CN116284838B - Method for manufacturing nano spherical metal nickel powder - Google Patents
Method for manufacturing nano spherical metal nickel powder Download PDFInfo
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- CN116284838B CN116284838B CN202310116484.5A CN202310116484A CN116284838B CN 116284838 B CN116284838 B CN 116284838B CN 202310116484 A CN202310116484 A CN 202310116484A CN 116284838 B CN116284838 B CN 116284838B
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 239000002184 metal Substances 0.000 title claims abstract description 40
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- 108010010803 Gelatin Proteins 0.000 claims abstract description 62
- 239000008273 gelatin Substances 0.000 claims abstract description 62
- 229920000159 gelatin Polymers 0.000 claims abstract description 62
- 235000019322 gelatine Nutrition 0.000 claims abstract description 62
- 235000011852 gelatine desserts Nutrition 0.000 claims abstract description 62
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 39
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 39
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 39
- 238000002360 preparation method Methods 0.000 claims abstract description 20
- UJTPZISIAWDGFF-UHFFFAOYSA-N ethenylsulfonylbenzene Chemical compound C=CS(=O)(=O)C1=CC=CC=C1 UJTPZISIAWDGFF-UHFFFAOYSA-N 0.000 claims abstract description 16
- RRIWRJBSCGCBID-UHFFFAOYSA-L nickel sulfate hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O RRIWRJBSCGCBID-UHFFFAOYSA-L 0.000 claims abstract description 14
- 229940116202 nickel sulfate hexahydrate Drugs 0.000 claims abstract description 14
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 13
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 31
- RHQDFWAXVIIEBN-UHFFFAOYSA-N Trifluoroethanol Chemical compound OCC(F)(F)F RHQDFWAXVIIEBN-UHFFFAOYSA-N 0.000 claims description 21
- 239000000843 powder Substances 0.000 claims description 19
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 9
- YOCIJWAHRAJQFT-UHFFFAOYSA-N 2-bromo-2-methylpropanoyl bromide Chemical compound CC(C)(Br)C(Br)=O YOCIJWAHRAJQFT-UHFFFAOYSA-N 0.000 claims description 8
- 230000001376 precipitating effect Effects 0.000 claims description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 230000004048 modification Effects 0.000 claims description 5
- 238000012986 modification Methods 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000012153 distilled water Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 238000002390 rotary evaporation Methods 0.000 claims description 2
- 239000002245 particle Substances 0.000 abstract description 23
- OOIBFPKQHULHSQ-UHFFFAOYSA-N (3-hydroxy-1-adamantyl) 2-methylprop-2-enoate Chemical compound C1C(C2)CC3CC2(O)CC1(OC(=O)C(=C)C)C3 OOIBFPKQHULHSQ-UHFFFAOYSA-N 0.000 abstract description 17
- 230000009467 reduction Effects 0.000 abstract description 17
- 239000003638 chemical reducing agent Substances 0.000 abstract description 3
- 239000002270 dispersing agent Substances 0.000 abstract description 3
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 235000019441 ethanol Nutrition 0.000 description 7
- 239000002105 nanoparticle Substances 0.000 description 7
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 6
- 230000002776 aggregation Effects 0.000 description 6
- 239000012086 standard solution Substances 0.000 description 6
- 238000002329 infrared spectrum Methods 0.000 description 5
- 229910001453 nickel ion Inorganic materials 0.000 description 5
- 238000005054 agglomeration Methods 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 3
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 239000003985 ceramic capacitor Substances 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- 238000004483 ATR-FTIR spectroscopy Methods 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000012869 ethanol precipitation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- BHZOKUMUHVTPBX-UHFFFAOYSA-M sodium acetic acid acetate Chemical compound [Na+].CC(O)=O.CC([O-])=O BHZOKUMUHVTPBX-UHFFFAOYSA-M 0.000 description 1
- 239000004449 solid propellant Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- ORZHVTYKPFFVMG-UHFFFAOYSA-N xylenol orange Chemical compound OC(=O)CN(CC(O)=O)CC1=C(O)C(C)=CC(C2(C3=CC=CC=C3S(=O)(=O)O2)C=2C=C(CN(CC(O)=O)CC(O)=O)C(O)=C(C)C=2)=C1 ORZHVTYKPFFVMG-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H1/00—Macromolecular products derived from proteins
Abstract
The invention discloses a method for manufacturing nano spherical metal nickel powder, and relates to the field of nano material preparation. According to the method, hydrazine hydrate is used as a reducing agent to reduce nickel sulfate hexahydrate, polyvinylpyrrolidone and phenylvinyl sulfone modified gelatin are used as dispersing agents, and the prepared nano spherical metal nickel powder has good reduction rate and smaller particle size; the invention also adopts 3-hydroxy-1-adamantyl methacrylate modified polyvinylpyrrolidone to prepare nano spherical metal nickel powder, so that the nano spherical metal nickel powder has better nickel powder reduction rate and smaller particle size.
Description
Technical Field
The invention belongs to the technical field of nano material preparation, and particularly relates to a method for manufacturing nano spherical metal nickel powder.
Background
The nano particles as powder materials have wide application prospects in various fields of catalysts, hard alloy binders, conductive slurry raw materials, additives of solid fuel propellants, ceramic capacitors, magnetic recording materials, magnetic liquid raw materials, microwave absorbing materials and the like in the chemical industry, so that the nano particles have extremely important application values in research fields of metallurgy, chemical industry, electronics, national defense, aerospace and the like. Since the 90 s, research on application development of nanoparticles is developed in a wider field due to high importance of countries around the world, the scientific term of nanoparticles is straddled into the industry, and the purely scientific exploration is changed into new technology and new material development, so that the nanoparticles enter the industrialization stage, and the nanoparticles become a new subject branch at present.
The nickel powder has the characteristics of good conductivity, chemical stability, weldability, welding resistance and the like, is low in price, and gradually replaces precious metals such as gold, silver and the like to be applied to the field of conductive paste in recent years, and the prepared conductive paste has the advantages of low resistance, good welding resistance, no ion migration, good linearity, resolution, screen printing performance and the like, and has been widely applied to the electronic industries such as thick film hybrid integrated circuits, resistors, multilayer ceramic capacitors, resistor networks, sensitive element surface assembly technologies and the like, so that the nickel powder becomes one of the most effective means for reducing the cost of current electronic products. However, these precise and miniature electronic components have extremely high requirements on the nickel powder used, the nickel powder must have the characteristics of high purity, high dispersion and the like, but as the particle size of the nickel powder is reduced, the specific surface area and specific surface energy are increased, the chemical activity is increased, the mutual attraction and agglomeration are easy to occur in the preparation and post-treatment processes, the particle coarsening and agglomeration are caused, the nickel powder with extremely poor dispersibility completely loses the original superiority in practical use, the processing characteristics and the product performance of the material are seriously affected, so that the improvement of the agglomeration state of the powder is an effective way for improving the performance of the nickel powder, and is one of the difficulties in the preparation of the nickel powder at present. The invention provides a method for preparing nano spherical metal nickel powder, which is used for preparing nano nickel powder with good dispersion performance.
Disclosure of Invention
The invention aims to provide a method for manufacturing nano spherical metal nickel powder, which has good nickel powder reduction rate and smaller particle size.
The technical scheme adopted by the invention for achieving the purpose is as follows:
a modified gelatin comprising gelatin and a surface modifying group; the surface modification group comprises a sulfonyl group and an aromatic ring; the gelatin comprises edible gelatin; the relative molecular mass of the gelatin is 50000-70000.
According to an embodiment of the present invention, the above modified gelatin is prepared from a phenylvinyl sulfone grafted modified gelatin.
The invention discloses a preparation method of modified gelatin, wherein the modified gelatin prepared by grafting modified gelatin with phenyl vinyl sulfone is used for preparing nano spherical metal nickel powder, so that the nano spherical metal nickel powder has good nickel powder reduction rate and smaller particle size; the reason is probably that after the phenyl vinyl sulfone is used for modifying the gelatin, the organic chains block aggregation among particles, so that the dispersion performance is good, and the occurrence of agglomeration growth is avoided; in addition, hydrophobic groups in the phenylvinyl sulfone are covered on the surface of the nickel crystal nucleus, so that the surface energy tends to be consistent, and therefore, the nickel powder tends to be spherical.
Specifically, the preparation method of the modified gelatin comprises the following steps:
adding gelatin (Gel) into trifluoroethanol (the mass volume ratio of the gelatin to the trifluoroethanol is 1g:10-15 mL), dissolving for 10-13h at 35-38 ℃, adding triethylamine, and stirring at constant temperature for 20-25min to obtain a solution a; dissolving 2-bromoisobutyryl bromide in trifluoroethanol (the volume ratio of the 2-bromoisobutyryl bromide to the trifluoroethanol is 1:1.8-2.3), slowly adding the trifluoroethanol into a solution a at the temperature of 0-3 ℃, reacting at the constant temperature for 2-2.5h, heating to 35-38 ℃ for reacting for 20-26h, precipitating with ethanol, dissolving with trifluoroethanol, precipitating with tetrahydrofuran, washing with ethanol, centrifuging and drying to obtain Gel-Br; gel-Br is added into trifluoroethanol (the mass volume ratio of the Gel-Br to the trifluoroethanol is 1g:50-55 mL), dissolved for 10-13h at the temperature of 35-38 ℃, phenylvinyl sulfone and 1,4, 7-pentamethyldiethylenetriamine are added, dissolved for 1-1.5h, cuprous bromide is added under the nitrogen atmosphere, the mixture is reacted for 24-30h at the temperature of 30-35 ℃, rotary evaporation is carried out, and the modified gelatin is prepared through chloroform extraction, ethanol precipitation, centrifugation and drying.
According to the embodiment of the invention, the mass volume ratio of the gelatin to the triethylamine is as follows: 1g, 0.5-0.8mL; the mass volume ratio of the gelatin to the 2-bromoisobutyryl bromide is as follows: 1g:1-1.2mL; the mass ratio of Gel-Br to phenyl vinyl sulfone is: 1:5-5.5; the mass volume ratio of Gel-Br to 1,4, 7-pentamethyldiethylenetriamine is as follows: 1g, 0.08-0.12mL; the mass ratio of Gel-Br to cuprous bromide is: 1:0.05-0.055.
The invention also discloses application of the modified gelatin obtained by the preparation method in preparation of nano spherical metal nickel powder.
The invention also discloses a manufacturing method of the nano spherical metal nickel powder, which comprises the following steps: the nano spherical metal nickel powder is prepared by taking nickel sulfate hexahydrate as a raw material, hydrazine hydrate as a reducing agent, polyvinylpyrrolidone and modified gelatin as dispersing agents, reacting for 30-40min at 70-80 ℃, centrifuging, washing and drying.
Specifically, the manufacturing method of the nano spherical metal nickel powder comprises the following steps:
adding deionized water (the mass volume ratio of nickel sulfate hexahydrate to deionized water is 1g:6-8 mL) into a mixture of nickel sulfate hexahydrate, polyvinylpyrrolidone and modified gelatin to prepare a V solution, adding deionized water (the volume ratio of hydrazine hydrate to deionized water is 1:8-10) into hydrazine hydrate and anhydrous sodium carbonate to prepare a W solution, slowly adding the V solution into the W solution at 70-80 ℃, continuing to perform constant temperature reaction for 30-40min after the V solution is added, centrifuging to separate solid from liquid, washing 5-7 times by adopting distilled water and ethanol in sequence, and drying under reduced pressure to prepare the nano spherical metal nickel powder.
According to an embodiment of the invention, the mass ratio of the nickel sulfate hexahydrate to the modified gelatin is as follows: 1:0.04-0.05.
According to the embodiment of the invention, the mass volume ratio of the nickel sulfate hexahydrate to the hydrazine hydrate is as follows: 1g, 0.6-0.8mL.
According to the embodiment of the invention, the mass volume ratio of the anhydrous sodium carbonate to the hydrazine hydrate is as follows: 1g, 0.45-0.55mL.
According to an embodiment of the invention, the mass ratio of polyvinylpyrrolidone to modified gelatin is as follows: 1:0.8-1.2.
According to an embodiment of the present invention, the average particle size of the above nano spherical metallic nickel powder is < 95nm.
In order to further improve the performance of the nano spherical metal nickel powder, the invention also carries out modification treatment on polyvinylpyrrolidone.
The invention also discloses a preparation method of the modified polyvinylpyrrolidone, which comprises the following steps: the modified polyvinylpyrrolidone is prepared by adopting the grafting reaction of N-vinyl pyrrolidone and 3-hydroxy-1-adamantyl methacrylate.
The invention provides a preparation method of modified polyvinylpyrrolidone, which takes 3-hydroxy-1-adamantyl methacrylate as a modifier to carry out grafting modification on N-vinylpyrrolidone, and the prepared modified polyvinylpyrrolidone is used for preparing nano spherical metal nickel powder, so that the nano spherical metal nickel powder has better nickel powder reduction rate and smaller particle size; the reason is probably because the cross-linking structure formed by the 3-hydroxy-1-adamantyl methacrylate and the polyvinylpyrrolidone prevents the aggregation and growth of nickel powder particles, and the existence of the O-H, C-O and other structures in the 3-hydroxy-1-adamantyl methacrylate enables the modified polyvinylpyrrolidone to be easily adsorbed on the surfaces of the nickel powder particles through the hydrogen bond action, so that a layer of polymer protective film is formed, the steric hindrance effect is increased, the attractive force among the nano particles is weakened, and the dispersion performance is enhanced.
Specifically, the preparation method of the modified polyvinylpyrrolidone comprises the following steps:
adding N-vinyl pyrrolidone and 3-hydroxy-1-adamantyl methacrylate into a mixed solvent of methanol and deionized water (wherein the mass volume ratio of the total amount of the N-vinyl pyrrolidone and the 3-hydroxy-1-adamantyl methacrylate to the mixed solvent is 1g:5-7mL; the volume ratio of methanol to deionized water is 1:0.25-0.5), heating to 65-75 ℃ in a nitrogen atmosphere, adding azodiisobutyronitrile (the mass ratio of the total amount of the N-vinyl pyrrolidone and the 3-hydroxy-1-adamantyl methacrylate to the azodiisobutyronitrile is 1:0.0025-0.0035), reacting for 5-6h, cooling to room temperature, centrifuging, washing 3-5 times by absolute ethyl alcohol, and drying at 30-35 ℃ for 20-24h to obtain the modified polyvinyl pyrrolidone.
According to an embodiment of the present invention, the mass ratio of the N-vinylpyrrolidone to the 3-hydroxy-1-adamantyl methacrylate is: 1:0.8-1.5.
According to an embodiment of the present invention, the modified polyvinylpyrrolidone has a relative molecular weight of 20000 to 40000.
The invention also discloses the application of the modified polyvinylpyrrolidone prepared by the preparation method in the nano spherical metal nickel powder.
The beneficial effects of the invention include:
the invention has obtained the preparation method of a kind of nanometer spherical metal nickel powder, this method uses nickel sulfate hexahydrate as raw materials, use hydrazine hydrate as reducing agent, use polyvinylpyrrolidone, phenyl vinyl sulfone modified gelatin as dispersing agent, the nanometer spherical metal nickel powder prepared has good nickel powder reduction rate and smaller particle diameter; the invention also adopts 3-hydroxy-1-adamantyl methacrylate to modify polyvinylpyrrolidone, and then uses the modified polyvinylpyrrolidone in the preparation of nano spherical metal nickel powder, so that the nano spherical metal nickel powder has better nickel powder reduction rate and smaller particle size.
Therefore, the invention provides a method for manufacturing nano spherical metal nickel powder, and the nano spherical metal nickel powder prepared by the method has good nickel powder reduction rate and smaller particle size.
Drawings
FIG. 1 is an SEM image of nano-spherical metallic nickel powder prepared in example 1;
FIG. 2 shows the infrared spectrum of modified gelatin and gelatin prepared in example 1;
FIG. 3 is an infrared spectrum of modified polyvinylpyrrolidone prepared in example 3 and polyvinylpyrrolidone.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more clear and clear, the technical solutions of the present invention are described in further detail below with reference to the specific embodiments:
example 1:
the preparation process of nanometer spherical metal nickel powder includes the following steps:
adding deionized water (the mass volume ratio of nickel sulfate hexahydrate to deionized water is 1g:6 mL) into a mixture of nickel sulfate hexahydrate, polyvinylpyrrolidone and modified gelatin to prepare a V solution, adding deionized water (the volume ratio of hydrazine hydrate to deionized water is 1:8) into hydrazine hydrate and anhydrous sodium carbonate to prepare a W solution, slowly adding the V solution into the W solution at 70 ℃, continuing to perform constant temperature reaction for 30min after the V solution is added, centrifuging to separate solid from liquid, washing with distilled water and ethanol for 5 times sequentially, and drying under reduced pressure to prepare nano spherical metal nickel powder, wherein an SEM (scanning electron microscope) diagram of the nano spherical metal nickel powder is shown in figure 1; wherein, the mass ratio of the nickel sulfate hexahydrate to the modified gelatin is as follows: 1:0.04; the mass volume ratio of the nickel sulfate hexahydrate to the hydrazine hydrate is as follows: 1g:0.6ml; the mass volume ratio of anhydrous sodium carbonate to hydrazine hydrate is as follows: 1g:0.45ml; the mass ratio of polyvinylpyrrolidone to modified gelatin is as follows: 1:0.8.
A method for preparing modified gelatin comprising:
adding gelatin (relative molecular weight of gelatin is 70000) into trifluoroethanol (mass volume ratio of the gelatin to the trifluoroethanol is 1g:10 mL), dissolving at 37 ℃ for 10h, adding triethylamine, and stirring at constant temperature for 20min to obtain a solution a; dissolving 2-bromoisobutyryl bromide in trifluoroethanol (the volume ratio of the 2-bromoisobutyryl bromide to the trifluoroethanol is 1:2), then slowly adding the trifluoroethanol into the solution a at the temperature of 0 ℃, reacting for 2 hours at constant temperature, heating to 37 ℃ for 24 hours, precipitating with ethanol, dissolving with trifluoroethanol, precipitating with tetrahydrofuran, washing with ethanol, centrifuging and drying to obtain Gel-Br; gel-Br is added into trifluoroethanol (the mass volume ratio of the Gel-Br to the trifluoroethanol is 1g:50 mL), dissolved for 10 hours at 37 ℃, added with phenylvinyl sulfone and 1,4, 7-pentamethyldiethylenetriamine, dissolved for 1 hour, added with cuprous bromide under the nitrogen atmosphere, reacted for 24 hours at 30 ℃, rotary evaporated, extracted by chloroform, precipitated by ethanol, centrifuged and dried to prepare modified gelatin; wherein the mass volume ratio of the gelatin to the triethylamine is as follows: 1g:0.5ml; the mass volume ratio of the gelatin to the 2-bromoisobutyryl bromide is as follows: 1g 1mL; the mass ratio of Gel-Br to phenyl vinyl sulfone is: 1:5; the mass volume ratio of Gel-Br to 1,4, 7-pentamethyldiethylenetriamine is as follows: 1g:0.08ml; the mass ratio of Gel-Br to cuprous bromide is: 1:0.05.
Example 2:
the manufacturing method of the nano spherical metal nickel powder is different from that of the embodiment 1: gelatin is used to replace modified gelatin.
Example 3:
the manufacturing method of the nano spherical metal nickel powder is different from that of the embodiment 1: modified polyvinylpyrrolidone is used instead of polyvinylpyrrolidone.
The preparation method of the modified polyvinylpyrrolidone comprises the following steps:
adding N-vinyl pyrrolidone and 3-hydroxy-1-adamantyl methacrylate into a mixed solvent of methanol and deionized water (wherein the mass volume ratio of the total amount of the N-vinyl pyrrolidone and the 3-hydroxy-1-adamantyl methacrylate to the mixed solvent is 1g:5mL; the volume ratio of methanol to deionized water is 1:0.25), heating to 65 ℃ under the nitrogen atmosphere, adding azobisisobutyronitrile (the mass ratio of the total amount of the N-vinyl pyrrolidone and the 3-hydroxy-1-adamantyl methacrylate to the azobisisobutyronitrile is 1:0.0025), reacting for 5 hours, cooling to room temperature, centrifuging, washing with absolute ethyl alcohol for 3 times, and drying at 30 ℃ for 24 hours to obtain modified polyvinyl pyrrolidone with the relative molecular weight of 35000; wherein the mass ratio of the N-vinyl pyrrolidone to the 3-hydroxy-1-adamantyl methacrylate is as follows: 1:1.5.
Example 4:
the manufacturing method of the nano spherical metal nickel powder is different from that of the embodiment 2: modified polyvinylpyrrolidone is used instead of polyvinylpyrrolidone.
The preparation method of the modified polyvinylpyrrolidone is the same as in example 3.
Test example:
1. infrared spectroscopy testing
Characterization by ATR-FTIR total reflection Fourier infrared spectrometer with scanning wavelength range of 400-4000cm -1 Resolution of 4cm -1 。
The modified gelatin and gelatin prepared in example 1 were subjected to the above test, and the results are shown in fig. 2. As can be seen from FIG. 2, the infrared spectrum of the modified gelatin is 1400-1600cm -1 The infrared characteristic absorption peak of benzene ring exists at 1147cm -1 、1332cm -1 Infrared characteristic absorption peaks of sulfonyl exist at the position; indicating that phenylvinylsulfone is involved in the formation reaction of the modified gelatin.
The modified polyvinylpyrrolidone prepared in example 3 and polyvinylpyrrolidone were subjected to the above test, and the results are shown in fig. 3. As can be seen from FIG. 3, the infrared spectrum of the modified polyvinylpyrrolidone was 3649cm compared with the infrared spectrum of polyvinylpyrrolidone -1 An infrared characteristic absorption peak of-OH exists at the position; indicating that 3-hydroxy-1-adamantyl methacrylate participates in the formation reaction of modified polyvinylpyrrolidone.
2. Particle size test
The average particle size of the samples was measured using a WJL-626 laser particle sizer.
Table 1 particle size test results of nano spherical metallic nickel powder sample
| Experimental grouping | Average particle diameter/nm |
| Example 1 | 76 |
| Example 2 | 85 |
| Example 3 | 63 |
| Example 4 | 71 |
The above-described test was performed on the nano-spherical metallic nickel powder prepared in example 1-example 4, and the results are shown in table 1. As can be seen from table 1, the average particle size of the nano spherical metallic nickel powder is significantly reduced in example 1 compared with example 2 and example 3 compared with example 4, which indicates that after phenylvinyl sulfone is used for preparing the nano spherical metallic nickel powder, the modified gelatin is used for preparing the nano spherical metallic nickel powder, so that the nano spherical metallic nickel powder has smaller particle size; example 3 also showed a decrease in the average particle size of the nano-spherical metallic nickel powder compared with example 1 and example 4 compared with example 2, indicating that after the modified polyvinylpyrrolidone of 3-hydroxy-1-adamantyl methacrylate was used for the preparation of the nano-spherical metallic nickel powder, the nano-spherical metallic nickel powder also had a smaller particle size.
3. Nickel powder reduction rate test
Taking 10mL of reaction solution after the reaction of the nano spherical metal nickel powder is finished, adding 70mL of deionized water, adopting a hydrochloric acid solution with the concentration of 50wt% to adjust the pH value to 4.5, then slowly adding 20mL of acetic acid-sodium acetate solution buffer with the pH value of 5.5, then adding 40mL of EDTA standard solution with the concentration of 0.05mol/L and 0.3mL of xylenol orange indicator with the concentration of 0.25wt%, and then adopting ZnCl with the concentration of 0.02mol/L 2 And (3) titrating the standard solution until the solution turns red, and calculating the content of nickel ions in the reaction solution, wherein the calculation formula is as follows:
U=[(40×E-Z×V)×0.0587×1000]/(1000×10)
wherein U is the concentration of nickel ions in the reaction liquid after the reaction is completed, and g/L; e is the concentration of EDTA standard solution and mol/L; z is ZnCl 2 Concentration of standard solution, mol/L; v is ZnCl 2 Volume of standard solution, mL;0.0587 is the mass of nickel ion coordinated by 1mL of EDTA standard solution with the concentration of 1mol/L, g.
The nickel powder reduction rate is calculated as follows:
S/%=[(U0-U)/U0]×100%
wherein S is the reduction rate; u is the concentration of nickel ions in the reaction liquid after the reaction is completed; u0 is the initial nickel ion concentration.
TABLE 2 Nickel powder reduction test results
| Experimental grouping | Reduction rate/% |
| Example 1 | 95.9 |
| Example 2 | 93.5 |
| Example 3 | 98.8 |
| Example 4 | 96.4 |
The above-described test was performed on the nano-spherical metallic nickel powder prepared in example 1-example 4, and the results are shown in table 2. As can be seen from table 2, compared with example 2 and example 3 and example 4, the reduction rate of the nano spherical metal nickel powder is significantly improved, which indicates that after the phenylvinyl sulfone is used for modifying gelatin, the modified gelatin is used for preparing the nano spherical metal nickel powder, so that the nano spherical metal nickel powder has good reduction rate; the reduction rate of the nano spherical metallic nickel powder is also increased in example 3 compared with example 1 and example 4 compared with example 2, which shows that after the modified polyvinylpyrrolidone of 3-hydroxy-1-adamantyl methacrylate is used for preparing the nano spherical metallic nickel powder, the nano spherical metallic nickel powder also has good reduction rate.
The conventional technology in the above embodiments is known to those skilled in the art, and thus is not described in detail herein.
The foregoing is merely illustrative of the present invention, and the present invention is not limited thereto, and any person skilled in the art will readily recognize that variations or substitutions are within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (4)
1. A modified gelatin, characterized in that: the modified gelatin comprises gelatin and a surface modification group thereof; the surface modification group comprises a sulfonyl group and an aromatic ring; the gelatin comprises edible gelatin; the relative molecular mass of the gelatin is 50000-70000;
the modified gelatin is prepared by grafting phenyl vinyl sulfone to the modified gelatin;
a method for preparing modified gelatin comprising:
adding gelatin into trifluoroethanol, dissolving at 35-38deg.C for 10-13 hr, adding triethylamine, stirring at constant temperature for 20-25min to obtain solution a; dissolving 2-bromoisobutyryl bromide in trifluoroethanol, slowly adding the trifluoroethanol into a solution a at the temperature of 0-3 ℃ for constant temperature reaction for 2-2.5 hours, heating to the temperature of 35-38 ℃ for reaction for 20-26 hours, precipitating with ethanol, dissolving with trifluoroethanol, precipitating with tetrahydrofuran, washing with ethanol, centrifuging, and drying to obtain Gel-Br; adding Gel-Br into trifluoroethanol, dissolving for 10-13 hours at 35-38 ℃, adding phenyl vinyl sulfone and 1,4, 7-pentamethyl diethylenetriamine, dissolving for 1-1.5 hours, adding cuprous bromide in a nitrogen atmosphere, reacting for 24-30 hours at 30-35 ℃, performing rotary evaporation, extracting by chloroform, precipitating by ethanol, centrifuging and drying to obtain modified gelatin;
the mass volume ratio of the gelatin to the triethylamine is as follows: 1g, 0.5-0.8mL; the mass volume ratio of the gelatin to the 2-bromoisobutyryl bromide is as follows: 1g:1-1.2mL; the mass ratio of Gel-Br to phenyl vinyl sulfone is: 1:5-5.5; the mass volume ratio of Gel-Br to 1,4, 7-pentamethyldiethylenetriamine is as follows: 1g, 0.08-0.12mL; the mass ratio of Gel-Br to cuprous bromide is: 1:0.05-0.055.
2. The preparation process of nanometer spherical metal nickel powder includes the following steps:
adding deionized water into a mixture of nickel sulfate hexahydrate, polyvinylpyrrolidone and modified gelatin according to claim 1 to prepare a V solution, adding deionized water into hydrazine hydrate and anhydrous sodium carbonate to prepare a W solution, slowly adding the V solution into the W solution at 70-80 ℃, continuing to react for 30-40min at constant temperature after the V solution is added, centrifuging to separate solid from liquid, washing for 5-7 times by adopting distilled water and ethanol in sequence, and drying under reduced pressure to prepare nano spherical metal nickel powder;
the mass ratio of the nickel sulfate hexahydrate to the modified gelatin is as follows: 1:0.04-0.05;
the mass volume ratio of the nickel sulfate hexahydrate to the hydrazine hydrate is as follows: 1g, 0.6-0.8mL;
the mass ratio of polyvinylpyrrolidone to modified gelatin is as follows: 1:0.8-1.2.
3. The method for manufacturing nano spherical metal nickel powder according to claim 2, wherein: the average grain diameter of the nano spherical metal nickel powder is less than 95nm.
4. Use of the modified gelatin of claim 1 for the preparation of nanosphere-shaped metallic nickel powders.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE69602058D1 (en) * | 1995-06-15 | 1999-05-20 | Eastman Kodak Co | Imaging element containing an electrically conductive layer with improved abrasion resistance |
| CN105017537A (en) * | 2014-04-30 | 2015-11-04 | 北京化工大学 | Gelatin and polyester copolymerized composite biological material and preparation method thereof |
| CN114209882A (en) * | 2021-12-27 | 2022-03-22 | 长春市儿童医院(吉林省儿童医疗中心长春市儿科医学研究所) | Silver nanoparticle-collagen gelatin stent material and preparation method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE69602058D1 (en) * | 1995-06-15 | 1999-05-20 | Eastman Kodak Co | Imaging element containing an electrically conductive layer with improved abrasion resistance |
| CN105017537A (en) * | 2014-04-30 | 2015-11-04 | 北京化工大学 | Gelatin and polyester copolymerized composite biological material and preparation method thereof |
| CN114209882A (en) * | 2021-12-27 | 2022-03-22 | 长春市儿童医院(吉林省儿童医疗中心长春市儿科医学研究所) | Silver nanoparticle-collagen gelatin stent material and preparation method thereof |
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