CN115650278B - Nanometer copper hydroxide and preparation method thereof - Google Patents
Nanometer copper hydroxide and preparation method thereof Download PDFInfo
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- CN115650278B CN115650278B CN202211316742.6A CN202211316742A CN115650278B CN 115650278 B CN115650278 B CN 115650278B CN 202211316742 A CN202211316742 A CN 202211316742A CN 115650278 B CN115650278 B CN 115650278B
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- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 title claims abstract description 84
- 239000005750 Copper hydroxide Substances 0.000 title claims abstract description 84
- 229910001956 copper hydroxide Inorganic materials 0.000 title claims abstract description 84
- 238000002360 preparation method Methods 0.000 title claims abstract description 42
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 79
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 79
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 79
- 239000007864 aqueous solution Substances 0.000 claims abstract description 31
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 29
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229940116318 copper carbonate Drugs 0.000 claims abstract description 21
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 239000000725 suspension Substances 0.000 claims abstract description 11
- ZMMDPCMYTCRWFF-UHFFFAOYSA-J dicopper;carbonate;dihydroxide Chemical compound [OH-].[OH-].[Cu+2].[Cu+2].[O-]C([O-])=O ZMMDPCMYTCRWFF-UHFFFAOYSA-J 0.000 claims abstract description 8
- 239000007787 solid Substances 0.000 claims abstract description 8
- PTVDYARBVCBHSL-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu] PTVDYARBVCBHSL-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 3
- 239000002245 particle Substances 0.000 claims description 40
- 238000001291 vacuum drying Methods 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 3
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 61
- 238000000034 method Methods 0.000 abstract description 8
- 230000000052 comparative effect Effects 0.000 description 14
- 238000001514 detection method Methods 0.000 description 9
- 239000002994 raw material Substances 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 210000004027 cell Anatomy 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 102000004190 Enzymes Human genes 0.000 description 3
- 108090000790 Enzymes Proteins 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 239000004563 wettable powder Substances 0.000 description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 241000700605 Viruses Species 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 239000003899 bactericide agent Substances 0.000 description 2
- 210000000170 cell membrane Anatomy 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- -1 mordants Substances 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 206010059866 Drug resistance Diseases 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 229910002794 Si K Inorganic materials 0.000 description 1
- 241001122767 Theaceae Species 0.000 description 1
- 230000003113 alkalizing effect Effects 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000003674 animal food additive Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000009991 scouring Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
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- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The application relates to the technical field of nanometer basic sodium hydroxide, in particular to nanometer copper hydroxide and a preparation method thereof, wherein the preparation method of the nanometer copper hydroxide comprises the following preparation steps: s1, preparing polyvinylpyrrolidone aqueous solution with concentration more than or equal to 1 mol/L; s2, simultaneously dropwise adding the polyvinylpyrrolidone aqueous solution and ammonia water into the suspension of basic copper carbonate and water at the temperature of 25-35 ℃ while stirring, wherein the reaction end point is pH=7.5-9.5; wherein, in the suspension of basic cupric carbonate and water, the weight ratio of basic cupric carbonate to water is 1: (3-10); s3, filtering the turbid liquid obtained in the step S2 to obtain a solid; s4, drying the solid obtained in the step S3 to obtain nano copper hydroxide; the method has the advantage of simplifying the preparation method for preparing the nano copper hydroxide.
Description
Technical Field
The application relates to the technical field of nanometer basic sodium hydroxide, in particular to nanometer copper hydroxide and a preparation method thereof.
Background
Copper hydroxide is commonly used as an analytical reagent, and can also be used for medicines, pollution-free pesticides, catalysts, mordants, pigments, feed additives, paper stains and the like. And copper hydroxide is a main raw material for preparing a novel pollution-free green low-toxicity bactericide. Copper hydroxide can enter virus cells to kill viruses, but cannot enter plant cells, is safe to crops, does not generate drug resistance, can be used in the picking period of crops, such as tea leaves and fruits, and is harmless to people and livestock. Therefore, copper hydroxide is an environment-friendly protective bactericide advocated by various countries.
Along with the development of nano technology, nano basic sodium hydroxide is developed gradually and enters the market for application. The development of nano technology provides a wider market prospect for the application of copper hydroxide. The specific surface area of the nanometer basic sodium hydroxide is larger, so that the surface atoms are equivalent to bulk atoms, the surface atomic activity is greatly improved, the free active copper ions are doubly improved, and the released copper ions react with fungi and genes in cells, namely react with-SH-containing enzymes on cell membranes to deactivate the enzymes and react with cations such as H on the surfaces of the cells + 、Ca 2+ 、Mg 2+ 、K + The exchange, the protein of the cell membrane of the thallus is coagulated and permeated into the thallus to combine with certain enzymes, which affects the activity and causes the death of the germ; the nanometer basic sodium hydroxide wettable powder is uniformly sprayed, has extremely strong adhesiveness, is resistant to rain and scouring, has a lasting period of 20-25 days, and does not need to be re-sprayed after rain. And the traditional Boerdosol has large spraying quantity, and the liquid medicine is dripped into the ground to cause the land to be alkalized. The sterilization effect of the nano basic sodium hydroxide wettable powder is improved, and the dosage of the nano basic sodium hydroxide wettable powder is greatly higher than that of the traditional copper hydroxide wettable powderThe method reduces the residue, sprays uniformly, prevents the liquid medicine from dripping into the ground, and prevents the land from alkalizing; the nanometer basic sodium hydroxide can be directly diluted and sprayed, so that the spraying labor amount is reduced.
The application of nano sodium hydroxide is gradually wide, and the demand of nano sodium hydroxide is gradually increased. However, the related preparation method still has great difficulty, and the cost is high, which is unfavorable for mass production.
Disclosure of Invention
In order to simplify the preparation method of nano copper hydroxide, the application provides nano copper hydroxide and a preparation method thereof.
In a first aspect, the present application provides a method for preparing nano copper hydroxide, which adopts the following technical scheme:
the preparation method of the nano copper hydroxide comprises the following preparation steps:
s1, preparing polyvinylpyrrolidone aqueous solution with concentration more than or equal to 1 mol/L;
s2, simultaneously dropwise adding the polyvinylpyrrolidone aqueous solution and ammonia water into the suspension of basic copper carbonate and water at the temperature of 25-35 ℃ while stirring, wherein the reaction end point is pH=7.5-9.5; wherein, in the suspension of basic cupric carbonate and water, the weight ratio of basic cupric carbonate to water is 1: (3-10);
s3, filtering the turbid liquid obtained in the step S2 to obtain a solid;
s4, drying the solid obtained in the step S3 to obtain the nano copper hydroxide.
By adopting the technical scheme, polyvinylpyrrolidone is added, so that the polyvinylpyrrolidone can be adsorbed on the particle surfaces of nano copper hydroxide when the nano copper hydroxide is formed, thereby forming steric hindrance and limiting the continuous increase of the particles, so that the average particle size of the prepared nano copper hydroxide is smaller, and the specific surface area of the prepared nano copper hydroxide is larger; in addition, the preparation raw materials are simple, except polyvinylpyrrolidone, ammonia water and basic copper carbonate, no additional raw materials are needed, and the reaction temperature is at room temperature.
As preferable: the mass fraction of the ammonia water is 10-25%.
By adopting the technical scheme, the mass fraction of the ammonia water is in the range, so that the average particle size of the nano copper hydroxide is smaller, but when the mass fraction is too small, the consumption of the polyvinylpyrrolidone is larger, and the cost is increased; when the mass fraction is too large, the average particle size of the nano sodium hydroxide is increased to a certain extent.
As preferable: the dropping speed of the polyvinylpyrrolidone aqueous solution and the ammonia water is 8-12mL/min.
By adopting the technical scheme, the dripping speed of the polyvinylpyrrolidone aqueous solution and the ammonia water is an important factor for controlling the average particle size of the nano copper hydroxide, and when the dripping speed of the polyvinylpyrrolidone aqueous solution and the ammonia water is too high, the average particle size of the nano sodium hydroxide is obviously increased; when the mass fraction of the ammonia water is 25%, the average particle size of the nano sodium hydroxide is increased to 98nm when the dropping speed reaches 15mL/min, so that the dropping speeds of the polyvinylpyrrolidone aqueous solution and the ammonia water are not excessively large.
As preferable: the concentration of the polyvinylpyrrolidone aqueous solution is 1-3mol/L.
By adopting the technical scheme, the particle size of the nano copper hydroxide is gradually reduced along with the increase of the concentration of the polyvinylpyrrolidone, and the concentration of the polyvinylpyrrolidone is an important factor for controlling the average particle size of the nano copper hydroxide; the concentration is too small, and the average grain diameter of the nano sodium hydroxide can be increased to more than 120 nm; the concentration is too large, which is not beneficial to cost control.
As preferable: the weight part ratio of the basic copper carbonate to the polyvinylpyrrolidone is 1: (0.5-2.5).
By adopting the technical scheme, the dosage of the polyvinylpyrrolidone is too high, the preparation cost is increased, and the dosage of the polyvinylpyrrolidone is reduced under the condition that the average particle size of the nano sodium hydroxide meets the requirement, thereby being beneficial to reducing the cost.
As preferable: the average molecular weight of the polyvinylpyrrolidone is 45000-58000.
By adopting the technical scheme, when the molecular weight of the polyvinylpyrrolidone is within the range of 45000-58000, the average particle size of the nano copper hydroxide is not changed greatly, and is 50nm or less, the average molecular weight of the polyvinylpyrrolidone is not reduced to 45000 or less, and when the average molecular weight is reduced to 40000, the average particle size of the copper hydroxide is greatly increased, and 356nm can be achieved.
As preferable: and S4, adopting vacuum drying, wherein the vacuum drying temperature is 30-60 ℃.
By adopting the technical scheme, when the vacuum drying temperature is too high, the nano sodium hydroxide structure is easy to lose water and collapse.
As preferable: the preparation steps of the polyvinylpyrrolidone aqueous solution are as follows:
the method comprises the steps of respectively calculating the dosage of polyvinylpyrrolidone and water according to the concentration of polyvinylpyrrolidone aqueous solution, weighing polyvinylpyrrolidone and water according to the dosage, adding polyvinylpyrrolidone into one fifth to one third of the volume of water, performing ultrasonic dispersion at 25-30 ℃ for 25-35min, adding the rest water, mixing uniformly, and standing for 25-35min for standby.
By adopting the technical scheme, the dissolution rate of polyvinylpyrrolidone can be improved by dispersing through ultrasound.
In a second aspect, the present application provides a nano copper hydroxide, which adopts the following technical scheme:
a nano copper hydroxide produced by the method for producing a nano copper hydroxide according to any one of claims 1 to 8.
As preferable: the average grain diameter of the nano copper hydroxide is 5-50nm.
In summary, the present application includes at least one of the following beneficial technical effects:
1. by adding polyvinylpyrrolidone, the nano copper hydroxide can be adsorbed on the particle surfaces of the nano copper hydroxide when the nano copper hydroxide is formed, so that steric hindrance is formed, the continuous increase of the particles is limited, the average particle size of the prepared nano copper hydroxide is smaller, and the specific surface area of the prepared nano copper hydroxide is larger.
2. As the concentration of polyvinylpyrrolidone increases, the particle size of nano copper hydroxide is gradually reduced; along with the gradual decrease of the dropping speed of the polyvinylpyrrolidone aqueous solution and the ammonia water, the average particle diameter of the nano sodium hydroxide is also reduced to a certain extent; when the dripping speed of the polyvinylpyrrolidone aqueous solution and the ammonia water is too high, the average particle size of the nano sodium hydroxide is obviously increased; when the average molecular weight of polyvinylpyrrolidone is within the range of 45000-58000, the average particle size of nano copper hydroxide is smaller, and when the average molecular weight is reduced to 40000, the average particle size of copper hydroxide is greatly increased; the concentration of polyvinylpyrrolidone, the dropping speed of aqueous solution of polyvinylpyrrolidone and ammonia water, and the average molecular weight of polyvinylpyrrolidone are all important factors for controlling the average particle size of nano copper hydroxide.
3. The average particle size of the nano copper hydroxide prepared by the method is below 50nm, and the minimum particle size can reach 5nm; the conversion rate of the basic copper carbonate is 90.1% or more; after the reaction is finished, the weight parts ratio of basic copper carbonate to polyvinylpyrrolidone is 1: (0.5-2.5); it is demonstrated that nano copper hydroxide with smaller average particle size can be prepared by controlling the reaction conditions in the presence of polyvinylpyrrolidone.
Drawings
Fig. 1 and 2 are SEM images of copper hydroxide prepared in example 14.
Fig. 3 is an EDS diagram of copper hydroxide prepared in example 14.
Fig. 4 is an XRD pattern of copper hydroxide prepared in example 14.
Detailed Description
The present application is described in further detail below in conjunction with the detailed description.
Raw materials
The raw materials used in the examples of the present application are all common commercial products.
Examples
Example 1
The preparation method of the nano copper hydroxide comprises the following preparation steps:
s1, preparing a polyvinylpyrrolidone aqueous solution with the concentration of 1 mol/L:
calculating the dosage of polyvinylpyrrolidone and water respectively by the concentration of the polyvinylpyrrolidone aqueous solution, weighing polyvinylpyrrolidone and water according to the dosage, adding polyvinylpyrrolidone into one-fourth volume of water, performing ultrasonic dispersion for 30min at 30 ℃, adding the rest water, mixing uniformly, and standing for 30min for later use; wherein the molecular weight of polyvinylpyrrolidone is 45000;
s2, simultaneously dropwise adding the polyvinylpyrrolidone aqueous solution and ammonia water into a suspension of basic copper carbonate and water at the temperature of 30 ℃, wherein the dropwise adding speed of the polyvinylpyrrolidone aqueous solution and the ammonia water is 12mL/min, and stirring is carried out while dropwise adding, and the reaction end point is pH=7.5; wherein, in the suspension of basic cupric carbonate and water, the weight ratio of basic cupric carbonate to water is 1:10; wherein the mass fraction of the ammonia water is 10%;
s3, filtering the turbid liquid obtained in the step S2 to obtain a solid;
and S4, carrying out vacuum drying on the solid obtained in the step S3, wherein the vacuum drying temperature is 30 ℃, and obtaining the nano copper hydroxide.
Example 2
The preparation method of nano copper hydroxide is different from example 1 in that the mass fraction of ammonia water is 15%, and the rest steps are the same as those of example 1.
Example 3
The preparation method of nano copper hydroxide is different from example 1 in that the mass fraction of ammonia water is 20%, and the rest steps are the same as those of example 1.
Example 4
The preparation method of nano copper hydroxide is different from example 1 in that the mass fraction of ammonia water is 25%, and the rest steps are the same as those of example 1.
Example 5
The preparation method of nano copper hydroxide is different from example 2 in that the concentration of polyvinylpyrrolidone aqueous solution is 2mol/L, and the rest steps are the same as those of example 2.
Example 6
The preparation method of nano copper hydroxide is different from example 2 in that the concentration of polyvinylpyrrolidone aqueous solution is 3mol/L, and the rest steps are the same as in example 2.
Example 7
The preparation method of nano copper hydroxide is different from example 5 in that the dripping speed of the polyvinylpyrrolidone aqueous solution and the ammonia water is 10mL/min, and the rest steps are the same as those of example 5.
Example 8
The preparation method of nano copper hydroxide is different from example 5 in that the dripping speed of the polyvinylpyrrolidone aqueous solution and the ammonia water is 8mL/min, and the rest steps are the same as those of example 5.
Example 9
The preparation method of nano copper hydroxide is different from example 8 in that the average molecular weight of polyvinylpyrrolidone is 50000, and the rest steps are the same as in example 8.
Example 10
The preparation method of nano copper hydroxide is different from example 8 in that the average molecular weight of polyvinylpyrrolidone is 58000, and the rest steps are the same as in example 8.
Example 11
The preparation method of nano copper hydroxide is different from example 8 in that the reaction end point in S2 is ph=8, and the rest steps are the same as example 8.
Example 12
The preparation method of nano copper hydroxide is different from example 8 in that the reaction end point in S2 is ph=9.5, and the rest steps are the same as example 8.
Example 13
The preparation method of nano copper hydroxide is different from example 11 in that in the suspension of basic copper carbonate and water, the weight ratio of basic copper carbonate to water is 1:7, the rest of the procedure is the same as in example 11.
Example 14
The preparation method of nano copper hydroxide is different from example 11 in that in the suspension of basic copper carbonate and water, the weight ratio of basic copper carbonate to water is 1:3, the rest of the procedure is the same as in example 11.
Example 15
The preparation method of nano copper hydroxide is different from example 1 in that the vacuum drying temperature in S4 is 60 ℃, and the rest steps are the same as those in example 1.
Comparative example
Comparative example 1
The preparation method of nano copper hydroxide is different from example 1 in that polyvinylpyrrolidone is replaced by equal parts by weight of fatty alcohol polyoxypropylene ether SPO-30, and the rest steps are the same as those of example 1.
Comparative example 2
The preparation method of nano copper hydroxide is different from example 4 in that the dripping speed of the polyvinylpyrrolidone aqueous solution and the ammonia water is 15mL/min, and the rest steps are the same as those of example 4.
Comparative example 3
The preparation method of nano copper hydroxide is different from example 1 in that the concentration of polyvinylpyrrolidone aqueous solution is 0.5mol/L, and the rest steps are the same as in example 1.
Comparative example 4
The preparation method of nano copper hydroxide is different from example 1 in that the average molecular weight of polyvinylpyrrolidone is 40000, and the rest steps are the same as example 1.
Comparative example 5
The preparation method of nano copper hydroxide is different from example 1 in that the vacuum drying temperature in S4 is 70 ℃, and the rest steps are the same as those of example 1.
Performance test
Detection method/test method
Preparing nano copper hydroxide according to the preparation methods of examples 1-13 and comparative examples 1-5, detecting the average particle size by a scanning electron microscope, and calculating the weight part ratio of the basic copper carbonate to the polyvinylpyrrolidone consumption when the reaction is completed; the detection results are shown in Table 1.
Basic copper carbonate conversion: basic copper carbonate conversion = (molar amount of product actually obtained/molar amount of product theoretically produced) = 100%.
Wherein, the product obtained in comparative example 5 was dried in vacuum, and the structure thereof had a certain collapse, and the data thereof were not examined.
The particle size of the nano copper hydroxide prepared in example 14 was found to be about 5nm on average in FIGS. 1 and 2.
EDS spectrum processing in fig. 3: peaks that are not ignored; all elements analyzed (normalized), the number of repetitions was 5; wherein the standard samples are as follows:
the detection data are as follows:
| element(s) | Weight of (E) | Atoms |
| Percentage of | Percentage of | |
| C K | 25.52 | 45.36 |
| O K | 29.33 | 39.14 |
| Si K | 0.43 | 0.33 |
| Cl K | 0.51 | 0.31 |
| Cu L | 44.25 | 14.87 |
| Ta M | -0.03 | 0.00 |
| Total amount of | 100.00 |
The XRD pattern in fig. 4 is the same as the characteristic peak of nano copper hydroxide, and it can be confirmed that the prepared product is nano copper hydroxide.
TABLE 1 detection results for examples 1-15 and comparative examples 1-4
As can be seen from the detection data of examples 1-15 and comparative examples 1-5 and Table 1, the average particle size of the nano copper hydroxide prepared by the method is below 50nm, and the minimum particle size can reach 5nm; the conversion rate of the basic copper carbonate is 90.1% or more; after the reaction is finished, the weight parts ratio of basic copper carbonate to polyvinylpyrrolidone is 1: (0.5-2.5); it is demonstrated that nano copper hydroxide with smaller average particle size can be prepared by controlling the reaction conditions in the presence of polyvinylpyrrolidone.
As can be seen from the detection data of examples 1-4, the average particle size of the nano copper hydroxide is increased slightly when the mass fraction of the ammonia water is increased; however, the consumption of polyvinylpyrrolidone is less when the reaction is finished, which is beneficial to reducing the cost.
As can be seen from the examination data of examples 2 and examples 5 to 6, the particle size of the nano copper hydroxide gradually decreases as the concentration of polyvinylpyrrolidone increases; in combination with comparative example 3, the concentration of polyvinylpyrrolidone should not be too small; from the detection data of examples 5 and 7-8, the average particle size of the nano sodium hydroxide is also reduced to a certain extent along with the gradual reduction of the dropping speed of the polyvinylpyrrolidone aqueous solution and the ammonia water; when the dripping speed of the polyvinylpyrrolidone aqueous solution and the ammonia water is too high in combination with comparative example 2, the average particle size of the nano sodium hydroxide is obviously increased; it is explained that the concentration of polyvinylpyrrolidone, the dropping speed of aqueous polyvinylpyrrolidone solution and aqueous ammonia are all important factors for controlling the average particle size of nano copper hydroxide.
From the examination data of examples 8 and examples 9 to 10, it can be seen that the average particle size of the nano copper hydroxide does not vary much when the molecular weight of polyvinylpyrrolidone is within the range of 45000 to 58000. However, in combination with the test data of comparative example 4, it was not preferable that the average molecular weight of polyvinylpyrrolidone was reduced to 45000 or less, and when the average molecular weight was reduced to 40000, the average particle size of copper hydroxide was greatly increased.
As can be seen from the detection data of examples 8 and examples 11-12, the conversion rate of basic copper carbonate is improved to a certain extent along with the increase of the pH at the end point of the reaction, the average particle size of nano sodium hydroxide is not obviously influenced, and the consumption of polyvinylpyrrolidone is increased to a certain extent.
As can be seen from the examination data of examples 11 and examples 13 to 14, when the concentration of the basic copper carbonate suspension is reduced, the particle size of the nano copper hydroxide is reduced, but the conversion rate of the basic copper carbonate is reduced to a minimum of 5nm, and meanwhile, the consumption of polyvinylpyrrolidone is increased to some extent.
As can be seen from the detection data of example 1 and example 15, the vacuum drying temperature of the nano copper hydroxide is below 60 ℃; in combination with comparative example 5, the vacuum drying temperature is not too high.
The foregoing embodiments are all preferred examples of the present application, and are not intended to limit the scope of the present application in any way, therefore: all equivalent changes in structure, shape and principle of this application should be covered in the protection scope of this application.
Claims (1)
1. A preparation method of nano copper hydroxide is characterized in that: the preparation method comprises the following preparation steps:
s1, preparing a polyvinylpyrrolidone aqueous solution with the concentration of 2 mol/L;
s2, simultaneously dropwise adding the polyvinylpyrrolidone aqueous solution and ammonia water into a suspension of basic copper carbonate and water at the temperature of 30 ℃, and stirring while dropwise adding, wherein the reaction end point is pH=8; wherein, in the suspension of basic cupric carbonate and water, the weight ratio of basic cupric carbonate to water is 1:3, a step of;
s3, filtering the turbid liquid obtained in the step S2 to obtain a solid;
s4, drying the solid obtained in the step S3 to obtain nano copper hydroxide;
the mass fraction of the ammonia water is 15%;
the dropping speed of the polyvinylpyrrolidone aqueous solution and the ammonia water is 8mL/min;
the weight part ratio of the basic copper carbonate to the polyvinylpyrrolidone is 1:2.5;
the average molecular weight of the polyvinylpyrrolidone is 45000;
in the step S4, vacuum drying is adopted, and the vacuum drying temperature is 30 ℃;
the preparation steps of the polyvinylpyrrolidone aqueous solution are as follows:
calculating the dosage of polyvinylpyrrolidone and water respectively by the concentration of the polyvinylpyrrolidone aqueous solution, weighing polyvinylpyrrolidone and water according to the dosage, adding polyvinylpyrrolidone into one-fourth volume of water, performing ultrasonic dispersion for 30min at 30 ℃, adding the rest water, mixing uniformly, and standing for 30min for later use;
the average particle size of the nano copper hydroxide prepared by the preparation method of the nano copper hydroxide is 5nm.
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| Title |
|---|
| "杀菌剂用纳米氢氧化铜的制备及应用性能研究研究";徐爽;《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》(第12期);正文第30-60页 * |
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| Publication number | Publication date |
|---|---|
| CN115650278A (en) | 2023-01-31 |
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Denomination of invention: A nano copper hydroxide and its preparation method Granted publication date: 20240326 Pledgee: Zhejiang Fuyang Rural Commercial Bank branch of the new Limited by Share Ltd. Pledgor: Hangzhou Haoteng Technology Co.,Ltd. Registration number: Y2024980032756 |