CN104259472B - A kind of organic composite of superfine sheet copper powder and preparation method thereof - Google Patents
A kind of organic composite of superfine sheet copper powder and preparation method thereof Download PDFInfo
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- CN104259472B CN104259472B CN201410445488.9A CN201410445488A CN104259472B CN 104259472 B CN104259472 B CN 104259472B CN 201410445488 A CN201410445488 A CN 201410445488A CN 104259472 B CN104259472 B CN 104259472B
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- copper
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Abstract
The invention discloses organic composite of a kind of superfine sheet copper powder and preparation method thereof, first by copper-bath complexation, adjust solution PH to 12 14；Being subsequently adding the organic composite being made up of polyvinylpyrrolidone with imidazoline type amphoteric surfactant, organic composite automatically forms micelle soft template, induction copper ion reduction in the solution；It is eventually adding reductant solution, under ultrasound condition, reacts 30 180min, take off a layer precipitate washing, centrifugal and drying, obtain the ultrafine flake copper powder being dried.Instant invention overcomes chemical reduction method and prepare copper powder shortcoming in preparation technology and properties of product, can prepare at room temperature, easily controllable product morphology and particle diameter distribution width and free from environmental pollution.
Description
Technical field
The invention belongs to metal dust and manufacture field, be specifically related to organic composite and the system thereof of a kind of superfine sheet copper powder
Preparation Method.
Background technology
Superfine cupper powder is a kind of functional material important for printed circuit and conducting function composite.Its pattern,
Grain size is to affect the reason that electric conductivity is important, and spherical copper powder is point cantact, and flake copper is that face contact is conducive to conduction, people
Attempt using various methods to prepare flake copper, such as: grinding, pressing mold, evaporative precipitation, vapour deposition etc., but these method institutes
The product morphology of preparation is uncontrollable, particle diameter distribution width.In recent years chemical solution method due to possess easy and simple to handle, product morphology can
The features such as control, even particle size and equipment requirements are low are paid much attention to.
Though recently there being patent report to use chemical method to obtain flake copper, such as Chinese patent CN1613588A discloses
The chemical preparation process of a kind of ultrafine flake copper powder, it uses NH by redox reaction under conditions of 60-95 DEG C3·H2O
It is that ultrafine flake copper powder prepared by chelating agent with ethylenediamine, but NH3·H2O and ethylenediamine are volatile under at heating state, very big shadow
Environment, the health of harm operator are rung.The composition generating product when simultaneously preparing superfine cupper powder by chemical method is difficult to
Control, easily generate copper oxide or Red copper oxide, affect electric conductivity.Therefore, develop can prepare at normal temperatures highly purified
The preparation method of superfine sheet copper powder is the technical issues that need to address.
Summary of the invention
Solving the technical problem that: for the deficiencies in the prior art, what the present invention provided a kind of superfine sheet copper powder has unit
Compound and preparation method thereof, prepares highly purified superfine sheet copper powder, narrow diameter distribution, morphology controllable at normal temperatures.
Technical scheme: the organic composite of a kind of superfine sheet copper powder that the present invention provides, is by polyvinylpyrrolidone
Form with imidazoline type amphoteric surfactant in mass ratio 1 (1-4)；
The molecular structure characteristic of described polyvinylpyrrolidone is:, described imidazoline type amophoteric surface active
Agent molecular structure characteristic is:, wherein R is the carbochain containing 10-20 carbon atom；R1For hydrogen-based, alkyl,
Amide groups or Laurel acidic group；R2For hydrogen-based, alkyl or sulfonic group.
The preparation method of the superfine sheet copper powder that the present invention provides, comprises the following steps:
(1) being dissolved in deionized water by copper sulfate, stirring makes it be completely dissolved, and control copper-bath concentration is 0.08-
1mol/L, adds tetrasodium ethylenediamine tetraacetate in solution, is evenly stirred until solution from the light blue navy blue that becomes, formation complexation
Copper-bath, controlling the mol ratio of tetrasodium ethylenediamine tetraacetate and copper sulfate in solution is 1 (2-8)；
(2) hydro-oxidation potassium solid particle in the complexation copper-bath that step (1) configures, stirs, regulates molten
Liquid PH to 12-14, obtains the complexation copper-bath of alkaline environment, and wherein in solution, the concentration of potassium hydroxide is 0.2-
0.7mol/L；
(3) the complexation copper-bath of the alkaline environment obtained to step (2) adds by polyvinylpyrrolidone, imidazoles
The organic composite that quinoline type amphoteric surfactant in mass ratio 1 (1-4) forms, stirring to solution becomes transparency liquid, organic
The mass concentration of compositions is 5-20g/L；
(4) potassium borohydride is dissolved in deionized water, is configured to potassium borohydride aqueous solution, potassium borohydride and copper sulfate material
Amount ratio be 14；
(5) the potassium borohydride aqueous solution that step (4) is configured with 10-200 drip/that the speed of min adds step (3) is prepared
Transparency liquid in, and at room temperature ultrasonic reaction 30-180min in power 50-100W, the ultrasonic machine of frequency 40KHZ, take
Lower sediment thing；
(6) precipitate prepared by step (5) is washed with deionized 3-5 time, washing with alcohol 1-5 time, then at 3000-
Centrifugal 2-5min under the rotating speed of 8000r/min, and in 40-80 DEG C of vacuum, gained solid product is dried 2-5h, obtain being dried is super
Fine platy copper powder.
Described polyvinylpyrrolidone and imidazoline type amphoteric surfactant automatically form micelle soft template in the solution,
Induction copper ion reduction, grows into platy particle, and then obtains the superfine sheet copper powder of good dispersion property.
Beneficial effect: instant invention overcomes chemical reduction method and prepare copper powder shortcoming in preparation technology and properties of product,
Prepare superfine sheet copper powder at room temperature, it is easy to control product morphology and the particle size dispersion of distribution and free from environmental pollution.
Accompanying drawing explanation
Fig. 1 is the shape appearance figure of embodiment 1 gained superfine sheet copper powder；
Fig. 2 is the shape appearance figure of embodiment 2 gained superfine sheet copper powder；
Fig. 3 is the shape appearance figure of embodiment 3 gained superfine sheet copper powder.
Detailed description of the invention
Embodiment 1
Step one, being dissolved in 500ml deionized water by the copper sulfate of 0.04mol, stirring makes it be completely dissolved, to copper sulfate
Solution adds the tetrasodium ethylenediamine tetraacetate of 0.02mol, is evenly stirred until solution and is become navy blue from light blue, obtain complexation
Copper-bath；
Step 2, add 19.6g potassium hydroxide in step one gained complexation copper-bath, regulation solution PH to 14,
Obtain the complexation copper-bath of alkaline environment；
Step 3, add by 7.5g lauryl imidazolinium betaine in the alkaline complexation copper-bath of step 2 gained
With the organic composite of 2.5g PVP K30 composition, stirring makes it be completely dissolved, obtains transparency liquid；
Step 4, being dissolved in the deionized water of 500ml by the potassium borohydride of 0.01mol in another container, stirring makes it
It is completely dissolved, obtains potassium borohydride aqueous solution；
Step 5, potassium borohydride aqueous solution step 4 configured add step 3 with the speed of 200/min and obtain
Transparency liquid in, and ultrasonic reaction 180min in power 50W, the ultrasonic machine of frequency 40KHZ at room temperature, take lower sediment
Thing；
Step 6, the precipitate that step 5 obtains is washed with deionized 3 times, by washing with alcohol 1 time, uses 3000r/
The rotating speed of min is centrifuged 5min, uses vacuum drying oven 2h at 80 DEG C.
Experimental result, from accompanying drawing 1, obtained product is the copper powder of ganoid lamellar, particle projection major diameter
It it is 1 μm.
Embodiment 2
Step one, being dissolved in 500ml deionized water by the copper sulfate of 0.5mol, stirring makes it be completely dissolved, in solution
Add the tetrasodium ethylenediamine tetraacetate of 0.125mol, be evenly stirred until solution and become navy blue from light blue, obtain complexation sulphuric acid
Copper solution；
In step 2, addition 11.2g potassium hydroxide pellet step one gained complexation copper-bath, regulation solution PH arrives
13, obtain the complexation copper-bath of alkaline environment；
Step 3, add by 4g carboxylic acid type imidazoline and the poly-second of 1g in the alkaline complexation copper-bath of step 2 gained
The organic composite of alkene pyrrolidone K30 composition, stirring makes it be completely dissolved, obtains transparency liquid.
Step 4, being dissolved in the deionized water of 250ml by the potassium borohydride of 0.125mol in another container, stirring makes it
It is completely dissolved, obtains potassium borohydride aqueous solution；
Step 5, potassium borohydride aqueous solution step 4 configured add what step 3 obtained with the speed of 10/min
In transparency liquid, and ultrasonic reaction 30min in power 100W, the ultrasonic machine of frequency 40KHZ at room temperature, take lower sediment
Thing.
Step 6, the precipitate that step 5 obtains is washed with deionized 5 times, by washing with alcohol 3 times, uses 5000r/
The rotating speed of min is centrifuged 3min, dries 4h with vacuum drying oven at 60 DEG C.
Experimental result, from accompanying drawing 2, obtained product is ganoid flake copper, particle projection major diameter 0.5
μm。
Embodiment 3
Step one, being dissolved in 500ml deionized water by the copper sulfate of 0.25mol, stirring makes it be completely dissolved, in solution
Add the tetrasodium ethylenediamine tetraacetate of 0.03125mol, be evenly stirred until solution and become navy blue from light blue, obtain complexation sulfur
Acid copper solution；
Step 2, add in 5.6g potassium hydroxide pellet step one gained complexation copper-bath, regulation solution PH to 12,
Obtain the complexation copper-bath of alkaline environment；
Step 3, toward the alkaline complexation copper-bath of step 2 gained adding by 1.25g sulfonic acid type imidazoline and
The organic composite of 1.25g polyvinylpyrrolidone K60 composition, stirring makes it be completely dissolved, obtains transparency liquid.
Step 4, in another container, the potassium borohydride of 0.0625mol is dissolved in the deionized water of 312.5ml, stirring
Make it be completely dissolved, obtain potassium borohydride aqueous solution；
Step 5, potassium borohydride aqueous solution step 4 configured add step 3 with the speed of 100/min and obtain
Transparency liquid in, and ultrasonic reaction 120min in power 75W, the ultrasonic machine of frequency 40KHZ at room temperature, take lower sediment
Thing.
Step 6, the precipitate that step 5 obtains is washed with deionized 4 times, by washing with alcohol 5 times, uses 8000r/
The rotating speed of min is centrifuged 2min, dries 5h with vacuum drying oven at 40 DEG C.
Experimental result, from accompanying drawing 3, obtained product is ganoid flake copper, particle projection major diameter
0.75μm。
Claims (4)
1. the organic composite of a superfine sheet copper powder, it is characterised in that be by polyvinylpyrrolidone and imidazoline type both sexes
Surfactant in mass ratio 1 (1-4) forms；The molecular structure characteristic of described polyvinylpyrrolidone is:, institute
Stating imidazoline type amphoteric surfactant molecular structure characteristic is:, wherein R is former containing 10-20 carbon
The carbochain of son；R1 is hydrogen-based, alkyl, amide groups or Laurel acidic group；R2 is hydrogen-based, alkyl or sulfonic group.
The preparation method of the organic composite of a kind of superfine sheet copper powder the most as claimed in claim 1, it is characterised in that include
Following steps:
(1) being dissolved in deionized water by copper sulfate, stirring makes it be completely dissolved to obtain copper-bath, adds second two in solution
Amine tetraacethyl four sodium, is evenly stirred until solution from the light blue navy blue that becomes, forms the copper-bath of complexation, control in solution
The mol ratio of tetrasodium ethylenediamine tetraacetate and copper sulfate is 1 (2-8)；
(2) hydro-oxidation potassium solid particle in the complexation copper-bath that step (1) configures, stirs, and regulates solution PH
To 12-14, obtaining the complexation copper-bath of alkaline environment, wherein in solution, the concentration of potassium hydroxide is 0.2-0.7mol/L；
(3) the complexation copper-bath of the alkaline environment obtained to step (2) adds by polyvinylpyrrolidone, imidazoline type
The organic composite that amphoteric surfactant in mass ratio 1 (1-4) forms, stirring to solution becomes transparency liquid, organic assembling
The mass concentration of thing is 5-20g/L；
(4) in another container, potassium borohydride is dissolved in deionized water, is configured to potassium borohydride aqueous solution, control potassium borohydride
It is 14 with the amount ratio of copper sulfate material；
(5) the potassium borohydride aqueous solution that step (4) is configured with 10-200 drip/speed of min add prepared by step (3) saturating
In prescribed liquid, and at room temperature ultrasonic reaction 30-180min in ultrasonic machine, take off a layer precipitate；
(6) precipitate prepared by step (5) is washed with deionized 3-5 time, washing with alcohol 1-5 time, then at 3000-
Centrifugal 2-5min under the rotating speed of 8000r/min, and in 40-80 DEG C of vacuum, gained solid product is dried 2-5h, obtain being dried is super
Fine platy copper powder.
The preparation method of the organic composite of a kind of superfine sheet copper powder the most according to claim 2, it is characterised in that institute
Stating copper-bath concentration is 0.08-1mol/L.
The preparation method of the organic composite of a kind of superfine sheet copper powder the most according to claim 2, it is characterised in that institute
Stating ultrasonic machine power is 50-100W, frequency 40KHZ.
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107570725A (en) * | 2017-09-11 | 2018-01-12 | 南通意特化工有限公司 | A kind of chemical preparation process of ultrafine flake copper powder |
| CN109732101B (en) * | 2018-03-16 | 2021-11-23 | 南京林业大学 | Preparation method of flaky nickel powder |
| CN109877336B (en) * | 2018-03-16 | 2021-11-23 | 南京林业大学 | Preparation method of flaky copper powder |
| CN109663932B (en) * | 2018-03-16 | 2021-11-23 | 南京林业大学 | Preparation method of flaky silver powder |
| CN113523269B (en) * | 2021-06-08 | 2023-06-16 | 五邑大学 | Copper powder and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5850047A (en) * | 1996-03-11 | 1998-12-15 | Murata Manufacturing Co., Ltd. | Production of copper powder |
| CN101417341A (en) * | 2008-11-07 | 2009-04-29 | 江苏科技大学 | Method for preparing metal nickel nano hollow bal |
| CN102941350A (en) * | 2012-11-06 | 2013-02-27 | 南京工业大学 | Preparation method of copper nanoparticles |
| CN102947436A (en) * | 2010-04-12 | 2013-02-27 | 株式会社资生堂 | Concentrated liquid detergent composition and process for production thereof |
| CN103143724A (en) * | 2013-03-16 | 2013-06-12 | 安徽工业大学 | Preparation method of nanometer silver colloid in different shapes |
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2014
- 2014-09-03 CN CN201410445488.9A patent/CN104259472B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5850047A (en) * | 1996-03-11 | 1998-12-15 | Murata Manufacturing Co., Ltd. | Production of copper powder |
| CN101417341A (en) * | 2008-11-07 | 2009-04-29 | 江苏科技大学 | Method for preparing metal nickel nano hollow bal |
| CN102947436A (en) * | 2010-04-12 | 2013-02-27 | 株式会社资生堂 | Concentrated liquid detergent composition and process for production thereof |
| CN102941350A (en) * | 2012-11-06 | 2013-02-27 | 南京工业大学 | Preparation method of copper nanoparticles |
| CN103143724A (en) * | 2013-03-16 | 2013-06-12 | 安徽工业大学 | Preparation method of nanometer silver colloid in different shapes |
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