CN108031839A - Copper nanoparticle of in-stiu coating organic matter and preparation method thereof - Google Patents

Abstract

The invention provides a nano-copper powder coated with organic matter in situ and a preparation method thereof. The preparation method is to add copper salt to an aqueous solution containing a dispersant and optionally a water-soluble macromolecule, dissolve and mix evenly, and add Adjust the pH of the alkaline solution to 10±0.5, then add a reducing agent, heat up to 30-100°C and react for 30-240 minutes, then react under ultrasonic conditions for 10-60 minutes, cool, centrifuge, separate the precipitate, and dry to obtain the in-situ package Nano-copper powder coated with organic matter. The nano-copper powder prepared by the method of the invention has uniform particle size, good dispersibility and good stability, and the dispersant coated on the surface of the copper particles can effectively prevent oxidation of the copper particles. The preparation method is simple, low in equipment requirements, large in economic benefits and broad in application prospects.

Description

Nano-copper powder coated with organic matter in situ and preparation method thereof

technical field

The invention relates to the technical field of material engineering, in particular to a nano-copper powder coated with organic matter in situ and a preparation method thereof.

Background technique

In recent years, the liquid-phase reduction method is the most reported and researched method for preparing nano-copper powder. Through a suitable reducing agent, the copper-containing compound is reduced to copper powder in solution. This method can be used to prepare nanoscale noble metal powders with good dispersibility and uniform particle size distribution, but the activity of copper is much stronger than that of precious metals such as gold and silver. How to solve the problem of surface oxidation of the obtained copper nanoparticles is still a problem in the production process. key.

The liquid-phase reduction method adopts the strategy of first complexation and then reduction, but this method has the problems of low reactant concentration and low production efficiency. Due to the traditional mechanical stirring method used in the preparation process, it is easy to cause the aggregation and oxidation of nano-copper powder; The prepared nano-copper powder often needs to be passivated in oleic acid. Therefore, it is urgent to develop a low-cost, simple and convenient method suitable for industrial production of organic-coated nano-copper powder.

Contents of the invention

The purpose of the present invention is to provide a preparation method for preparing copper nanoparticles with high oxidation resistance with simple operation and low production cost.

Another object of the present invention is to provide the nano-copper powder whose surface is in-situ coated with organic matter prepared according to the above method.

In order to achieve the purpose of the present invention, the present invention provides a method for preparing nano-copper powder coated with organic matter in situ, adding copper salt to an aqueous solution containing a dispersant and optionally a water-soluble macromolecule, dissolving and mixing uniformly, Add alkaline solution to adjust the pH to 10±0.5, then add reducing agent, heat up to 30-100°C and react for 30-240 minutes, then react under ultrasonic conditions (such as 40KHz) for 10-60 minutes, cool, centrifuge, separate the precipitate, and dry That is, the nano-copper powder coated with organic matter in situ is obtained.

In the present invention, the dispersant is selected from at least one of naphthalene sulfonate formaldehyde condensate, lignin sulfonate, alkylnaphthalene sulfonate or methylene bis-naphthalene sulfonate; preferably the dispersant The agent is naphthalenesulfonate formaldehyde condensate.

The reducing agent is at least one selected from hydrazine hydrate, ascorbic acid, sodium borohydride, glucose, sodium hypophosphite, formaldehyde, etc.; preferably, the reducing agent is hydrazine hydrate.

The water-soluble macromolecule is selected from at least one of polyvinylpyrrolidone, polyvinyl alcohol or polyethylene glycol and the like.

The copper salt is at least one selected from copper sulfate, copper nitrate, copper chloride, copper acetate or copper formate.

Preferably, lignosulfonate, alkyl naphthalene sulfonate or methylene bis-naphthalene sulfonate are sodium lignosulfonate, alkyl naphthalene sulfonate or sodium methylene bis-naphthalene sulfonate respectively in the present invention .

Preferably, the alkali solution in the present invention is a sodium hydroxide solution, more preferably a 1 mol/L sodium hydroxide solution.

In the aforementioned method, the concentration of the dispersant in the aqueous solution is 0.5-20 g/L, preferably 1-18 g/L, more preferably 2.5-10 g/L, most preferably 5-6.5 g/L.

In the aforementioned method, the concentration of the water-soluble macromolecules in the aqueous solution is 0-30 g/L, preferably 1-20 g/L, more preferably 5-15 g/L, most preferably 6-9 g/L.

In the aforementioned method, the concentration of the copper salt in the aqueous solution is 10-100mmol/L, preferably 20-80mmol/L, more preferably 30-50mmol/L.

In the aforementioned method, the molar ratio of the reducing agent to the copper salt is 20-66:1.

In the aforementioned method, after adding the reducing agent, the reaction temperature is preferably 50°C.

As a preferred embodiment of the present invention, the dispersant is naphthalenesulfonate formaldehyde condensate, and the reducing agent is hydrazine hydrate.

As another preferred embodiment of the present invention, the added reducing agent is hydrazine hydrate, and the molar ratio of copper ion to hydrazine hydrate is 1:20-70, preferably 1:30-66, more preferably 1:50-60.

The method of the present invention does not need to be carried out under an inert atmosphere or a protective atmosphere, and can be carried out directly in air.

As another preferred embodiment of the present invention, the method includes the following steps:

(1) A certain amount of dispersant is added into deionized water to make it fully dissolved, and the amount of dispersant added is 0.5-20g/L;

(2) adding the water-soluble macromolecule to the solution obtained in step (1) to fully dissolve it;

(3) Add copper salt to the mixed solution obtained, make it dissolve completely and mix evenly, the addition of copper salt is 10-100mmol/L;

(4) adding an alkali solution to the mixed solution obtained in step (3) to adjust the pH to 10 ± 0.5;

(5) adding a reducing agent to the mixed solution obtained in step (4) under stirring conditions;

(6) After mixing evenly, raise the temperature of the mixed solution obtained in step (5) to 50°C, react under this condition for 30-240 minutes, and then sonicate for 30 minutes, wait for it to cool to room temperature, centrifuge, and take out the reddish-brown precipitate at the bottom, which is the surface Copper nanoparticles coated with organic matter.

As another preferred embodiment of the present invention, the method includes the following steps:

1) adding the naphthalenesulfonate formaldehyde condensate into deionized water for dissolution to obtain a solution I having a naphthalenesulfonate formaldehyde condensate content of 0.5-20 g/L;

2) adding the water-soluble macromolecules to the solution I for dissolution to obtain a solution II with a water-soluble macromolecules content of 1-20 g/L;

3) adding copper salt to solution II to dissolve, and obtaining solution III with a copper salt content of 10-100 mmol/L;

4) adjust the pH of solution III to 10±0.5 with 1mol/L sodium hydroxide solution;

5) adding hydrazine hydrate to the mixed solution in step 4) under normal temperature stirring conditions to obtain solution IV;

6) Warm up the solution IV to 50°C, react at this temperature for 30-240 minutes, then sonicate for 30 minutes, and finally cool to room temperature, centrifuge, separate the precipitate, and dry.

The present invention also provides nano copper powder coated with organic matter in situ prepared according to the method described above. The copper powder has good dispersibility in water, no agglomeration phenomenon, relatively uniform size, a particle diameter of 100-200nm, and an organic coating layer with a thickness of 10-20nm.

The nano-copper powder coated with organic matter in situ of the present invention is suitable for the fields of conductive paste, ink-jet printing and the like.

Compared with the prior art, the present invention has the following advantages:

(1) Using compounds such as naphthalenesulfonate formaldehyde condensates and water-soluble macromolecules as templates, adopting a one-step reduction method, while reducing nano-copper particles, a layer of organic matter is coated on the surface to prepare nano-particles with a core-shell structure. For the copper particles, the particle size of the core layer is 100-200nm, and the thickness of the organic coating layer on the surface is 10-20nm. It overcomes the problems of low reactant concentration, low reaction yield, high cost, and unsuitability for industrial production in the traditional method of preparing nano-copper powder by complexing copper salt and then reducing it in liquid phase.

(2) The traditional mechanical stirring method is improved to ultrasonic vibration stirring. At the same time, by controlling the pH value of the reaction system, the agglomeration and oxidation of copper powder are effectively avoided. The operation method is simple, the equipment requirements are low, the economic benefit is large, and the preparation In the process, no inert gas needs to be introduced for protection, and the prepared nano-copper powder has high purity, and there are no impurity peaks of cupric oxide and cuprous oxide.

(3) The effects of compounds (dispersants) and water-soluble macromolecules such as naphthalenesulfonate formaldehyde condensate among the present invention are: on the one hand both can control the size and the shape of nanoparticle, can disperse nanoparticle again on the other hand, prevent The nanoparticles are agglomerated, and the dispersant coated on the surface can also protect the copper particles in the inner layer, prevent them from oxidation, and improve the oxidation resistance of the nano-copper powder.

(4) The organic-coated nano-copper powder prepared by the method of the present invention is very stable, does not oxidize after being placed in the air for 6 months, and has good oxidation resistance.

Description of drawings

Figure 1 is the X-ray diffraction pattern (A) of the organic-coated nano-copper powder prepared in Example 1 of the present invention and the X-ray diffraction pattern (B) of the synthesized organic-coated nano-copper particles placed for 6 months.

FIG. 2 is a TGA diagram of the organic-coated nano-copper powder prepared in Example 1 of the present invention.

FIG. 3 is a TEM image of the organic-coated nano-copper powder prepared in Example 1 of the present invention.

FIG. 4 is an XPS diagram of organic-coated nano-copper powder prepared in Example 1 of the present invention.

Detailed ways

The following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art, and the raw materials used are all commercially available products.

The preparation method of the nano-copper powder of embodiment 1 coating organic matter in situ

1) A certain amount of naphthalenesulfonate formaldehyde condensate is added to deionized water until it is fully dissolved, so that the concentration of naphthalenesulfonate formaldehyde condensate is 5g/L;

2) Add a certain amount of polyvinylpyrrolidone to the solution obtained in step 1), and wait for it to fully dissolve, so that the final concentration of polyvinylpyrrolidone is 9g/L;

3) Add copper sulfate pentahydrate to the solution obtained in step 2), stir until it is fully dissolved, so that the final concentration of copper ions is 10mmol/L;

4) Adjust the solution obtained in step 3) with 1mol/L sodium hydroxide solution until the pH value of the solution is 10±0.5;

5) Warm up the solution obtained in step 4) to 50°C, add dropwise a hydrazine hydrate solution with a mass fraction of 50%, so that the molar ratio of hydrazine hydrate to copper ions is 66:1, and then keep it at this temperature for 150min to obtain Reddish-brown nano copper colloidal solution;

6) After the reaction, the copper colloid solution obtained in step 5) was ultrasonicated at 40 MHz for 30 min, then centrifuged at 10,000 rpm for 5 min, and the precipitate was separated, and dried to form organic-coated copper nanoparticles.

The X-ray diffraction pattern of the organic-coated nano-copper powder prepared in Example 1 is shown in FIG. 1 . It can be seen from the figure that the three diffraction peaks with strong signals correspond to the (111), (200), and (220) crystal planes of copper, and the other peaks with weaker intensity belong to the surface-coated organic compounds: naphthalenesulfonate Naphthalene sulfonate formaldehyde condensate and polyvinylpyrrolidone did not find the peaks of cupric oxide and cuprous oxide, indicating that the use of naphthalenesulfonate formaldehyde condensate and polyvinylpyrrolidone as templates can synthesize surface-coated organic compounds in a non-protective atmosphere. , Unoxidized copper particles.

After the product was placed for 6 months, it was subjected to X-ray diffraction analysis (Figure 1), and it was found that its XRD diffraction peaks did not change, and there were no cuprous oxide and cupric oxide diffraction peaks. The final product has not been oxidized, which further shows that it is very stable in the air and has good oxidation resistance.

FIG. 2 is a TGA graph of the organic-coated nano-copper powder prepared in Example 1. FIG. It can be seen from the figure that the synthesized composite particles will lose weight to different degrees with the increase of temperature under nitrogen atmosphere, which is related to the decomposition of organic matter on the surface. In addition, according to the weight loss of the TGA curve, the surface coating can also be roughly estimated. The amount of organic matter is about 30%.

FIG. 3 is a TEM image of the organic-coated nano-copper powder prepared in Example 1. FIG. It can be seen from the figure that the particle size of the organic-coated copper nanoparticles is about 100 nm, and the thickness of the organic coating layer is about 10 nm.

FIG. 4 is an XPS diagram of the organic-coated nano-copper powder prepared in Example 1. FIG. It can be seen from the figure that in addition to the signal peak of copper, there are signal peaks of S, Na, O, C, and N on the surface of copper particles. The peak is from polyvinylpyrrolidone.

The preparation method of the nano-copper powder of embodiment 2 coating organic matter in situ

1) A certain amount of naphthalenesulfonate formaldehyde condensate is added to deionized water until it is fully dissolved, so that the concentration of naphthalenesulfonate formaldehyde condensate is 5g/L;

2) Add a certain amount of polyvinylpyrrolidone to the solution obtained in step 1), and wait for it to fully dissolve so that the final concentration of polyvinylpyrrolidone is 6g/L;

3) Add copper nitrate to the solution obtained in step 2), stir until it is fully dissolved, so that the final concentration of copper ions is 50mmol/L;

4) Adjust the solution obtained in step 3) with 1mol/L sodium hydroxide solution until the pH value of the solution is 10±0.5;

5) Warm up the solution obtained in step 4) to 50°C, add dropwise a hydrazine hydrate solution with a mass fraction of 50%, so that the molar ratio of hydrazine hydrate to copper ions is 50:1, and then keep it at this temperature for 100min to obtain Reddish-brown nano copper colloidal solution;

6) After the reaction, the copper colloid solution obtained in step 5) was ultrasonicated at 40 MHz for 30 min, then centrifuged at 10,000 rpm for 5 min, and the precipitate was separated, and dried to form organic-coated copper nanoparticles.

The preparation method of the nano-copper powder of embodiment 3 coating organic matter in situ

1) A certain amount of naphthalenesulfonate formaldehyde condensate is added to deionized water until it is fully dissolved, so that the concentration of naphthalenesulfonate formaldehyde condensate is 20g/L;

2) Add a certain amount of polyvinylpyrrolidone to the solution obtained in step 1), and wait for it to fully dissolve, so that the final concentration of polyvinylpyrrolidone is 9g/L;

3) Add copper chloride to the solution obtained in step 2), stir until it is fully dissolved, so that the final concentration of copper ions is 30mmol/L;

4) Adjust the solution obtained in step 3) with 1mol/L sodium hydroxide solution until the pH value of the solution is 10±0.5;

5) Warm up the solution obtained in step 4) to 60°C, add dropwise an ascorbic acid solution with a mass fraction of 30%, so that the molar ratio of ascorbic acid to copper ions is 60:1, and then keep it at this temperature for 150 minutes to obtain a reddish-brown color The nanometer copper colloidal solution;

6) After the reaction, the copper colloid solution obtained in step 5) was ultrasonicated at 40 MHz for 30 min, then centrifuged at 10,000 rpm for 5 min, and the precipitate was separated, and dried to form organic-coated copper nanoparticles.

The preparation method of the nano-copper powder of embodiment 4 coating organic matter in situ

1) A certain amount of naphthalenesulfonate formaldehyde condensate is added to deionized water until it is fully dissolved, so that the concentration of naphthalenesulfonate formaldehyde condensate is 5g/L;

2) Add a certain amount of polyethylene glycol to the solution obtained in step 1), and wait for it to fully dissolve so that the final concentration of polyethylene glycol is 9g/L;

3) Add copper acetate to the solution obtained in step 2), stir until it is fully dissolved, so that the final concentration of copper ions is 10mmol/L;

4) Adjust the solution obtained in step 3) with 1mol/L sodium hydroxide solution until the pH value of the solution is 10±0.5;

5) Warm up the solution obtained in step 4) to 40°C, add dropwise a hydrazine hydrate solution with a mass fraction of 50%, so that the molar ratio of hydrazine hydrate to copper ions is 66:1, and then keep it at this temperature for 150min to obtain Reddish-brown nano copper colloidal solution;

6) After the reaction, the copper colloid solution obtained in step 5) was ultrasonicated at 40 MHz for 30 min, then centrifuged at 10,000 rpm for 5 min, and the precipitate was separated, and dried to form organic-coated copper nanoparticles.

The preparation method of the nano-copper powder of embodiment 5 coating organic matter in situ

1) A certain amount of sodium dodecyl naphthalene sulfonate is added to deionized water until it is fully dissolved, so that the concentration of sodium dodecyl naphthalene sulfonate is 2.5g/L;

2) Add a certain amount of polyvinylpyrrolidone to the solution obtained in step 1), and wait for it to fully dissolve, so that the final concentration of polyvinylpyrrolidone is 9g/L;

3) Add copper formate to the solution obtained in step 2), stir until it is fully dissolved, so that the final concentration of copper ions is 10mmol/L;

4) Adjust the solution obtained in step 3) with 1mol/L sodium hydroxide solution until the pH value of the solution is 10±0.5;

5) Warm up the solution obtained in step 4) to 65°C, add dropwise a hydrazine hydrate solution with a mass fraction of 50%, so that the molar ratio of hydrazine hydrate to copper ions is 66:1, and then keep it at this temperature for 150min to obtain Reddish-brown nano copper colloidal solution;

6) After the reaction, the copper colloid solution obtained in step 5) was ultrasonicated at 40 MHz for 30 min, then centrifuged at 10,000 rpm for 5 min, and the precipitate was separated, and dried to form organic-coated copper nanoparticles.

The preparation method of the nano-copper powder of embodiment 6 coating organic matter in situ

1) Add a certain amount of sodium lignosulfonate into deionized water until it is fully dissolved, so that the concentration of sodium lignosulfonate is 6.5g/L;

2) Add a certain amount of polyethylene glycol to the solution obtained in step 1), and wait for it to fully dissolve so that the final concentration of polyethylene glycol is 9g/L;

3) Add copper sulfate pentahydrate to the solution obtained in step 2), stir until it is fully dissolved, so that the final concentration of copper ions is 10mmol/L;

4) Adjust the solution obtained in step 3) with 1mol/L sodium hydroxide solution until the pH value of the solution is 10±0.5;

5) Warm up the solution obtained in step 4) to 50°C, add dropwise a glucose solution with a mass fraction of 45%, so that the molar ratio of glucose to copper ions is 50:1, and then keep at this temperature for 180min to obtain a reddish-brown color The nanometer copper colloidal solution;

6) After the reaction, the copper colloid solution obtained in step 5) was ultrasonicated at 40 MHz for 30 min, then centrifuged at 10,000 rpm for 5 min, and the precipitate was separated, and dried to form organic-coated copper nanoparticles.

The preparation method of the nano-copper powder of embodiment 7 coating organic matter in situ

1) A certain amount of methylene bis-naphthalene sulfonic acid is added to deionized water until it is fully dissolved, so that the concentration of methylene bis-naphthalene sulfonic acid is 8.5g/L;

2) Add a certain amount of polyethylene glycol to the solution obtained in step 1), and wait for it to fully dissolve so that the final concentration of polyethylene glycol is 9g/L;

3) Add copper sulfate pentahydrate to the solution obtained in step 2), stir until it is fully dissolved, so that the final concentration of copper ions is 10mmol/L;

4) Adjust the solution obtained in step 3) with 1mol/L sodium hydroxide solution until the pH value of the solution is 10±0.5;

5) Warm up the solution obtained in step 4) to 70°C, add dropwise a sodium borohydride solution with a mass fraction of 60%, so that the molar ratio of sodium borohydride to copper ions is 50:1, and then keep at this temperature for 210min , to obtain a reddish-brown nano copper colloidal solution;

6) After the reaction, the copper colloid solution obtained in step 5) was ultrasonicated at 40 MHz for 30 min, then centrifuged at 10,000 rpm for 5 min, and the precipitate was separated, and dried to form organic-coated copper nanoparticles.

The preparation method of the nano-copper powder of embodiment 8 coating organic matter in situ

1) A certain amount of naphthalenesulfonate formaldehyde condensate is added to deionized water until it is fully dissolved, so that the concentration of naphthalenesulfonate formaldehyde condensate is 20g/L;

2) Add copper sulfate pentahydrate to the solution obtained in step 1), stir until it is fully dissolved, so that the final concentration of copper ions is 10mmol/L;

3) Adjust the solution obtained in step 2) with 1mol/L sodium hydroxide solution until the pH value of the solution is 10±0.5;

4) Warm up the solution obtained in step 3) to 60°C, add dropwise a hydrazine hydrate solution with a mass fraction of 80%, so that the molar ratio of hydrazine hydrate to copper ions is 66:1, and then keep it at this temperature for 30 minutes to obtain Reddish-brown nano copper colloidal solution;

5) After the reaction, the copper colloid solution obtained in step 4) was ultrasonicated at 40 MHz for 30 min, and then centrifuged at 10,000 rpm for 5 min to separate and precipitate the organic-coated copper nanoparticles after drying.

Embodiment 9 and the comparison of existing liquid-phase reduction method for preparing nano-copper powder

Nano-copper powder was prepared according to the method in Example 1 as an experimental group.

Control group 1: adopt CN1686648A embodiment 1 method to prepare nano-copper powder, specifically as follows:

1) Use distilled water to prepare 100ml of copper nitrate aqueous solution with a concentration of 0.01mol/L, slowly add ammonia water with a concentration of 5.0%, the solution becomes turbid when the ammonia water is added, and gradually becomes clear with the addition of ammonia water, stop when the solution becomes completely clear Add ammonia water;

2) Add 2.5g of polyvinylpyrrolidone and 1g of sodium lauryl sulfate to the solution obtained in step 1), and heat the mixed solution to 60°C;

3) During stirring, add the hydrazine hydrate aqueous solution with a temperature of 60°C and a concentration of 2.5% into the mixed solution obtained in step 2), when the pH value reaches 9, stop adding the hydrazine hydrate aqueous solution, and add 0.01ml of liquid in the solution Paraffin, continue to stir for 60 minutes, then age for 20 hours to obtain a suspension containing nano-copper;

4) Under an argon atmosphere, the suspension is centrifuged, first washed with distilled water and then with ethanol for 3 times;

5) Put the nano-copper powder cleaned in step 4) into a vacuum drying oven, and dry at 70°C.

Control group 2: adopt CN103769598A embodiment 1 method to prepare nano-copper powder, specifically as follows:

(1) Add 36g CuSO ₄ ·5H ₂ O to pure water to prepare 250ml of copper salt solution with a concentration of 0.54mol/L, put the solution in a 500ml reactor and preheat it to 50°C.

(2) Quickly add ammonia water with a mass percentage concentration of 20% under stirring to form a certain degree of blue turbid liquid, and the molar ratio of ammonia water to copper salt is 2:1. Slowly add a reducing agent hydrazine hydrate solution with a mass percent concentration of 80%, and the molar ratio of hydrazine hydrate to copper salt is 2:1.

(3) Quickly inject 30ml of dispersant solution with a mass concentration of 6g/L when 1/2 of the hydrazine hydrate remains, and keep warm for 2 hours after the addition.

(4) Filtrate and wash the resulting brick-red powder, first wash twice with boiled pure water, then wash twice with ethanol, and finally soak in BHT ethanol solution with a concentration of 2.5g/L for 20 minutes.

(5) Afterwards, the supernatant was poured out, and vacuum-dried to obtain copper powder.

Control group 3: adopt CN102205422A embodiment 1 method to prepare nano-copper powder, specifically as follows:

Take by weighing 500g copper sulfate pentahydrate and be dissolved in 3L deionized water, stir to make it dissolve completely, slowly add the strong ammoniacal liquor (28%) of 875g until solution is clear and transparent, be heated to 45 ℃; Take by weighing 2g sodium lauryl sulfate ( SDS) and 1g OP-10 were dissolved in 1L deionized water, and then the aqueous solution of the dispersant was slowly added to the copper sulfate aqueous solution, and stirred to disperse it evenly to form a mixed solution A. Weigh 540g of glucose and add it to A, stir to dissolve it to form a mixed solution B, add B to a 6L stainless steel high-temperature reaction kettle with a Teflon liner, tighten the reaction kettle, put it in an oven and heat it to 120°C , keep it warm for 2 hours, then cool down to room temperature naturally, take out the mixed solution, filter out the precipitate, wash it several times with deionized water and ethanol, put it in a vacuum drying oven, and dry it at 40°C for 4 hours to finally obtain high-purity, high-quality Surface active nano copper powder.

Table 1 Experimental group and comparison group 1-3 preparation method and nanometer copper powder product

atmosphere during preparation Are Antioxidants Added During Storage? Oxidation resistance of nano copper powder products Control group 1 Separate under protective atmosphere No need for additional antioxidants Not determined Control group 2 no protective atmosphere Additional antioxidants are required for storage Not determined Control group 3 no protective atmosphere No need for additional antioxidants Not determined test group no protective atmosphere No need for additional antioxidants Still not oxidized after 6 months at room temperature

Although the present invention has been described in detail with general descriptions and specific embodiments above, it is obvious to those skilled in the art that some modifications or improvements can be made on the basis of the present invention. Therefore, the modifications or improvements made on the basis of not departing from the spirit of the present invention all belong to the protection scope of the present invention.

Claims (10)

1. a kind of preparation method of the copper nanoparticle of in-stiu coating organic matter, it is characterised in that mantoquita is added to containing scattered In agent and the optionally aqueous solution containing water-soluble macromolecule, dissolve and be uniformly mixed, add aqueous slkali and adjust pH to 10 ± 0.5, Then reducing agent is added, after being warming up to 30-100 DEG C of reaction 30-240min, 10-60min is reacted under ultrasound condition, is cooled down, Centrifugation, precipitation and separation, up to the copper nanoparticle of in-stiu coating organic matter after drying；

Wherein, the dispersant is selected from naphthalenesulfonate formaldehyde condensation compound, lignosulfonates, alkylnaphthalene sulfonate or di-2-ethylhexylphosphine oxide At least one of naphthalene sulfonate；It is preferred that the dispersant is naphthalenesulfonate formaldehyde condensation compound；

The reducing agent in hydrazine hydrate, ascorbic acid, sodium borohydride, glucose, sodium hypophosphite, formaldehyde at least one Kind；It is preferred that the reducing agent is hydrazine hydrate.

2. according to the method described in claim 1, it is characterized in that, the water-soluble macromolecule be selected from polyvinylpyrrolidone, At least one of polyvinyl alcohol or polyethylene glycol.

3. according to the method described in claim 1, it is characterized in that, the mantoquita is selected from copper sulphate, copper nitrate, copper chloride, vinegar At least one of sour copper or copper formate.

4. according to the method described in claim 1, it is characterized in that, the concentration of dispersant is 0.5-20g/L in the aqueous solution, It is preferred that 1-18g/L, more preferably 2.5-10g/L, most preferably 5-6.5g/L.

5. according to the method described in claim 1, it is characterized in that, the concentration of water-soluble macromolecule is 0- in the aqueous solution 30g/L, preferably 1-20g/L, more preferably 5-15g/L, most preferably 6-9g/L.

6. according to the method described in claim 1, it is characterized in that, the concentration of mantoquita is 10-100mmol/ in the aqueous solution L, preferably 20-80mmol/L, more preferably 30-50mmol/L.

7. according to the method described in claim 1, it is characterized in that, the molar ratio of the reducing agent and mantoquita is 20-66:1.

8. according to the method described in claim 1, it is characterized in that, it is warming up to 50 DEG C of reactions after adding reducing agent.

9. according to claim 1-8 any one of them methods, it is characterised in that comprise the following steps：

1) naphthalenesulfonate formaldehyde condensation compound is added in deionized water and dissolved, obtaining naphthalenesulfonate formaldehyde condensation compound content is The solution I of 0.5-20g/L；

2) water-soluble macromolecule is added in solution I and dissolved, obtain the solution II that water-soluble macromolecule content is 1-20g/L；

3) mantoquita dissolving is added into solution II, obtains the solution III that mantoquita content is 10-100mmol/L；

4) pH to 10 ± 0.5 of solution III is adjusted with the sodium hydroxide solution of 1mol/L；

5) hydrazine hydrate is added in the mixed liquor under the conditions of stirring at normal temperature to step 4), obtains solution IV, copper ion in solution IV Molar ratio with hydrazine hydrate is 1:20-70, preferably 1:30-66, more preferably 1:50-60；

6) solution IV is warming up to 50 DEG C, reacts 30-240min, then ultrasound 30min at such a temperature, be finally cooled to room temperature, Centrifugation, precipitation and separation are dry.

10. the copper nanoparticle of the in-stiu coating organic matter prepared according to any one of claim 1-9 the method.