CN108031839A - Copper nanoparticle of in-stiu coating organic matter and preparation method thereof - Google Patents
Copper nanoparticle of in-stiu coating organic matter and preparation method thereof Download PDFInfo
- Publication number
- CN108031839A CN108031839A CN201810014435.XA CN201810014435A CN108031839A CN 108031839 A CN108031839 A CN 108031839A CN 201810014435 A CN201810014435 A CN 201810014435A CN 108031839 A CN108031839 A CN 108031839A
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- China
- Prior art keywords
- solution
- copper
- added
- organic matter
- mantoquita
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 239000010949 copper Substances 0.000 title claims abstract description 90
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 89
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 60
- 239000005416 organic matter Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000011248 coating agent Substances 0.000 title claims abstract description 20
- 238000000576 coating method Methods 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 41
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 239000002270 dispersing agent Substances 0.000 claims abstract description 16
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 15
- 238000001556 precipitation Methods 0.000 claims abstract description 15
- 238000010792 warming Methods 0.000 claims abstract description 15
- 229920002521 macromolecule Polymers 0.000 claims abstract description 14
- 239000007864 aqueous solution Substances 0.000 claims abstract description 13
- 238000000926 separation method Methods 0.000 claims abstract description 13
- 238000002604 ultrasonography Methods 0.000 claims abstract description 13
- 238000005119 centrifugation Methods 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 100
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- 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 description 25
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 25
- 150000001875 compounds Chemical class 0.000 claims description 23
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 21
- 238000009833 condensation Methods 0.000 claims description 19
- 230000005494 condensation Effects 0.000 claims description 19
- NVVZQXQBYZPMLJ-UHFFFAOYSA-N formaldehyde;naphthalene-1-sulfonic acid Chemical group O=C.C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 NVVZQXQBYZPMLJ-UHFFFAOYSA-N 0.000 claims description 19
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 18
- 229910001431 copper ion Inorganic materials 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 15
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 14
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 14
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 9
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 8
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 8
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 239000008103 glucose Substances 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 239000011668 ascorbic acid Substances 0.000 claims description 4
- 229960005070 ascorbic acid Drugs 0.000 claims description 4
- 235000010323 ascorbic acid Nutrition 0.000 claims description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 4
- 239000012279 sodium borohydride Substances 0.000 claims description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 4
- 229920001732 Lignosulfonate Polymers 0.000 claims description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- HFDWIMBEIXDNQS-UHFFFAOYSA-L copper;diformate Chemical compound [Cu+2].[O-]C=O.[O-]C=O HFDWIMBEIXDNQS-UHFFFAOYSA-L 0.000 claims description 3
- PSZYNBSKGUBXEH-UHFFFAOYSA-M naphthalene-1-sulfonate Chemical compound C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-M 0.000 claims description 3
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 2
- 235000021419 vinegar Nutrition 0.000 claims 1
- 239000000052 vinegar Substances 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 11
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000005253 cladding Methods 0.000 abstract description 3
- 239000006185 dispersion Substances 0.000 abstract description 2
- 239000012298 atmosphere Substances 0.000 description 11
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 7
- 239000000908 ammonium hydroxide Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000003963 antioxidant agent Substances 0.000 description 6
- 230000003078 antioxidant effect Effects 0.000 description 6
- 235000006708 antioxidants Nutrition 0.000 description 6
- 230000001681 protective effect Effects 0.000 description 6
- 239000007859 condensation product Substances 0.000 description 5
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 5
- 239000003292 glue Substances 0.000 description 5
- 239000006193 liquid solution Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 4
- 238000013019 agitation Methods 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000000843 powder Substances 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 description 2
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 229960004643 cupric oxide Drugs 0.000 description 2
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 2
- 229940112669 cuprous oxide Drugs 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical class C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- HNURKXXMYARGAY-UHFFFAOYSA-N 2,6-Di-tert-butyl-4-hydroxymethylphenol Chemical compound CC(C)(C)C1=CC(CO)=CC(C(C)(C)C)=C1O HNURKXXMYARGAY-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- SNEYJZBZIICCIN-UHFFFAOYSA-N C1(=CC=CC2=CC=CC=C12)S(=O)(=O)O.C(CCCCCCCCCCC)[Na] Chemical compound C1(=CC=CC2=CC=CC=C12)S(=O)(=O)O.C(CCCCCCCCCCC)[Na] SNEYJZBZIICCIN-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- YDEXUEFDPVHGHE-GGMCWBHBSA-L disodium;(2r)-3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Na+].[Na+].COC1=CC=CC(C[C@H](CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O YDEXUEFDPVHGHE-GGMCWBHBSA-L 0.000 description 1
- -1 distilled water compound Chemical class 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 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
- 230000005484 gravity Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- LCRMGUFGEDUSOG-UHFFFAOYSA-N naphthalen-1-ylsulfonyloxymethyl naphthalene-1-sulfonate;sodium Chemical compound [Na].C1=CC=C2C(S(=O)(OCOS(=O)(=O)C=3C4=CC=CC=C4C=CC=3)=O)=CC=CC2=C1 LCRMGUFGEDUSOG-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012266 salt solution Substances 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
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 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
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
- B22F1/102—Metallic powder coated with organic material
-
- 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
- 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
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
Abstract
The present invention provides a kind of copper nanoparticle of in-stiu coating organic matter and preparation method thereof, the preparation method is that mantoquita is added to containing dispersant and optionally in the aqueous solution containing water-soluble macromolecule, dissolve and be uniformly mixed, add aqueous slkali and adjust pH to 10 ± 0.5, then add reducing agent, after being warming up to 30 100 DEG C of 30 240min of reaction, 10 60min are reacted under ultrasound condition, are cooled down, centrifugation, precipitation and separation, up to the copper nanoparticle of in-stiu coating organic matter after drying.Using copper nanoparticle uniform particle diameter made from the method for the present invention, good dispersion, stability are good, and the dispersant of copper particle surface cladding effectively can prevent it from aoxidizing.The preparation method is simple, and equipment requirement is low, and economic benefit is big, has a extensive future.
Description
Technical field
The present invention relates to field of material engineering technology, specifically, is related to a kind of copper nanoparticle of in-stiu coating organic matter
And preparation method thereof.
Background technology
In recent years, liquid phase reduction is to be reported the method that copper nanoparticle is prepared with one kind of most study, by suitable
Reducing agent, copper-containing compound is reduced to copper powder in the solution.This method can be used to prepare that dispersibility is good, size distribution
Uniform nanoscale precious metal powder, but the activity of copper is more much better than than noble metals such as gold and silver, how to solve gained copper nanoparticle
The surface oxidation problem of son is still the key in its production process.
Liquid phase reduction is using being first complexed the strategy that restores, but there are reactant concentration is low, production efficiency for this method
The problem of not high, due to using traditional mechanical agitation mode in preparation process, be easy to cause copper nanoparticle and reunite, aoxidize；It is right
In the copper nanoparticle of preparation, often also need to be placed in oleic acid to be passivated.It would therefore be highly desirable to develop a kind of inexpensive, simple side
Just, suitable for industrialized production Coated with Organic Matter copper nanoparticle method.
The content of the invention
The object of the present invention is to provide the low copper nano particles for preparing high antioxidant of a kind of simple operations, production cost
Preparation method.
It is a further object of the present invention to provide the copper nanoparticle of the surface in situ cladding organic matter prepared according to the method described above.
In order to realize the object of the invention, a kind of preparation side of the copper nanoparticle of in-stiu coating organic matter provided by the invention
Method, mantoquita is added to containing dispersant and optionally in the aqueous solution containing water-soluble macromolecule, dissolves and is uniformly mixed, and is added
Aqueous slkali adjusts pH to 10 ± 0.5, then adds reducing agent, after being warming up to 30-100 DEG C of reaction 30-240min, then at ultrasonic bar
10-60min is reacted under part (such as 40KHz), is cooled down, centrifugation, precipitation and separation, up to the Nanometer Copper of in-stiu coating organic matter after drying
Powder.
In the present invention, the dispersant be selected from naphthalenesulfonate formaldehyde condensation compound, lignosulfonates, alkylnaphthalene sulfonate or
At least one of di-2-ethylhexylphosphine oxide naphthalene sulfonate etc.；It is preferred that the dispersant is naphthalenesulfonate formaldehyde condensation compound.
The reducing agent in hydrazine hydrate, ascorbic acid, sodium borohydride, glucose, sodium hypophosphite, formaldehyde etc. extremely
Few one kind；It is preferred that the reducing agent is hydrazine hydrate.
The water-soluble macromolecule is selected from least one of polyvinylpyrrolidone, polyvinyl alcohol or polyethylene glycol etc..
The mantoquita is selected from least one of copper sulphate, copper nitrate, copper chloride, copper acetate or copper formate etc..
Preferably, lignosulfonates, alkylnaphthalene sulfonate or di-2-ethylhexylphosphine oxide naphthalene sulfonate are respectively wooden in the present invention
Plain sodium sulfonate, Negel or sodium methylene bis-naphthalene sulfonate.
Preferably, heretofore described aqueous slkali is sodium hydroxide solution, more preferably the sodium hydroxide solution of 1mol/L.
Foregoing method, the concentration of dispersant is 0.5-20g/L, preferably 1-18g/L, more preferably 2.5- in the aqueous solution
10g/L, most preferably 5-6.5g/L.
Foregoing method, the concentration of water-soluble macromolecule is 0-30g/L, preferably 1-20g/L in the aqueous solution, more preferably
5-15g/L, most preferably 6-9g/L.
Foregoing method, the concentration of mantoquita is 10-100mmol/L, preferably 20-80mmol/L in the aqueous solution, more excellent
Select 30-50mmol/L.
Foregoing method, the molar ratio of the reducing agent and mantoquita is 20-66:1.
Foregoing method, after adding reducing agent, reaction temperature is preferably 50 DEG C.
As the preferred embodiment of the present invention, the dispersant is naphthalenesulfonate formaldehyde condensation compound, the reduction
Agent is hydrazine hydrate.
As another preferred embodiment of the present invention, the reducing agent of addition is hydrazine hydrate, copper ion and hydrazine hydrate
Molar ratio is 1:20-70, preferably 1:30-66, more preferably 1:50-60.
The method of the present invention can be carried out directly in atmosphere without being carried out under inert atmosphere or protective atmosphere.
As another preferred embodiment of the present invention, the described method comprises the following steps：
(1) a certain amount of dispersant is added in deionized water, it is fully dissolved, the dispersant addition is
0.5-20g/L；
(2) water-soluble macromolecule is added in the solution obtained by step (1), it is fully dissolved；
(3) mantoquita is added into obtained mixed liquor, it is completely dissolved and is uniformly mixed, the addition of mantoquita is 10-
100mmol/L；
(4) aqueous slkali is added in the mixed liquor obtained to step (3) and adjusts pH to 10 ± 0.5；
(5) reducing agent is added in the mixed liquor obtained under agitation to step (4)；
(6) mixed liquor that step (5) obtains is warming up to 50 DEG C after mixing, reacts 30-240min under this condition,
Ultrasound 30min again, treats that it is cooled to room temperature, and centrifugation, takes out bottom red-brown precipitation, is the nanometer that surface has coated organic matter
Copper particle.
As another preferred embodiment of the present invention, the described method comprises the following steps：
1) naphthalenesulfonate formaldehyde condensation compound is added in deionized water and dissolved, obtain naphthalenesulfonate formaldehyde condensation compound content
For the solution I of 0.5-20g/L；
2) water-soluble macromolecule is added in solution I and dissolved, obtain the solution that water-soluble macromolecule content is 1-20g/L
II；
3) mantoquita dissolving is added into solution II, obtains the solution III that mantoquita content is 10-100mmol/L；
4) pH to 10 ± 0.5 of solution III is adjusted with the sodium hydroxide solution of 1mol/L；
5) hydrazine hydrate is added in the mixed liquor under the conditions of stirring at normal temperature to step 4), obtains solution IV；
6) solution IV is warming up to 50 DEG C, reacts 30-240min, then ultrasound 30min at such a temperature, be finally cooled to room
Temperature, centrifugation, precipitation and separation are dry.
The present invention also provides the copper nanoparticle of the in-stiu coating organic matter prepared according to method described above.The copper powder exists
Good dispersion in water, soilless sticking phenomenon, and size is more homogeneous, particle diameter 100-200nm, the thickness of Coated with Organic Matter layer is
10-20nm。
The copper nanoparticle of the in-stiu coating organic matter of the present invention is suitable for the fields such as electrocondution slurry, ink jet printing.
Compared with prior art, the present invention has the following advantages：
(1) by the use of the compounds such as naphthalenesulfonate formaldehyde condensation compound and water-soluble macromolecule as template, reduced using a step
Method, while reduced nano copper particle, coats one layer of organic matter on its surface, the Nanometer Copper of core shell structure is prepared
Grain, for its stratum nucleare grain size in 100-200nm, the thickness of surface organic matter clad is 10-20nm.Overcome traditional pair
Mantoquita is first complexed the liquid-phase reduction restored and prepares that reactant concentration existing for copper nanoparticle method is low, reaction yield is low, cost
The problems such as high, unsuitable industrialized production.
(2) traditional mechanical agitation mode is improved and is stirred for ultrasonic vibration, while by controlling the pH of reaction system
Value, efficiently avoid reunion and the oxidative phenomena of copper powder, and operating method is simple, and equipment requirement is low, and economic benefit is big, and prepare
During need not be passed through inert gas and protected, obtained copper nanoparticle purity is high, and non-oxidation copper and cuprous oxide impurity
The presence at peak.
(3) compound (dispersant) such as naphthalenesulfonate formaldehyde condensation compound and water-soluble macromolecule act in the present invention
In：On the one hand the size and shape of nano particle, another aspect and energy dispersing nanoparticles can be controlled, prevent nano particle from sending out
It is raw to reunite, while surface coated dispersant can also protect the copper particle of internal layer, prevent it from aoxidizing, improve copper nanoparticle
Inoxidizability.
(4) it is highly stable using Coated with Organic Matter copper nanoparticle made from the method for the present invention, place 6 months in atmosphere
Do not aoxidize yet afterwards, inoxidizability is good.
Brief description of the drawings
Fig. 1 is the X-ray diffractogram (A) of Coated with Organic Matter copper nanoparticle prepared by the embodiment of the present invention 1 and will synthesize
Obtained Coated with Organic Matter nano copper particle place 6 months after X-ray diffractogram (B).
Fig. 2 is the TGA figures of Coated with Organic Matter copper nanoparticle prepared by the embodiment of the present invention 1.
Fig. 3 is the TEM figures of Coated with Organic Matter copper nanoparticle prepared by the embodiment of the present invention 1.
Fig. 4 is the XPS figures of Coated with Organic Matter copper nanoparticle prepared by the embodiment of the present invention 1.
Embodiment
Following embodiments are used to illustrate the present invention, but are not limited to the scope of the present invention.Unless otherwise specified, embodiment
In the conventional means that are well known to those skilled in the art of used technological means, raw materials used is commercial goods.
The preparation method of the copper nanoparticle of 1 in-stiu coating organic matter of embodiment
1) a certain amount of naphthalenesulfonate formaldehyde condensation compound is added into deionized water, until it is fully dissolved so that naphthalene
The concentration of sulfonate and formaldehyde condensation product is 5g/L；
2) a certain amount of polyvinylpyrrolidone is added in the solution obtained to step 1), treats that it is fully dissolved so that
The concentration of final polyvinylpyrrolidone is 9g/L；
3) cupric sulfate pentahydrate is added in the solution obtained to step 2), stirs to it and fully dissolve so that final copper ion
Concentration be 10mmol/L；
4) with the sodium hydroxide solution set-up procedure 3 of 1mol/L) obtained solution, until the pH value of solution is 10 ± 0.5；
5) solution for obtaining step 4) is warming up to 50 DEG C, and the hydrazine hydrate solution for adding that mass fraction is 50% is added dropwise, makes
The molar ratio for obtaining hydrazine hydrate and copper ion is 66：1,150min is then kept at such a temperature, obtains the Nanometer Copper glue of rufous
Liquid solution；
6) the copper colloidal solution that after reaction, step 5) is obtained ultrasound 30min under the conditions of 40MHz, then with
10000rpm centrifuges 5min, precipitation and separation, is the copper nano particles of Coated with Organic Matter after dry.
The X-ray diffractogram of Coated with Organic Matter copper nanoparticle prepared by embodiment 1 is shown in Fig. 1.Signal as we can see from the figure
Stronger three diffraction maximums correspond respectively to (111), (200), (220) crystal face of copper, and the weaker peak of other intensity belongs to respectively
In surface coated organic matter：Naphthalenesulfonate formaldehyde condensation compound and polyvinylpyrrolidone, do not find that cupric oxide and oxidation are sub-
The peak of copper, illustrates to use naphthalenesulfonate formaldehyde condensation compound and polyvinylpyrrolidone for template, can be under non-protective atmosphere
Synthetic surface cladding organic matter, unoxidized copper particle.
After product is placed 6 months, then X-ray diffraction analysis (Fig. 1) are carried out to it, it turns out that its XRD diffraction maximum is not sent out
Changing, without the appearance of cuprous oxide and cupric oxide diffraction maximum, it follows that product does not aoxidize after placing 6 months, into
And illustrate that it is sufficiently stable in atmosphere, there is good inoxidizability.
Fig. 2 is the TGA figures of Coated with Organic Matter copper nanoparticle prepared by embodiment 1.It can be seen from the figure that synthesis is compound
In a nitrogen atmosphere, with the increase of temperature, there is different degrees of weightlessness in particle, this is related with the organic matter decomposition on surface, separately
The outer reduced gravity situations according to TGA curves, the amount that also can substantially estimate surface coated organic matter are 30% or so.
Fig. 3 is the TEM figures of Coated with Organic Matter copper nanoparticle prepared by embodiment 1.Coated with Organic Matter as we can see from the figure
Its particle diameter of copper nano particles in 100nm or so, the thickness of Coated with Organic Matter layer is 10nm or so.
Fig. 4 is the XPS figures of Coated with Organic Matter copper nanoparticle prepared by embodiment 1.Copper particle surface as we can see from the figure
In addition to the signal peak of copper, there are the signal peak of S, Na, O, C, N, the signal peak of S and Na come from naphthalene sulphonate formaldehyde condensation
Thing, the signal peak of N come from polyvinylpyrrolidone.
The preparation method of the copper nanoparticle of 2 in-stiu coating organic matter of embodiment
1) a certain amount of naphthalenesulfonate formaldehyde condensation compound is added into deionized water, until it is fully dissolved so that naphthalene
The concentration of sulfonate and formaldehyde condensation product is 5g/L；
2) a certain amount of polyvinylpyrrolidone is added in the solution obtained to step 1), treats that it is fully dissolved so that
The concentration of final polyvinylpyrrolidone is 6g/L；
3) copper nitrate is added in the solution obtained to step 2), stirs to it and fully dissolve so that finally copper ion is dense
Spend for 50mmol/L；
4) with the sodium hydroxide solution set-up procedure 3 of 1mol/L) obtained solution, until the pH value of solution is 10 ± 0.5；
5) solution for obtaining step 4) is warming up to 50 DEG C, and the hydrazine hydrate solution for adding that mass fraction is 50% is added dropwise, makes
The molar ratio for obtaining hydrazine hydrate and copper ion is 50：1,100min is then kept at such a temperature, obtains the Nanometer Copper glue of rufous
Liquid solution；
6) the copper colloidal solution that after reaction, step 5) is obtained ultrasound 30min under the conditions of 40MHz, then with
10000rpm centrifuges 5min, precipitation and separation, is the copper nano particles of Coated with Organic Matter after dry.
The preparation method of the copper nanoparticle of 3 in-stiu coating organic matter of embodiment
1) a certain amount of naphthalenesulfonate formaldehyde condensation compound is added into deionized water, until it is fully dissolved so that naphthalene
The concentration of sulfonate and formaldehyde condensation product is 20g/L；
2) a certain amount of polyvinylpyrrolidone is added in the solution obtained to step 1), treats that it is fully dissolved so that
The concentration of final polyvinylpyrrolidone is 9g/L；
3) copper chloride is added in the solution obtained to step 2), stirs to it and fully dissolve so that finally copper ion is dense
Spend for 30mmol/L；
4) with the sodium hydroxide solution set-up procedure 3 of 1mol/L) obtained solution, until the pH value of solution is 10 ± 0.5；
5) solution for obtaining step 4) is warming up to 60 DEG C, and the ascorbic acid solution for adding that mass fraction is 30% is added dropwise,
So that the molar ratio of ascorbic acid and copper ion is 60：1,150min is then kept at such a temperature, obtains the nanometer of rufous
Copper colloidal solution；
6) the copper colloidal solution that after reaction, step 5) is obtained ultrasound 30min under the conditions of 40MHz, then with
10000rpm centrifuges 5min, precipitation and separation, is the copper nano particles of Coated with Organic Matter after dry.
The preparation method of the copper nanoparticle of 4 in-stiu coating organic matter of embodiment
1) a certain amount of naphthalenesulfonate formaldehyde condensation compound is added into deionized water, until it is fully dissolved so that naphthalene
The concentration of sulfonate and formaldehyde condensation product is 5g/L；
2) a certain amount of polyethylene glycol is added in the solution obtained to step 1), treats that it is fully dissolved so that is final poly-
The concentration of ethylene glycol is 9g/L；
3) copper acetate is added in the solution obtained to step 2), stirs to it and fully dissolve so that finally copper ion is dense
Spend for 10mmol/L；
4) with the sodium hydroxide solution set-up procedure 3 of 1mol/L) obtained solution, until the pH value of solution is 10 ± 0.5；
5) solution for obtaining step 4) is warming up to 40 DEG C, and the hydrazine hydrate solution for adding that mass fraction is 50% is added dropwise, makes
The molar ratio for obtaining hydrazine hydrate and copper ion is 66：1,150min is then kept at such a temperature, obtains the Nanometer Copper glue of rufous
Liquid solution；
6) the copper colloidal solution that after reaction, step 5) is obtained ultrasound 30min under the conditions of 40MHz, then with
10000rpm centrifuges 5min, precipitation and separation, is the copper nano particles of Coated with Organic Matter after dry.
The preparation method of the copper nanoparticle of 5 in-stiu coating organic matter of embodiment
1) a certain amount of dodecyl sodium naphthalene sulfonate is added into deionized water, until it is fully dissolved so that 12
The concentration of Negel is 2.5g/L；
2) a certain amount of polyvinylpyrrolidone is added in the solution obtained to step 1), treats that it is fully dissolved so that
The concentration of final polyvinylpyrrolidone is 9g/L；
3) copper formate is added in the solution obtained to step 2), stirs to it and fully dissolve so that finally copper ion is dense
Spend for 10mmol/L；
4) with the sodium hydroxide solution set-up procedure 3 of 1mol/L) obtained solution, until the pH value of solution is 10 ± 0.5；
5) solution for obtaining step 4) is warming up to 65 DEG C, and the hydrazine hydrate solution for adding that mass fraction is 50% is added dropwise, makes
The molar ratio for obtaining hydrazine hydrate and copper ion is 66：1,150min is then kept at such a temperature, obtains the Nanometer Copper glue of rufous
Liquid solution；
6) the copper colloidal solution that after reaction, step 5) is obtained ultrasound 30min under the conditions of 40MHz, then with
10000rpm centrifuges 5min, precipitation and separation, is the copper nano particles of Coated with Organic Matter after dry.
The preparation method of the copper nanoparticle of 6 in-stiu coating organic matter of embodiment
1) a certain amount of sodium lignin sulfonate is added into deionized water, until it is fully dissolved so that sulfomethylated lignin
The concentration of sour sodium is 6.5g/L；
2) a certain amount of polyethylene glycol is added in the solution obtained to step 1), treats that it is fully dissolved so that is final poly-
The concentration of ethylene glycol is 9g/L；
3) cupric sulfate pentahydrate is added in the solution obtained to step 2), stirs to it and fully dissolve so that final copper ion
Concentration be 10mmol/L；
4) with the sodium hydroxide solution set-up procedure 3 of 1mol/L) obtained solution, until the pH value of solution is 10 ± 0.5；
5) solution for obtaining step 4) is warming up to 50 DEG C, and the glucose solution for adding that mass fraction is 45% is added dropwise, makes
The molar ratio for obtaining glucose and copper ion is 50：1,180min is then kept at such a temperature, obtains the Nanometer Copper glue of rufous
Liquid solution；
6) the copper colloidal solution that after reaction, step 5) is obtained ultrasound 30min under the conditions of 40MHz, then with
10000rpm centrifuges 5min, precipitation and separation, is the copper nano particles of Coated with Organic Matter after dry.
The preparation method of the copper nanoparticle of 7 in-stiu coating organic matter of embodiment
1) a certain amount of di-2-ethylhexylphosphine oxide naphthalene sulfonic acids is added into deionized water, until it is fully dissolved so that methylene
The concentration of double naphthalene sulfonic acids is 8.5g/L；
2) a certain amount of polyethylene glycol is added in the solution obtained to step 1), treats that it is fully dissolved so that is final poly-
The concentration of ethylene glycol is 9g/L；
3) cupric sulfate pentahydrate is added in the solution obtained to step 2), stirs to it and fully dissolve so that final copper ion
Concentration be 10mmol/L；
4) with the sodium hydroxide solution set-up procedure 3 of 1mol/L) obtained solution, until the pH value of solution is 10 ± 0.5；
5) solution for obtaining step 4) is warming up to 70 DEG C, and the sodium borohydride solution for adding that mass fraction is 60% is added dropwise,
So that the molar ratio of sodium borohydride and copper ion is 50：1,210min is then kept at such a temperature, obtains the nanometer of rufous
Copper colloidal solution；
6) the copper colloidal solution that after reaction, step 5) is obtained ultrasound 30min under the conditions of 40MHz, then with
10000rpm centrifuges 5min, precipitation and separation, is the copper nano particles of Coated with Organic Matter after dry.
The preparation method of the copper nanoparticle of 8 in-stiu coating organic matter of embodiment
1) a certain amount of naphthalenesulfonate formaldehyde condensation compound is added into deionized water, until it is fully dissolved so that naphthalene
The concentration of sulfonate and formaldehyde condensation product is 20g/L；
2) cupric sulfate pentahydrate is added in the solution obtained to step 1), stirs to it and fully dissolve so that final copper ion
Concentration be 10mmol/L；
3) with the sodium hydroxide solution set-up procedure 2 of 1mol/L) obtained solution, until the pH value of solution is 10 ± 0.5；
4) solution for obtaining step 3) is warming up to 60 DEG C, and the hydrazine hydrate solution for adding that mass fraction is 80% is added dropwise, makes
The molar ratio for obtaining hydrazine hydrate and copper ion is 66：1,30min is then kept at such a temperature, obtains the nano copper colloid of rufous
Solution；
5) the copper colloidal solution that after reaction, step 4) is obtained ultrasound 30min under the conditions of 40MHz, then with
10000rpm centrifuges 5min, precipitation and separation, is the copper nano particles of Coated with Organic Matter after dry.
Embodiment 9 prepares the comparison of copper nanoparticle method with existing liquid-phase reduction
Method according to embodiment 1 prepares copper nanoparticle, as experimental group.
Control group 1：Copper nanoparticle is prepared using 1 method of CN1686648A embodiments, it is specific as follows：
1) the copper nitrate aqueous solution 100ml for being 0.01mol/L with distilled water compound concentration, is slowly added to concentration as 5.0%
Ammonium hydroxide, solution turned cloudy when being initially added into ammonium hydroxide, clears up gradually with the addition of ammonium hydroxide, stops after solution becomes limpid completely
Only add ammonium hydroxide；
2) 2.5g polyvinylpyrrolidones, 1g lauryl sodium sulfate are added in the solution that step 1) obtains, will be mixed
Solution is heated to 60 DEG C；
3) in stirring, the hydrazine hydrate aqueous solution that temperature is 60 DEG C, concentration is 2.5% is added to the mixing that step 2) obtains
In solution, when pH value reaches 9, stop adding hydrazine hydrate aqueous solution, add 0.01ml atoleines in the solution, continue to stir
60 minutes, when then ageing 20 is small, obtain the suspension containing Nanometer Copper；
4) under an argon atmosphere, suspension is centrifuged, first with distilled water, after cleaned 3 times with ethanol；
5) copper nanoparticle after step 4) is cleaned is put into vacuum drying chamber, dry at 70 DEG C.
Control group 2：Copper nanoparticle is prepared using 1 method of CN103769598A embodiments, it is specific as follows：
(1) 36g CuSO are added in pure water4·5H2O, compound concentration are the copper salt solution 250ml of 0.54mol/L, will be molten
Liquid is placed in the reactor of 500ml and is preheated to 50 DEG C.
(2) the ammonium hydroxide that fast drop mass percentage concentration is 20% under agitation, forms a degree of blue turbid solution,
The molar ratio of ammonium hydroxide and mantoquita is 2:1.The reducing agent hydrazine hydrate solution that mass percentage concentration is 80%, hydrazine hydrate are slowly added dropwise again
Molar ratio with mantoquita is 2:1.
(3) treat to be rapidly injected the dispersant solution 30ml that mass concentration is 6g/L when hydrazine hydrate also surplus 1/2, fed
Bi Baowen 2h.
(4) filtration washing is carried out to the brick-red powder of generation, first with the pure water boiled 2 times, then 2 are washed with ethanol
BHT alcohol solution dippings 20 minutes that are secondary, being finally 2.5g/L with concentration.
(5) supernatant is poured out after, is dried in vacuo to obtain copper powder.
Control group 3：Copper nanoparticle is prepared using 1 method of CN102205422A embodiments, it is specific as follows：
Weigh 500g cupric sulfate pentahydrates to be dissolved in 3L deionized waters, stirring is allowed to be completely dissolved, and is slowly added to the dense of 875g
Ammonium hydroxide (28%) is as clear as crystal up to solution, is heated to 45 DEG C；Weigh 2g lauryl sodium sulfate (SDS) and 1g OP-10 are dissolved in
In 1L deionized waters, then the aqueous solution of dispersant is slowly added in copper sulfate solution, stirring is allowed to the shape that is uniformly dispersed
Into mixed liquor A.The glucose for weighing 540g is added in A, and stirring is allowed to dissolving and forms mixed liquid B, and B is added 6L carries poly- four
In the stainless steel high temperature reaction kettle of vinyl fluoride liner, reaction kettle is tightened, is put into baking oven and is heated to 120 DEG C, keeps the temperature 2h, then certainly
Room temperature is so cooled to, mixed liquor is taken out, filters out precipitation, cleaned several times, be placed in vacuum drying chamber with deionized water and ethanol,
The dry 4h at 40 DEG C, final obtained high-purity, the copper nanoparticle of high surface.
The comparison of 1 experimental group of table and control group 1-3 preparation methods and copper nanoparticle product
| Atmosphere during preparation | Whether antioxidant is added during preservation | The inoxidizability of copper nanoparticle product | |
| Control group 1 | It need to be separated under protective atmosphere | Without additional antioxidant | Undetermined |
| Control group 2 | Without protective atmosphere | Additional antioxidant is needed during preservation | Undetermined |
| Control group 3 | Without protective atmosphere | Without additional antioxidant | Undetermined |
| Experimental group | Without protective atmosphere | Without additional antioxidant | Room temperature is placed 6 months and not aoxidized yet |
Although above the present invention is described in detail with a general description of the specific embodiments,
On the basis of the present invention, it can be modified or improved, this will be apparent to those skilled in the art.Cause
This, these modifications or improvements, belong to the scope of protection of present invention without departing from theon the basis of the spirit of the present invention.
Claims (10)
1. a kind of preparation method of the copper nanoparticle of in-stiu coating organic matter, it is characterised in that mantoquita is added to containing scattered
In agent and the optionally aqueous solution containing water-soluble macromolecule, dissolve and be uniformly mixed, add aqueous slkali and adjust pH to 10 ± 0.5,
Then reducing agent is added, after being warming up to 30-100 DEG C of reaction 30-240min, 10-60min is reacted under ultrasound condition, is cooled down,
Centrifugation, precipitation and separation, up to the copper nanoparticle of in-stiu coating organic matter after drying；
Wherein, the dispersant is selected from naphthalenesulfonate formaldehyde condensation compound, lignosulfonates, alkylnaphthalene sulfonate or di-2-ethylhexylphosphine oxide
At least one of naphthalene sulfonate；It is preferred that the dispersant is naphthalenesulfonate formaldehyde condensation compound；
The reducing agent in hydrazine hydrate, ascorbic acid, sodium borohydride, glucose, sodium hypophosphite, formaldehyde at least one
Kind；It is preferred that the reducing agent is hydrazine hydrate.
2. according to the method described in claim 1, it is characterized in that, the water-soluble macromolecule be selected from polyvinylpyrrolidone,
At least one of polyvinyl alcohol or polyethylene glycol.
3. according to the method described in claim 1, it is characterized in that, the mantoquita is selected from copper sulphate, copper nitrate, copper chloride, vinegar
At least one of sour copper or copper formate.
4. according to the method described in claim 1, it is characterized in that, the concentration of dispersant is 0.5-20g/L in the aqueous solution,
It is preferred that 1-18g/L, more preferably 2.5-10g/L, most preferably 5-6.5g/L.
5. according to the method described in claim 1, it is characterized in that, the concentration of water-soluble macromolecule is 0- in the aqueous solution
30g/L, preferably 1-20g/L, more preferably 5-15g/L, most preferably 6-9g/L.
6. according to the method described in claim 1, it is characterized in that, the concentration of mantoquita is 10-100mmol/ in the aqueous solution
L, preferably 20-80mmol/L, more preferably 30-50mmol/L.
7. according to the method described in claim 1, it is characterized in that, the molar ratio of the reducing agent and mantoquita is 20-66:1.
8. according to the method described in claim 1, it is characterized in that, it is warming up to 50 DEG C of reactions after adding reducing agent.
9. according to claim 1-8 any one of them methods, it is characterised in that comprise the following steps：
1) naphthalenesulfonate formaldehyde condensation compound is added in deionized water and dissolved, obtaining naphthalenesulfonate formaldehyde condensation compound content is
The solution I of 0.5-20g/L；
2) water-soluble macromolecule is added in solution I and dissolved, obtain the solution II that water-soluble macromolecule content is 1-20g/L；
3) mantoquita dissolving is added into solution II, obtains the solution III that mantoquita content is 10-100mmol/L；
4) pH to 10 ± 0.5 of solution III is adjusted with the sodium hydroxide solution of 1mol/L；
5) hydrazine hydrate is added in the mixed liquor under the conditions of stirring at normal temperature to step 4), obtains solution IV, copper ion in solution IV
Molar ratio with hydrazine hydrate is 1:20-70, preferably 1:30-66, more preferably 1:50-60；
6) solution IV is warming up to 50 DEG C, reacts 30-240min, then ultrasound 30min at such a temperature, be finally cooled to room temperature,
Centrifugation, precipitation and separation are dry.
10. the copper nanoparticle of the in-stiu coating organic matter prepared according to any one of claim 1-9 the method.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109256556A (en) * | 2018-10-19 | 2019-01-22 | 陕西科技大学 | A kind of starlike Cu/Cu of the cross of core-shell structure2O/CuO@Ppy composite material and preparation method and application |
| CN110026560A (en) * | 2018-08-27 | 2019-07-19 | 南方科技大学 | Nano copper particle and its preparation method and application |
| CN110026550A (en) * | 2018-11-07 | 2019-07-19 | 扬州工业职业技术学院 | A kind of nano zero-valence copper and preparation method and application |
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| CN112296327A (en) * | 2019-07-25 | 2021-02-02 | 上海沪正实业有限公司 | Nano copper powder and application thereof in preparation of automobile decorative cloth |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101474678A (en) * | 2008-11-28 | 2009-07-08 | 中国兵器工业第五二研究所 | Method for preparing antioxidated superfine copper powder |
| CN103464774A (en) * | 2012-06-07 | 2013-12-25 | 荆门市格林美新材料有限公司 | Preparation method for low-agglomeration antioxidant copper nanoparticle powder |
| JP2017106088A (en) * | 2015-12-11 | 2017-06-15 | 住友金属鉱山株式会社 | Method for producing copper powder and method for producing conductive paste using the same |
| CN106942274A (en) * | 2017-03-30 | 2017-07-14 | 安徽省银锂子生物科技发展有限公司 | A kind of high-effective broad-spectrum fungicide of low content Nano silver solution |
| CN107142090A (en) * | 2017-06-21 | 2017-09-08 | 湖北久之洋红外***股份有限公司 | A kind of heat transmission nano-fluid, preparation method and applications |
| CN107326401A (en) * | 2017-05-22 | 2017-11-07 | 昆明理工大学 | A kind of preparation method of CNTs/Cu composite granules and CNTs/Cu composites |
-
2018
- 2018-01-08 CN CN201810014435.XA patent/CN108031839B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101474678A (en) * | 2008-11-28 | 2009-07-08 | 中国兵器工业第五二研究所 | Method for preparing antioxidated superfine copper powder |
| CN103464774A (en) * | 2012-06-07 | 2013-12-25 | 荆门市格林美新材料有限公司 | Preparation method for low-agglomeration antioxidant copper nanoparticle powder |
| JP2017106088A (en) * | 2015-12-11 | 2017-06-15 | 住友金属鉱山株式会社 | Method for producing copper powder and method for producing conductive paste using the same |
| CN106942274A (en) * | 2017-03-30 | 2017-07-14 | 安徽省银锂子生物科技发展有限公司 | A kind of high-effective broad-spectrum fungicide of low content Nano silver solution |
| CN107326401A (en) * | 2017-05-22 | 2017-11-07 | 昆明理工大学 | A kind of preparation method of CNTs/Cu composite granules and CNTs/Cu composites |
| CN107142090A (en) * | 2017-06-21 | 2017-09-08 | 湖北久之洋红外***股份有限公司 | A kind of heat transmission nano-fluid, preparation method and applications |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110026560A (en) * | 2018-08-27 | 2019-07-19 | 南方科技大学 | Nano copper particle and its preparation method and application |
| CN109256556A (en) * | 2018-10-19 | 2019-01-22 | 陕西科技大学 | A kind of starlike Cu/Cu of the cross of core-shell structure2O/CuO@Ppy composite material and preparation method and application |
| CN109256556B (en) * | 2018-10-19 | 2020-11-17 | 陕西科技大学 | Cross star-shaped Cu/Cu with core-shell structure2O/CuO @ Ppy composite material and preparation method and application thereof |
| CN110026550A (en) * | 2018-11-07 | 2019-07-19 | 扬州工业职业技术学院 | A kind of nano zero-valence copper and preparation method and application |
| CN110039069A (en) * | 2019-05-30 | 2019-07-23 | 江西省科学院能源研究所 | A kind of spongy Micron Copper Powder and preparation method thereof |
| CN110039069B (en) * | 2019-05-30 | 2021-05-14 | 江西省科学院能源研究所 | Spongy micron copper powder and preparation method thereof |
| CN112296327A (en) * | 2019-07-25 | 2021-02-02 | 上海沪正实业有限公司 | Nano copper powder and application thereof in preparation of automobile decorative cloth |
| CN112296326A (en) * | 2019-07-25 | 2021-02-02 | 上海沪正实业有限公司 | Nano copper powder and application thereof in preparation of antibacterial and mildewproof carpet |
| CN115119854A (en) * | 2022-06-14 | 2022-09-30 | 上海太和水科技发展股份有限公司 | Material for controlling growth of landscape filamentous algae and use method thereof |
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