CN110183592B - Nano-copper/silver hydrotalcite-like conductive composite material and preparation method thereof - Google Patents
Nano-copper/silver hydrotalcite-like conductive composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a nano-copper/silver hydrotalcite-like conductive composite material and a preparation method thereof, wherein the special structure of hydrotalcite-like, the designability of the layered structure of hydrotalcite-like, and the excellent conductive performance of nano-copper and nano-silver are utilized, the easy-forming processing advantage of a polymer material is combined, hydrazine hydrate is utilized as a reducing agent, PVP is utilized as a dispersing agent, a liquid phase reduction method and a coprecipitation one-step method are adopted to prepare a novel nano-copper/silver hydrotalcite-like and epoxy acrylate composite conductive film material, the conductive film material has good conductive performance, and can be used in the fields of conductive adhesive, antistatic coatings and the like; the method has the advantages of simple preparation process, wide application field and better social and economic benefits.
Description
Technical Field
The invention belongs to the technical field of conductive composite materials, and particularly relates to a nano copper/silver hydrotalcite-like conductive composite material and a preparation method thereof.
Background
The composite material with the conductive property, which is prepared by the polymer such as high polymer, rubber material and the like, the filling material with the conductive property and different types of composite materials through a series of processes, not only has excellent conductivity, but also has the advantages of diversity and high utilization value, such as easy processing into different shapes, light weight, excellent conductive property and mechanical property, low price and the like, and is widely applied to the chemical industry.
The hydrotalcite-like compound is a hydrotalcite-like powder material, has a layered double-metal hydroxide structure, and has a large design and adjustment space for the structure and the performance. The hydrotalcite-like compound is prepared into a special structure of a film material, and can expand the application field of the hydrotalcite-like compound in super-hydrophobicity, corrosivity, optical and electromagnetic domains of the film material, so that the hydrotalcite-like compound has a huge development space. Copper and silver have very good conductivity and high stability, show excellent performance in the chemical field and the physical field, and become the focus of chemical, physical, biological and other fields and the scientific research focus. The rapid development of nano materials attracts researchers to continuously research and discover that materials composed of nano materials have special properties, such as volume effect, surface effect, quantum size effect, quantum tunneling effect on the macro scale and other properties which are not possessed by materials in a macro scale. Although many reports have been made on the discussion of the conductive composite film, the preparation and research of the conductive composite material formed by hydrotalcite-like compound/nano silver or hydrotalcite-like compound and nano copper have not been reported yet.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a nano-copper/silver hydrotalcite-like conductive composite material and a preparation method thereof.
One of the technical schemes adopted by the invention for solving the technical problems is as follows:
a preparation method of a nano-copper/silver hydrotalcite-like conductive composite material comprises the following steps:
1) adding Cu (NO) to aqueous sodium stearate solution3)2Aqueous solution or AgNO3Mixing the aqueous solution uniformly, and simultaneously dropwise adding NaAlO into the aqueous solution2Solution and MgCl2Uniformly mixing the solution, adjusting the pH value to 9-10, and then aging at 75-85 ℃ for 10-14 h; after aging, carrying out solid-liquid separation, washing the solid part until the pH value of a washing liquid is 7-8, soaking the solid part with absolute ethyl alcohol, and carrying out solid-liquid separation to obtain copper ion-containing hydrotalcite or silver ion-containing hydrotalcite;
2) mixing PVP aqueous solution with the copper ion-containing hydrotalcite or the silver ion-containing hydrotalcite, adding water, carrying out ultrasonic oscillation treatment, adding absolute ethyl alcohol, then dropwise adding hydrazine hydrate, stirring for reaction after dropwise adding is finished, standing, removing supernate, washing the rest part with absolute ethyl alcohol, and carrying out solid-liquid separation to obtain nano copper/hydrotalcite-like compound or nano silver/hydrotalcite-like compound;
3) and uniformly mixing acrylic acid and acrylamide, adding the nano-copper/hydrotalcite-like compound or the nano-silver/hydrotalcite-like compound, completely dissolving the nano-copper/hydrotalcite-like compound or the nano-silver/hydrotalcite-like compound, adding epoxy acrylate, uniformly mixing, and curing to obtain the nano-copper hydrotalcite-like conductive composite material or the nano-silver hydrotalcite-like conductive composite material.
In one embodiment: in the nano-copper hydrotalcite-like conductive composite material, the ratio of magnesium to aluminum (molar ratio) is 2.5-3.5: 1.
In one embodiment: in the nano-silver hydrotalcite-like conductive composite material, the ratio (molar ratio) of magnesium, aluminum and silver is 2.5-3.5: 0.8-1.2: 2.5-3.5, and the content of nano-silver/hydrotalcite-like compound is 6-8%.
In one embodiment: in the step 2), the volume ratio of the total volume of the water in the PVP aqueous solution and the added water to the absolute ethyl alcohol is 2-4: 1-3.
In one embodiment: in the step 2), the concentration of hydrazine hydrate is 38-42%.
In one embodiment: in the step 3), the curing mode is ultraviolet irradiation curing, and a photoinitiator is also added into the reaction system in the step 3).
In one embodiment: the photoinitiator is 1173.
In one embodiment: in the step 3), the mass ratio of epoxy acrylate, acrylic acid and acrylamide to the nano-copper/hydrotalcite-like compound or the nano-silver/hydrotalcite-like compound is 3.1-3.2: 0.7-0.8: 0.9-1.1: 0.045-0.6.
In one embodiment: the nano copper/hydrotalcite-like compound is subjected to oxidation resistance treatment and then used for preparing a nano copper hydrotalcite-like compound conductive composite material, wherein the oxidation resistance treatment comprises the following steps: adding the nano copper/hydrotalcite-like compound into a mixed solution of absolute ethyl alcohol and butyl titanate with the volume ratio of 0.8-1.2: 0.8-1.2, stirring for 3-5 h at 65-75 ℃, standing for 22-26 h, filtering, washing and drying to obtain the nano copper/hydrotalcite-like compound.
The second technical scheme adopted by the invention for solving the technical problems is as follows:
the nano copper/silver hydrotalcite-like conductive composite material prepared by the preparation method.
Compared with the background technology, the technical scheme has the following advantages:
the invention utilizes the special structure of hydrotalcite-like compound, the designability of the layered structure of hydrotalcite-like compound, and the excellent conductivity of nano-copper and nano-silver, and combines the easy-forming processing advantages of polymer materials, utilizes hydrazine hydrate as a reducing agent, PVP as a dispersing agent, and adopts a liquid phase reduction method and a coprecipitation one-step method to prepare the novel conductive film material compounded by nano-copper/silver, hydrotalcite-like compound and epoxy acrylate, and has good conductivity; the method has the advantages of simple preparation process, wide application field and better social and economic benefits.
Drawings
The invention is further illustrated by the following figures and examples.
FIG. 1 shows the IR spectra of the nano-copper/hydrotalcite-like compound (a) and the hydrotalcite-like compound (b).
FIG. 2 is the IR spectrum of nano silver/hydrotalcite-like compound.
Fig. 3 is an ultraviolet spectrum of the nano silver/hydrotalcite-like compound/EA coating.
FIG. 4 is a fluorescence spectrum of nano silver/hydrotalcite-like compound/EA coating.
FIG. 5 shows the resistance of the nano-copper/hydrotalcite-like compound/EA coating.
Fig. 6 shows the resistance of the nano silver/hydrotalcite-like compound/EA coating.
Fig. 7 is a relationship between the resistance value of the nano silver/hydrotalcite-like compound/EA coating and the types and contents of the conductive particles, in which: a-3:1:10 (Mg: Al: Ag, the same applies below), b-3:1:7, c-3:1:5, d-3:1:1, e-3:1: 3.
Detailed Description
The present invention will be described in detail with reference to the following examples:
materials and equipment referred to in the following examples include:
experiment raw materials: absolute ethyl alcohol (C)2H5OH), Acrylic Acid (AA), sodium metaaluminate (NaAlO)2) Magnesium chloride (MgCl)2) Sodium stearate (C)17H35COONa), silver nitrate (AgNO)3) Copper nitrate (Cu (NO)3)2) 80% hydrazine hydrate (H)6N2O), polyvinylpyrrolidone (PVP), Acrylamide (AM), butyl Titanate (TiOC)4H9)4) And the like are all AR and are all purchased from Tianjin chemical reagent wholesale company.
Instruments and equipment: the system comprises a constant-temperature water bath kettle (Changzhou national appliances, Inc., HH-1), a precise reinforcement electric stirrer (Changzhou national appliances, Inc., JJ-1), a portable UV curing light source (Baodingda electronics, Inc., UV-1KW), a constant-temperature magnetic stirrer (Shenzhen Tiannan North China practical Co., Ltd., HT-3), an ultrasonic cleaner (Kunshan ultrasonic instruments, KQ218), a vacuum drying box (Shanghai Boxun practical Co., Ltd., DZF-6050), a volume and surface resistance measuring instrument (Beijing crown survey experimental instruments, EST121), an ultraviolet/visible spectrophotometer (Shimadzu, UV2250), and a Wailan fluorescence spectrophotometer (Shanghai research electric furnace Co., Ltd., SXSXZ-4-10).
Example 1 preparation of nano-copper hydrotalcite-like conductive composite Material
1) Preparation of hydrotalcite containing copper ions
Weighing MgCl24.066g was dissolved in 10mL of deionized water; weighing NaAlO20.8197g of sodium stearate is dissolved in deionized water, 1.001g of sodium stearate is weighed and added into 100mL of deionized water to be stirred and dissolved in a constant temperature water bath kettle at 40 ℃, and sodium stearate water solution with the mass fraction of about 1 percent is prepared; weighing Cu (NO)3)22.416g was dissolved in 10mL of deionized water. 50mL of an aqueous sodium stearate solution was weighed into a three-necked flask, and Cu (NO) was added3)2Stirring the aqueous solution for 5min while adding NaAlO2Solution and MgCl2Dropwise adding into the aqueous solution of sodium stearate, and stirring for 30min after dropwise addition. And (3) adjusting the pH value of the mixed system by using an aqueous solution of sodium hydroxide until the pH value of the mixed slurry is 9-10, stopping stirring, obtaining a light blue substance, and finally aging at 80 ℃ for 12 h. And after aging, carrying out suction filtration, washing the filter cake with deionized water until the pH of the filtrate is 7-8, soaking the filter cake with a small amount of absolute ethyl alcohol, and carrying out suction filtration to obtain the copper ion-containing hydrotalcite, wherein the hydrotalcite can be directly used without drying.
2) Preparation of nano-copper/hydrotalcite-like compound
Weighing 0.01g of PVP, dissolving in 5mL of deionized water, stirring and dissolving in a constant-temperature water bath kettle at 30 ℃, adding the dissolved PVP aqueous solution into a beaker filled with 1g of copper ion-containing hydrotalcite after suction filtration, adding 55mL of deionized water, placing in an ultrasonic cleaning machine, oscillating for 20min, adding 40mL of absolute ethanol (the ratio of the deionized water to the absolute ethanol is 3:2), slowly dropwise adding 20mL of 40% hydrazine hydrate into the mixed aqueous solution containing the copper ion-containing hydrotalcite under the stirring condition, enabling the solution to become red immediately, continuing stirring and reacting for 1h after the dropwise addition is finished, standing for 3h, pouring out supernatant, washing for 3 times with the absolute ethanol, and performing suction filtration to obtain the nano copper/hydrotalcite with the molar ratio of magnesium, aluminum and copper being 2:1: 1.
Magnesium was prepared using the above method: aluminum: the molar ratio of copper is 2:2:1 respectively; 3:1: 1; 3:2: 1; 3:3: 1; 4:1: 1; 4:2: 1; 5:1: 1; 5:3:1, and preparing a nano copper simple substance.
3) Oxidation resistant treatment of nano-copper/hydrotalcite-like compounds
Firstly, preparing 200mL of absolute ethyl alcohol and butyl titanate solution with the volume fraction of 1:1, adding the absolute ethyl alcohol and butyl titanate solution into 10g of nano copper/hydrotalcite-like compound, stirring the mixed solution for 4h at the constant temperature of 70 ℃ by using a constant-temperature magnetic stirrer, fully stirring, and standing for 24 h. And filtering and washing the treated nano copper/hydrotalcite-like compound, and drying in a vacuum drying oven at 60 ℃ for 12 hours.
4) Preparation of nano-copper hydrotalcite-like conductive composite material-nano-copper/hydrotalcite-like/EA coating
According to the formula shown in the table 1, a proper amount of Acrylic Acid (AA) and a proper amount of Acrylamide (AM) are taken, stirred and mixed for 10min by a glass rod, ultrasonically dissolved for 20min by an ultrasonic cleaning machine, then a proper amount of nano copper/hydrotalcite-like compound is added, stirred for 5min, continuously vibrated by the ultrasonic cleaning machine until nano copper/hydrotalcite-like compound powder is completely dissolved, then a proper amount of Epoxy Acrylate (EA) and 1173 initiator are added, and continuously stirred by the glass rod until no bubbles exist in a mixed system. And then pouring the product on a smooth square glass plate, wherein the glass plate needs to be cleaned by absolute ethyl alcohol, scraping the product by a scraper with the thickness of 85 mu m, irradiating for a certain time by using an ultraviolet lamp, and curing to obtain the nano copper hydrotalcite conductive composite material, namely the nano copper/hydrotalcite-like compound/EA coating. Respectively preparing nano copper/hydrotalcite-like compound/EA coatings containing nano copper/hydrotalcite-like compound with different proportions, measuring all resistance values of the coatings, and measuring the optimal ratio of magnesium to aluminum.
TABLE 1 formulation of UV-curable coating of nano-silver (copper)/hydrotalcite-like compound/EA
EXAMPLE 2 preparation of Nano silver hydrotalcite-like conductive composite Material
1) Preparation of hydrotalcite containing silver ions
Weighing MgCl26.099g was dissolved in 10mL deionized water; weighing NaAlO20.8197g was dissolved in deionized water; weighing 1.001g of sodium stearate, adding 100mL of deionized water, stirring and dissolving in a constant-temperature water bath kettle at 40 ℃, and preparing an aqueous solution with the mass fraction of about 1%; weighing AgNO31.6987g was dissolved in 10mL of deionized water. 50mL of sodium stearate aqueous solution is weighed and poured into a three-neck flask, and AgNO is added3The aqueous solution was stirred for 5 minutes while the NaAlO was added2Solution and MgCl2Added dropwise to an aqueous solution of sodium stearate and, after completion of the dropwise addition, stirring was continued for 30 minutes. And (3) adjusting the pH value of the mixed system by using an aqueous solution of sodium hydroxide until the pH value of the mixed slurry is 9-10, stopping stirring, obtaining a light blue substance, and finally aging at 80 ℃ for 12 h. And after aging, carrying out suction filtration, washing the filter cake with deionized water until the pH of the filtrate is 7-8, soaking the filter cake with a small amount of absolute ethyl alcohol, and carrying out suction filtration to obtain the silver ion-containing hydrotalcite, wherein the silver ion-containing hydrotalcite can be directly used without drying.
2) Preparation of nano silver/hydrotalcite-like compound
Weighing 0.02g of PVP, dissolving in 5mL of deionized water, stirring and dissolving in a constant-temperature water bath kettle at 30 ℃, adding the dissolved PVP aqueous solution into a beaker filled with 1g of silver ion-containing hydrotalcite after suction filtration, adding 55mL of deionized water, placing in an ultrasonic cleaning machine, oscillating for 20 minutes, adding 40mL of absolute ethanol (the ratio of the deionized water to the absolute ethanol is 3:2), slowly dripping 20mL of 40% hydrazine hydrate into the mixed aqueous solution containing the copper hydrotalcite under the stirring condition, changing the solution from white to grey, continuing stirring and reacting for 1 hour after the dripping is finished, standing for 3 hours, pouring out supernatant, washing for 3 times with the absolute ethanol, carrying out suction filtration to obtain nano silver/hydrotalcite, and placing in a vacuum drying oven at 60 ℃ for drying for 12 hours.
3) Preparation of nano silver hydrotalcite-like conductive composite material-nano silver/hydrotalcite-like compound/EA coating
According to the formula shown in the table 1, a proper amount of nano silver/hydrotalcite-like powder is weighed, added into acrylic acid and acrylamide in a fixed proportion, continuously stirred and mixed by using a glass rod, then ultrasonically oscillated by an ultrasonic machine until the nano silver/hydrotalcite-like powder is dissolved in an acrylic acid mixed solution, then a proper amount of epoxy acrylate and 1173 photoinitiator are added, continuously stirred by using the glass rod, then placed into an ultrasonic cleaning machine, and ultrasonically oscillated until no bubbles are generated in a mixed system. And then pouring the product on a smooth square glass plate, wherein the glass plate needs to be cleaned by absolute ethyl alcohol, scraping the product by a scraper with the thickness of 85 mu m, irradiating for a certain time by using an ultraviolet lamp, and curing to obtain the nano silver hydrotalcite-like conductive composite material, namely the nano silver/hydrotalcite-like compound/EA coating.
Example 3 Infrared spectroscopic analysis of Nano copper/silver hydrotalcite-like conductive composite Material
The infrared spectra of the products prepared in examples 1 and 2 were measured by FT-IR and were investigated at 4000-500 cm-1And (3) according to the change condition of the vibration expansion peak, grinding the solid powder and the potassium bromide according to the mass ratio of 1:40, pressing the ground solid powder and the potassium bromide into small slices, detecting the small slices, observing the fluctuation condition of the absorption characteristic peak, and analyzing the synthetic effect of the prepared product.
As can be seen from FIG. 1, curve a is at 3447cm-1Has a stretching vibration absorption peak of-OH between hydrotalcite-like slabs, 614cm-1Has telescopic vibration absorption peaks of Mg-OH and Al-OH of 1641cm-1Has a stretching vibration absorption peak of C ═ O in pyrrolidone group, 1110cm-1The infrared C ═ O absorption peak of the hybrid formed by the nano copper and PVP is analyzed, and the nano copper/hydrotalcite-like compound is synthesized experimentally. Curve b at 3447cm-1Is positioned at 614cm, which is the stretching vibration absorption peak of-OH between hydrotalcite-like slabs-1The Mg-OH and Al-OH telescopic vibration absorption peaks exist, and the magnesium-aluminum hydrotalcite is synthesized by the above analysis and experiments.
As can be seen from FIG. 2, at 3447cm-1Has a stretching vibration peak of-OH between hydrotalcite-like slabs, 614cm-1There exist telescopic vibration peaks of Mg-OH and Al-OH, 1673cm-1The infrared C ═ O absorption peak of the hybrid formed by the nano silver and the PVP exists, and the nano silver/hydrotalcite-like compound is synthesized through the above analysis and experiments.
Example 4 ultraviolet spectroscopy analysis of a nanosized copper/silver hydrotalcite-like conductive composite
And (3) detecting the ultraviolet-visible spectrum by using the cured nano silver/hydrotalcite-like compound/EA coating in the embodiment 2 by using an ultraviolet-visible spectrophotometer within the wavelength range of 200-800 nm.
As can be seen from FIG. 3, three characteristic absorption peaks appear in the UV-VIS spectrum of the nano-silver/hydrotalcite-like compound/EA coating, at 207nm, 427nm and 564nm, respectively. Wherein the newly appeared absorption peak at 427nm is the characteristic absorption peak of nano-silver, which indicates the presence of nano-silver in the composite material.
Example 5 fluorescence Spectroscopy analysis of Nano copper/silver hydrotalcite-like conductive composite Material
Under the conditions that 280nm is fixed as an excitation wavelength and the width of a slit is 5nm, the content of the nano silver/hydrotalcite-like compound is changed, and the fluorescence intensity of the nano silver/hydrotalcite-like compound/EA coating is detected to obtain the fluorescence spectrogram shown in the figure 4. As can be seen from FIG. 4, the fluorescence peak of the nano-silver/hydrotalcite-like compound/EA coating is at 348 nm. In general, the fluorescence intensity of the coating with the nano silver/hydrotalcite-like compound content of 10% is the maximum, and the fluorescence intensity gradually decreases with the decrease of the nano silver/hydrotalcite-like compound content. But when the content is between 3 percent, 5 percent and 7 percent, the fluorescence intensity of the nano silver/hydrotalcite-like compound/EA coating is not changed greatly. When the content of the nano silver/hydrotalcite-like compound is 1%, the fluorescence intensity of the nano silver/hydrotalcite-like compound/EA coating is the lowest.
Example 6 measurement of resistance value of Nano copper/silver hydrotalcite-like conductive composite Material
The cured coatings of examples 1 and 2 were placed in a volume and surface resistance measuring instrument to measure the resistance values, the surface conductivity of the composite film was characterized by the obtained resistance values, and the conductivity was judged from the resistance values.
Fixing the amount of copper nitrate, changing the proportion of magnesium and aluminum, and measuring the resistance value of the nano-copper/hydrotalcite-like compound/EA coating, wherein the result is shown in figure 5. As can be seen from FIG. 5, the magnesium-aluminum ratio has a significant influence on the conductivity of the nano-copper/hydrotalcite-like compound/EA coating, and the resistance values of the coating are all 108～109In the range of omega. The conductivity changes along with the change of the proportion of magnesium and aluminum. When the ratio of magnesium to aluminum is 2:1 and 2:2, the resistance value of the nano-copper/hydrotalcite-like compound/EA coating is higher, and when the ratio of magnesium to aluminum is 3:1, the conductivity is strongest, and the resistance value is 0.336 multiplied by 108Ω。
Fixing the composition of the coating, varying the nanometresThe silver/hydrotalcite-like compound content, the resistance value of the nano silver/hydrotalcite-like compound/EA coating is measured, and the result is shown in figure 6. As can be seen from FIG. 6, the prepared nano silver/hydrotalcite/EA coating has a resistance value of 0.26 × 106～1×106In the range of omega. The conductivity of the nano silver/hydrotalcite-like compound/EA coating is better than that of the nano copper/hydrotalcite-like compound/EA coating.
Fixing the composition of the composite coating, changing the types and the content of the conductive particles, and measuring the resistance value of the nano silver/hydrotalcite-like compound/EA coating, wherein the result is shown in figure 7. As can be seen from FIG. 7, the resistance values of the nano-silver/hydrotalcite-like compound/EA coating were all 106～107Between Ω, magnesium: aluminum: the ratio of silver is 3:1:3, and when the content of the nano silver/hydrotalcite-like compound in the nano silver/hydrotalcite-like compound/EA coating is 7 percent (mass fraction), the resistance value is 0.26 multiplied by 106Omega, the conductivity is best at this moment.
The above description is only a preferred embodiment of the present invention, and therefore should not be taken as limiting the scope of the invention, which is defined by the appended claims and their equivalents.
Claims (10)
1. A preparation method of a nano copper/silver hydrotalcite-like conductive composite material is characterized by comprising the following steps: the method comprises the following steps:
1) adding Cu (NO) to aqueous sodium stearate solution3)2Aqueous solution or AgNO3Mixing the aqueous solution uniformly, and simultaneously dropwise adding NaAlO into the aqueous solution2Solution and MgCl2Uniformly mixing the solution, adjusting the pH value to 9-10, and then aging at 75-85 ℃ for 10-14 h; after aging, carrying out solid-liquid separation, washing the solid part until the pH value of a washing liquid is 7-8, soaking the solid part with absolute ethyl alcohol, and carrying out solid-liquid separation to obtain copper ion-containing hydrotalcite or silver ion-containing hydrotalcite;
2) mixing PVP aqueous solution with the copper ion-containing hydrotalcite or the silver ion-containing hydrotalcite, adding water, carrying out ultrasonic oscillation treatment, adding absolute ethyl alcohol, then dropwise adding hydrazine hydrate, stirring for reaction after dropwise adding is finished, standing, removing supernate, washing the rest part with absolute ethyl alcohol, and carrying out solid-liquid separation to obtain nano copper/hydrotalcite-like compound or nano silver/hydrotalcite-like compound;
3) and uniformly mixing acrylic acid and acrylamide, adding the nano-copper/hydrotalcite-like compound or the nano-silver/hydrotalcite-like compound, completely dissolving the nano-copper/hydrotalcite-like compound or the nano-silver/hydrotalcite-like compound, adding epoxy acrylate, uniformly mixing, and curing to obtain the nano-copper hydrotalcite-like conductive composite material or the nano-silver hydrotalcite-like conductive composite material.
2. The preparation method of the nano copper/silver hydrotalcite-like conductive composite material according to claim 1, wherein the preparation method comprises the following steps: in the nano-copper hydrotalcite-like conductive composite material, the ratio of magnesium to aluminum is 2.5-3.5: 1.
3. The preparation method of the nano copper/silver hydrotalcite-like conductive composite material according to claim 1, wherein the preparation method comprises the following steps: in the nano-silver hydrotalcite-like conductive composite material, the proportion of magnesium, aluminum and silver is 2.5-3.5: 0.8-1.2: 2.5-3.5, and the content of nano-silver/hydrotalcite-like compound is 6-8%.
4. The preparation method of the nano copper/silver hydrotalcite-like conductive composite material according to claim 1, wherein the preparation method comprises the following steps: in the step 2), the volume ratio of the total volume of the water in the PVP aqueous solution and the added water to the absolute ethyl alcohol is 2-4: 1-3.
5. The preparation method of the nano copper/silver hydrotalcite-like conductive composite material according to claim 1, wherein the preparation method comprises the following steps: in the step 2), the concentration of hydrazine hydrate is 38-42%.
6. The preparation method of the nano copper/silver hydrotalcite-like conductive composite material according to claim 1, wherein the preparation method comprises the following steps: in the step 3), the curing mode is ultraviolet irradiation curing, and a photoinitiator is also added into the reaction system in the step 3).
7. The preparation method of the nano copper/silver hydrotalcite-like conductive composite material according to claim 6, wherein the preparation method comprises the following steps: the photoinitiator is 1173.
8. The preparation method of the nano copper/silver hydrotalcite-like conductive composite material according to claim 1, wherein the preparation method comprises the following steps: in the step 3), the mass ratio of epoxy acrylate, acrylic acid and acrylamide to the nano-copper/hydrotalcite-like compound or the nano-silver/hydrotalcite-like compound is 3.1-3.2: 0.7-0.8: 0.9-1.1: 0.045-0.6.
9. The preparation method of the nano copper/silver hydrotalcite-like conductive composite material according to claim 1, wherein the preparation method comprises the following steps: the nano copper/hydrotalcite-like compound is subjected to oxidation resistance treatment and then used for preparing a nano copper hydrotalcite-like compound conductive composite material, wherein the oxidation resistance treatment comprises the following steps: adding the nano copper/hydrotalcite-like compound into a mixed solution of absolute ethyl alcohol and butyl titanate with the volume ratio of 0.8-1.2: 0.8-1.2, stirring for 3-5 h at 65-75 ℃, standing for 22-26 h, filtering, washing and drying to obtain the nano copper/hydrotalcite-like compound.
10. A nano copper/silver hydrotalcite-like conductive composite material prepared by the preparation method according to any one of claims 1 to 9.
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1827702A (en) * | 2006-02-22 | 2006-09-06 | 北京化工大学 | Conductive polymer-intercalated hydrotalcite and method for preparing same |
| KR100704316B1 (en) * | 2006-05-29 | 2007-04-09 | 주식회사 동부한농 | Antibacterial resin including nano sized silver and method for producing the same |
| CN101980963A (en) * | 2008-03-31 | 2011-02-23 | 户田工业株式会社 | Particulate powder of hydrotalcite type compound, chlorinated-resin stabilizer comprising the particulate powder of hydrotalcite type compound, and chlorinated-resin composition |
| CN102139212A (en) * | 2011-01-14 | 2011-08-03 | 北京化工大学 | Method for preparing hydrotalcite supported silver catalyst and application thereof |
| JP2012188390A (en) * | 2011-03-10 | 2012-10-04 | Daicel Corp | Method for producing 1,2-propanediol |
| CN102921417A (en) * | 2012-10-25 | 2013-02-13 | 常州大学 | Method for preparing nanometer copper oxide catalyst |
| CN103464159A (en) * | 2013-09-11 | 2013-12-25 | 北京化工大学 | Copper-iron based catalyst and application thereof in preparing low mixed alcohols by catalyzing synthesis gas |
| CN103554335A (en) * | 2013-11-05 | 2014-02-05 | 北京理工大学 | High-abrasion-resistant light-cured acrylate/hydrotalcite nano composite material and production method thereof |
| CN103819591A (en) * | 2014-03-21 | 2014-05-28 | 中国科学院上海硅酸盐研究所 | Copper nano wire/polyacrylate composite material and preparation method thereof |
| CN108796549A (en) * | 2018-05-23 | 2018-11-13 | 深圳大学 | Metallic compound coats composite material, preparation method and the application of copper nano-wire |
-
2019
- 2019-04-23 CN CN201910329790.0A patent/CN110183592B/en not_active Expired - Fee Related
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1827702A (en) * | 2006-02-22 | 2006-09-06 | 北京化工大学 | Conductive polymer-intercalated hydrotalcite and method for preparing same |
| KR100704316B1 (en) * | 2006-05-29 | 2007-04-09 | 주식회사 동부한농 | Antibacterial resin including nano sized silver and method for producing the same |
| CN101980963A (en) * | 2008-03-31 | 2011-02-23 | 户田工业株式会社 | Particulate powder of hydrotalcite type compound, chlorinated-resin stabilizer comprising the particulate powder of hydrotalcite type compound, and chlorinated-resin composition |
| CN102139212A (en) * | 2011-01-14 | 2011-08-03 | 北京化工大学 | Method for preparing hydrotalcite supported silver catalyst and application thereof |
| JP2012188390A (en) * | 2011-03-10 | 2012-10-04 | Daicel Corp | Method for producing 1,2-propanediol |
| CN102921417A (en) * | 2012-10-25 | 2013-02-13 | 常州大学 | Method for preparing nanometer copper oxide catalyst |
| CN103464159A (en) * | 2013-09-11 | 2013-12-25 | 北京化工大学 | Copper-iron based catalyst and application thereof in preparing low mixed alcohols by catalyzing synthesis gas |
| CN103554335A (en) * | 2013-11-05 | 2014-02-05 | 北京理工大学 | High-abrasion-resistant light-cured acrylate/hydrotalcite nano composite material and production method thereof |
| CN103819591A (en) * | 2014-03-21 | 2014-05-28 | 中国科学院上海硅酸盐研究所 | Copper nano wire/polyacrylate composite material and preparation method thereof |
| CN108796549A (en) * | 2018-05-23 | 2018-11-13 | 深圳大学 | Metallic compound coats composite material, preparation method and the application of copper nano-wire |
Non-Patent Citations (5)
| Title |
|---|
| A recyclable/reusable hydrotalcite supported copper nano catalyst for 1,4-disubstituted-1,2,3-triazole synthesis via click chemistry approach;Mitali Chetia et al.;《Tetrahedron Letters》;20171216;第59卷;第397-401页 * |
| Monodispersed and Stable Nano Copper(0) from Copper-Aluminium Hydrotalcite: Importance in C-C Couplings of Deactivated Aryl Chlorides;Racha Arundhathi et al.;《Adv. Synth. Catal.》;20130222;第355卷;第751-756页 * |
| Preparation and properties of exfoliated nanocomposites through intercalated a photoinitiator into LDH interlayer used for UV curing coatings;Yan Yuan et al.;《Progress in Organic Coatings》;20101231;第69卷;第92-99页 * |
| 掺杂Cu2+离子水滑石[CdxMg(6-x)Al2(OH)16]2+[S•2H2O]2-导电性质的研究;包玉敏等;《高等学校化学学报》;19971130;第18卷(第11期);第1746-1749页 * |
| 酰胺-水滑石-环氧树脂防腐涂料的制备及性能;张小博;《电镀与涂饰》;20181231;第37卷(第6期);第242-246页 * |
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