CN105618787A - Preparation method of hydrophobic silver nanoparticles - Google Patents
Preparation method of hydrophobic silver nanoparticles Download PDFInfo
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- CN105618787A CN105618787A CN201610057326.7A CN201610057326A CN105618787A CN 105618787 A CN105618787 A CN 105618787A CN 201610057326 A CN201610057326 A CN 201610057326A CN 105618787 A CN105618787 A CN 105618787A
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- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
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Abstract
The invention relates to preparation of metal nanoparticles, in particular to a preparation method of hydrophobic silver nanoparticles. The method includes the steps of (1) preparing a silver-amine complex with silver nitrate as a raw material; (2) conducting a reaction on the solvothermal condition; (3) separating a solid from liquid centrifugally; and (4) scattering the solid particles obtained through separation into an oil soluble organic solvent. According to the preparation method, synthesis equipment is simple and convenient to operate, the condition demand is low, and the silver nanoparticles can be scattered in the oil soluble solvent well and have high stability; particularly silver nanoparticles with controllable dimensions can be obtained, specifically, the particle size ranges from 1 nm to 100 nm and the average particle size ranges from 40 nm to 50 nm.
Description
Technical field
The present invention relates to the preparation of metal nanoparticle, the preparation method being specifically related to a kind of hydrophobicity Nano silver grain.
Background technology
Nano silver grain has special optical property, has higher catalytic performance and broad spectrum antibacterial, all has potential using value in fields such as optics, catalysis, health cares. Particularly silver nano-grain is applied in transparency conductive electrode field in recent years so that the preparation of Nano silver grain becomes particularly because people gazes at. Silver nano ink for preparing transparency conductive electrode is typically all dispersion in organic solvent, it requires that Nano silver grain not only granule uniformly but also has hydrophobicity, can be dispersed stably in organic solvent.
At present, prepare the Nano silver grain that silver nano ink adopts mainly to there is several methods that. A kind of by aerdentalloy by chemical method remove aluminum manufacture obtain, mean particle size is 85nm. In order to prevent the gathering of Nano silver grain in emulsion method preparation process, with polymer (3%DisperbykTM106) Nano silver grain is wrapped up, increase its surface hydrophobicity so that can stable being present in water-in-oil emulsion system. Another kind is that silver oxalate and oleyl amine are reacted the complex generating argentiferous, oleyl amine and oxalic acid particle, and then this complex of heat resolve is thus synthesis contains the silver-colored ultra micron of oleyl amine protection. Recently, also have the carbon of aliphatic alkyl is add up to the aliphatic hydrocarbon monoamine of more than 6, the carbon of aliphatic alkyl adds up to the aliphatic alkyl monoamine of less than 5 and the carbon of aliphatic alkyl adds up to the amine mixed liquor of aliphatic hydrocarbon diamidogen of less than 8 and mixes generation with silver compound containing described silver compound and described amine complex, then described complex heat resolve being obtained Nano silver grain, its size is at several nm to tens of about nm; This nanoparticle heats below 200 DEG C and obtains silver conductive material.
But said method is all under organic stabilizer exists, and obtains the Nano silver grain of organic stabilizer cladding by thermally decomposing silver compound. The speed not only synthesized is slow, and the Nano silver grain uniformity prepared is not ideal enough, and the bad control of particle size.
Summary of the invention
In order to solve the problems referred to above, the preparation method that it is an object of the invention to provide a kind of hydrophobicity silver nano-grain; The method not only synthesis device is simple, easy to operate, condition is loose, aggregate velocity is fast, and Nano silver grain can well be dispersed in oil-based solvent, and it is strong that particle size controls Simultaneous Stabilization well.
The present invention is achieved through the following technical solutions:
The preparation method of a kind of hydrophobicity silver nano-grain, comprises the following steps:
(1), the preparation of argent-amine complex: silver nitrate solid is put in reactor one, is subsequently added into acetonitrile, after silver nitrate solid is completely dissolved, places into organic amine and be stirred, be finally separating to obtain faint yellow argent-amine complex, dry stand-by;
(2), the preparation of hydrophobicity Nano silver grain: take step (1) obtain dry faint yellow argent-amine complex put in reactor two, add SOLID ORGANIC amine and ethanol, heat the mixture to 50 DEG C��75 DEG C, it is continuously heating to 120 DEG C��190 DEG C after solid is melted, react 10��50 minutes, obtain hydrophobicity silver nanoparticle solution;
(3), will step (2) obtain hydrophobicity silver nanoparticle solution cooling, centrifugation, obtain described hydrophobicity silver nano-grain. Chloroform obtains product after washing, and finally, is distributed to as required by described hydrophobicity silver nano-grain in different oil-based solvent (need to be quickly dissolved in oil-based solvent by the pressed powder being centrifugally separating to obtain).
It is preferred that described organic amine is the one or more combination thing in tetradecy lamine, cetylamine and 18-amine.. Preparation hydrophobicity Nano silver grain, the Nano silver grain being synthetically derived has organic amine parcel, so stablizing, being uniformly dispersed in oil-dissolving solvent. In order to obtain this result, as well, because the organic group chain of link is more long on amino group, then the oil-soluble of organic amine is more good for the organic chain length point of aminated compounds adopted.
It is preferred that in step (1), the ratio of the amount of substance between described silver nitrate, organic amine and acetonitrile is 1:1.5��2.5:90��150. When synthesizing the presoma argent-amine complex of Nano silver grain, used raw material is to put into according to the metering ratio of the product obtained, and this input ratio regular meeting allows raw material be obtained by fully, it does not have cause some waste. And when reduction presoma argent-amine complex is this single step reaction of Nano silver grain, organic amine is excessive input as solvent, terminates to recycle afterwards in reaction. The advantage of the material adding proportion that therefore this synthetic method adopts is in that not result in the pollution of the loss of raw material and environment.
It is preferred that in step (1), put into organic amine and stir 6��12 hours, the temperature in reactor one is 20 DEG C��45 DEG C.
It is preferred that in step (1), drying temperature is 40 DEG C��120 DEG C. Add the organic amine powder in acetonitrile solution and want thin so that cetylamine and silver nitrate can quick, complete reactions.
It is preferred that in step (2), described faint yellow argent-amine complex, amount of substance between organic amine and ethanol ratio be 1:2��6:0.2��5.
It is preferred that in step (2), need first temperature rises to 50 DEG C��75 DEG C in temperature-rise period, just can continue to heat up after waiting solid completely melted.
It is preferred that in step (2), at 120 DEG C��190 DEG C, after reacting 10��50 minutes, thermal source will be removed at once, allow reactant liquor natural cooling.
It is preferred that in step (3), the rotating speed of centrifugation is 2000��6000r/min. In step (3), the solid at room temperature precipitated out contains the silver nano-grain of organic amine parcel and unnecessary cetylamine, it is necessary to dissolve unnecessary cetylamine with chloroform, in order to obtain the silver nano-grain of pure organic amine parcel.
The present invention comprises the following steps: 1) prepare argent-amine complex with silver nitrate for raw material; 2) react when solvent thermal; 3) centrifugation solid and liquid; 4) solid particle dispersions obtained will be separated in oil-soluble organic solvent. The present invention's is with chain alkyl amine for solvent and coating agent, when solvent thermal, can obtain, by controlling reaction temperature and response time, the silver nano-grain that size is controlled. The method provides a practicable approach for synthesis high-quality hydrophobicity silver nano-grain. The content of preparation process reducing agent, reaction temperature, response time all have controllability, and the Nano silver grain size finally given is controlled within the specific limits, disperses good stability in organic solvent. Especially, it is possible to by selecting the kind of organic amine and controlling response time and reaction temperature, Nano silver grain size well being controlled, the size range of Nano silver grain prepared by this method is 1��100nm, and average diameter is 40��50nm. Such as with cetylamine for organic amine, reacting 20min at 150 DEG C, obtain the Nano silver grain of size uniformity, particle size is between 40��50nm; And the size of the Nano silver grain obtained after being 25min when the prolongation response time is at 35��80nm
Accompanying drawing explanation
Fig. 1 is the prepared enlarged drawing obtaining hydrophobicity Nano silver grain of the present invention.
Specific embodiment
Below in conjunction with detailed description of the invention, the present invention is described in further detail, to help skilled artisan understands that the present invention.
Embodiment 1
The preparation method of a kind of hydrophobicity silver nano-grain: under stirring at room temperature, adds 350mL acetonitrile solution by 0.065mol silver nitrate, stirs after clarifying to solution, add 0.13mol cetylamine, continue stirring 8h, through filtering, after drying, obtain argent-amine complex [Ag (C16H33)2]NO3. This argent-amine complex (0.03mol) is put into round-bottomed flask, it is simultaneously introduced ethanol (0.056mol) and cetylamine (0.07mol), first 50 DEG C it are warming up to, it is continuously heating to 150 DEG C, after reaction 20min, remove thermal source, cooling, it is centrifugally separating to obtain product, then product is distributed in hexane. Sample characterizes turn out to be the Nano silver grain with cetylamine parcel through XRD, SEM, FT-IR and NMR, and particle size is homogeneous, between 40��50nm.
Embodiment 2
The preparation method of a kind of hydrophobicity silver nano-grain: adopt the preparation process of embodiment 1, by 0.03mol argent-amine complex [Ag (C16H33)2]NO3, 0.07mol cetylamine, 0.028mol ethanol be placed in round-bottomed flask, be first warming up to 50 DEG C, be continuously heating to 170 DEG C, after reaction 15min, remove thermal source, cooling, be centrifugally separating to obtain product, then product be distributed in hexamethylene. The particle size of the Nano silver grain obtained is at 35��60nm.
Embodiment 3
The preparation method of a kind of hydrophobicity silver nano-grain: adopting the preparation process of embodiment 2, prolongation response time is the 25min Nano silver grain obtaining cetylamine parcel, and particle diameter is at 35��80nm.
Embodiment 4
The preparation method of a kind of hydrophobicity silver nano-grain: adopting the preparation process of embodiment 2, reaction temperature rises to 180 DEG C, reacts 20min, and the material particle size scope obtained is at 38nm��110nm.
Embodiment 5
The preparation method of a kind of hydrophobicity silver nano-grain: adopt the preparation process of embodiment 1,0.065mol tetradecy lamine (C14H29NH2) it is added to the acetonitrile solution (400mL) containing 0.065mol silver nitrate, continue stirring 8h, through filtering, after drying, obtain argent-amine complex [Ag (C14H29)2]NO3. This argent-amine complex (0.03mol) is put into round-bottomed flask, it is simultaneously introduced ethanol (0.037mol) and tetradecy lamine (0.07mol), first 42 DEG C it are warming up to, then continue to be warming up to 150 DEG C, after reaction 20min, remove thermal source, cooling, being centrifugally separating to obtain product, be then distributed in heptane by product, the particle diameter of product is between 35��50nm.
Embodiment 6
The preparation method of a kind of hydrophobicity silver nano-grain: adopt the preparation process of embodiment 5, take the argent-amine complex [Ag (C of 0.02mol14H29)2]NO3Putting into and participate in solvothermal reaction in round-bottomed flask, the particle diameter of the product obtained is between 35��55nm.
Embodiment 7
The preparation method of a kind of hydrophobicity silver nano-grain: adopting the preparation process of embodiment 5, reduction temperature rises to 170 DEG C, the particle diameter of the product obtained is between 35��65nm.
Embodiment 8
The preparation method of a kind of hydrophobicity silver nano-grain: adopt the preparation process of embodiment 1,0.065mol 18-amine. (C18H37NH2) it is added to the acetonitrile solution (500mL) containing 0.065mol silver nitrate, continue stirring 8h, through filtering, after drying, obtain argent-amine complex [Ag (C18H37)2]NO3. This argent-amine complex (0.03mol) is put into round-bottomed flask, it is simultaneously introduced ethanol (0.06mol) and 18-amine. (0.08mol), first 58 DEG C it are warming up to, then continue to be warming up to 165 DEG C, after reaction 25min, remove thermal source, cooling, being centrifugally separating to obtain product, be then distributed in heptane by product, the particle diameter of product is between 38��60nm.
Embodiment 9
The preparation method of a kind of hydrophobicity silver nano-grain: adopting the preparation process of embodiment 8, reaction temperature rises to 180 DEG C, reacts 15min, and the particle diameter of product is between 38��65nm.
Embodiment 10
The preparation method of a kind of hydrophobicity silver nano-grain: adopting the preparation process of embodiment 8, reaction temperature rises to 180 DEG C, reacts 30min, and the particle diameter of product is between 45��90nm.
Embodiment 11
The preparation method of a kind of hydrophobicity silver nano-grain: adopt the preparation process of embodiment 8, adds ethanol 0.1mol, and reaction temperature, at 150 DEG C, obtains the particle diameter of product between 35��48nm.
Above-described embodiment, simply presently preferred embodiments of the present invention, not be used for limiting the scope of the present invention, therefore all equivalence changes done with the feature described in the claims in the present invention and principle or modify, all should include within the claims in the present invention scope.
Claims (10)
1. the preparation method of a hydrophobicity silver nano-grain, it is characterised in that comprise the following steps:
(1), the preparation of argent-amine complex
Silver nitrate solid is put in reactor one, is subsequently added into acetonitrile, after silver nitrate solid is completely dissolved, places into organic amine and be stirred, be finally separating to obtain faint yellow argent-amine complex, dry stand-by;
(2), the preparation of hydrophobicity Nano silver grain
Take the faint yellow argent-amine complex that step (1) obtains drying to put in reactor two, add SOLID ORGANIC amine and ethanol, by mixture reacting by heating 10��50 minutes, obtain hydrophobicity silver nanoparticle solution;
(3), will step (2) obtain hydrophobicity silver nanoparticle solution cooling, centrifugation, obtain described hydrophobicity silver nano-grain.
2. the preparation method of hydrophobicity silver nano-grain according to claim 1, it is characterised in that: mixture zone heating is reacted 10��50 minutes by step (2).
3. the preparation method of hydrophobicity silver nano-grain according to claim 2, it is characterized in that: in step (2), zone heating reacts particularly as follows: heat the mixture to 50 DEG C��75 DEG C, is continuously heating to 120 DEG C��190 DEG C, reacts 10��50 minutes after solid is melted.
4. the preparation method of hydrophobicity silver nano-grain according to claim 3, it is characterised in that: in step (2), at 120 DEG C��190 DEG C, after reacting 10��50 minutes, thermal source to be removed at once, allow reactant liquor natural cooling.
5. the preparation method of hydrophobicity silver nano-grain according to claim 4, it is characterised in that: in step (2), described faint yellow argent-amine complex, amount of substance between organic amine and ethanol ratio be 1:2��6:0.2��5.
6. the preparation method of hydrophobicity silver nano-grain according to claim 1, it is characterised in that: in step (1), the ratio of the amount of substance between described silver nitrate, organic amine and acetonitrile is 1:1.5��2.5:90��150.
7. the preparation method of hydrophobicity silver nano-grain according to claim 1, it is characterised in that: in step (1), putting into organic amine and stir 6��12 hours, the temperature in reactor one is 20 DEG C��45 DEG C.
8. the preparation method of hydrophobicity silver nano-grain according to claim 1, it is characterised in that: in step (1), drying temperature is 40 DEG C��120 DEG C.
9. the preparation method of hydrophobicity silver nano-grain according to claim 1, it is characterised in that: in step (3), the rotating speed of centrifugation is 2000��6000r/min.
10. the preparation method of hydrophobicity silver nano-grain according to any one in claim 1-9, it is characterised in that: it is the one or more combination thing in tetradecy lamine, cetylamine and 18-amine. by described organic amine.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115519131A (en) * | 2022-08-05 | 2022-12-27 | 南通领跑者新材料科技有限公司 | Preparation method of silver powder for conductive paste |
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| CN104018189A (en) * | 2014-06-05 | 2014-09-03 | 东北大学 | Preparation method for novel nano-silver wire |
| TW201542713A (en) * | 2014-04-25 | 2015-11-16 | Daicel Corp | Silver particle coating composition |
| CN105206350A (en) * | 2015-10-09 | 2015-12-30 | 重庆文理学院 | Preparing method for silver conductive thin film resisting water and oil |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102895192A (en) * | 2012-09-26 | 2013-01-30 | 上海交通大学 | Method for producing microsphere through oil-in-nanoparticle suspension-water-in-oil mode |
| CN103588164A (en) * | 2013-10-08 | 2014-02-19 | 上海交通大学 | Copper-silver micro-nano multi-stage structure super-hydrophobic surface and production method thereof |
| TW201542713A (en) * | 2014-04-25 | 2015-11-16 | Daicel Corp | Silver particle coating composition |
| CN104018189A (en) * | 2014-06-05 | 2014-09-03 | 东北大学 | Preparation method for novel nano-silver wire |
| CN105206350A (en) * | 2015-10-09 | 2015-12-30 | 重庆文理学院 | Preparing method for silver conductive thin film resisting water and oil |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115519131A (en) * | 2022-08-05 | 2022-12-27 | 南通领跑者新材料科技有限公司 | Preparation method of silver powder for conductive paste |
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