethylacetylamide, monoethanolamine, isopropylamine, triethylamine or dimethyl sulfoxide (DMSO).
5. the method for claim 1, is characterized in that described reducing agent is one or more in resorcinol, hydroquinones, sodium borohydride, hydrazine hydrate, glyoxal or ascorbic acid.
6. the method for claim 1, is characterized in that described silver-colored source is that inorganic acid silver or organic acid are silver-colored.
7. method as claimed in claim 7, is characterized in that described silver-colored source is silver nitrate, silver acetate, silver citrate.
8. the method for claim 1, it is characterized in that the silver content in described highly concentrated nano silver sol is 5wt% ~ 10wt%, the average grain diameter of particle is 40 ~ 80nm.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108015299A (en) * | 2017-11-06 | 2018-05-11 | 珠海纳金科技有限公司 | Nano-Ag particles and preparation method thereof |
| CN108161022A (en) * | 2017-12-28 | 2018-06-15 | 湖北工业大学 | A kind of method that alkylamine prepares oil-soluble nano silver as complexing agent |
| US20180354031A1 (en) * | 2015-05-20 | 2018-12-13 | National University Corporation Yamagata University | Method for manufacturing silver nanoparticle dispersion and method for manufacturing silver nanoparticle ink |
| CN111992734A (en) * | 2020-08-21 | 2020-11-27 | 山东建邦胶体材料有限公司 | Preparation method of nano-silver with controllable particle size |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1819969A (en) * | 2003-08-23 | 2006-08-16 | 郑哲相 | Nanocomposite solution with complex function and method for preparation thereof |
| CN101473845A (en) * | 2009-01-19 | 2009-07-08 | 上海华实纳米材料有限公司 | Method for preparing nano silver colloidal sol for preventing color change |
| CN101731272A (en) * | 2009-12-24 | 2010-06-16 | 中国人民解放军军事医学科学院基础医学研究所 | Method for preparing antibacterial nanometer silver colloid |
| CN102935513A (en) * | 2012-10-17 | 2013-02-20 | 武汉康银高科有限公司 | Stable nanometer silver colloidal sol and preparation method thereof |
| CN103042227A (en) * | 2012-12-18 | 2013-04-17 | 广东省微生物研究所 | Nano-silver sol antibacterial agent and preparation method thereof |
-
2014
- 2014-10-16 CN CN201410549598.XA patent/CN104308180A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1819969A (en) * | 2003-08-23 | 2006-08-16 | 郑哲相 | Nanocomposite solution with complex function and method for preparation thereof |
| CN101473845A (en) * | 2009-01-19 | 2009-07-08 | 上海华实纳米材料有限公司 | Method for preparing nano silver colloidal sol for preventing color change |
| CN101731272A (en) * | 2009-12-24 | 2010-06-16 | 中国人民解放军军事医学科学院基础医学研究所 | Method for preparing antibacterial nanometer silver colloid |
| CN102935513A (en) * | 2012-10-17 | 2013-02-20 | 武汉康银高科有限公司 | Stable nanometer silver colloidal sol and preparation method thereof |
| CN103042227A (en) * | 2012-12-18 | 2013-04-17 | 广东省微生物研究所 | Nano-silver sol antibacterial agent and preparation method thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20180354031A1 (en) * | 2015-05-20 | 2018-12-13 | National University Corporation Yamagata University | Method for manufacturing silver nanoparticle dispersion and method for manufacturing silver nanoparticle ink |
| US10821506B2 (en) * | 2015-05-20 | 2020-11-03 | National University Corporation Yamagata University | Method for producing silver nanoparticle dispersion and method for producing silver nanoparticle ink |
| CN108015299A (en) * | 2017-11-06 | 2018-05-11 | 珠海纳金科技有限公司 | Nano-Ag particles and preparation method thereof |
| CN108161022A (en) * | 2017-12-28 | 2018-06-15 | 湖北工业大学 | A kind of method that alkylamine prepares oil-soluble nano silver as complexing agent |
| CN111992734A (en) * | 2020-08-21 | 2020-11-27 | 山东建邦胶体材料有限公司 | Preparation method of nano-silver with controllable particle size |
| CN111992734B (en) * | 2020-08-21 | 2022-02-22 | 山东建邦胶体材料有限公司 | Preparation method of nano-silver with controllable particle size |
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Application publication date: 20150128 |