CN114985730A - Preparation method of antioxidant copper powder - Google Patents
Preparation method of antioxidant copper powder Download PDFInfo
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- CN114985730A CN114985730A CN202210461639.4A CN202210461639A CN114985730A CN 114985730 A CN114985730 A CN 114985730A CN 202210461639 A CN202210461639 A CN 202210461639A CN 114985730 A CN114985730 A CN 114985730A
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- copper powder
- powder
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 147
- 239000003963 antioxidant agent Substances 0.000 title claims abstract description 27
- 230000003078 antioxidant effect Effects 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 30
- 239000007788 liquid Substances 0.000 claims abstract description 27
- 238000003756 stirring Methods 0.000 claims abstract description 24
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000203 mixture Substances 0.000 claims abstract description 22
- 239000003607 modifier Substances 0.000 claims abstract description 22
- 230000003647 oxidation Effects 0.000 claims abstract description 15
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 15
- 238000004321 preservation Methods 0.000 claims abstract description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 84
- 239000000843 powder Substances 0.000 claims description 48
- 239000007787 solid Substances 0.000 claims description 37
- 238000005406 washing Methods 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 22
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 21
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 15
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 15
- 238000001914 filtration Methods 0.000 claims description 15
- 239000000047 product Substances 0.000 claims description 15
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 238000004140 cleaning Methods 0.000 claims description 14
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- 238000002791 soaking Methods 0.000 claims description 11
- 239000006185 dispersion Substances 0.000 claims description 10
- 239000012153 distilled water Substances 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 10
- 239000006228 supernatant Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 235000019441 ethanol Nutrition 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 5
- 230000003064 anti-oxidating effect Effects 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- 238000004821 distillation Methods 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 239000002085 irritant Substances 0.000 claims description 5
- 231100000021 irritant Toxicity 0.000 claims description 5
- 238000003760 magnetic stirring Methods 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- WPMYUUITDBHVQZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000012459 cleaning agent Substances 0.000 claims description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 3
- YEXOWHQZWLCHHD-UHFFFAOYSA-N 3,5-ditert-butyl-4-hydroxybenzoic acid Chemical compound CC(C)(C)C1=CC(C(O)=O)=CC(C(C)(C)C)=C1O YEXOWHQZWLCHHD-UHFFFAOYSA-N 0.000 claims description 3
- ZYAASQNKCWTPKI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propan-1-amine Chemical compound CO[Si](C)(OC)CCCN ZYAASQNKCWTPKI-UHFFFAOYSA-N 0.000 claims description 3
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 2
- 239000012756 surface treatment agent Substances 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 14
- 229910052814 silicon oxide Inorganic materials 0.000 abstract description 8
- 239000011241 protective layer Substances 0.000 abstract description 7
- 239000002184 metal Substances 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000010410 layer Substances 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 230000001681 protective effect Effects 0.000 abstract description 3
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 3
- 239000011229 interlayer Substances 0.000 abstract description 2
- 239000005543 nano-size silicon particle Substances 0.000 abstract description 2
- 238000009700 powder processing Methods 0.000 abstract description 2
- 238000004381 surface treatment Methods 0.000 abstract 1
- 235000006708 antioxidants Nutrition 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 11
- 239000010949 copper Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 229910052802 copper Inorganic materials 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 4
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 2
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 2
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000001577 tetrasodium phosphonato phosphate 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
- 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
- 229910001369 Brass Inorganic materials 0.000 description 1
- 229910000906 Bronze Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-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
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical group CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- LAKVEQZDAPXLDL-UHFFFAOYSA-M sodium;ethanol;octadecanoate Chemical compound [Na+].CCO.CCCCCCCCCCCCCCCCCC([O-])=O LAKVEQZDAPXLDL-UHFFFAOYSA-M 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 239000002470 thermal conductor Substances 0.000 description 1
- 230000004584 weight gain Effects 0.000 description 1
- 235000019786 weight gain Nutrition 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Powder Metallurgy (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
- Anti-Oxidant Or Stabilizer Compositions (AREA)
Abstract
The invention relates to the technical field of metal powder processing, in particular to a preparation method of antioxidant copper powder; the method comprises the steps of immersing the pretreated copper powder in absolute ethyl alcohol, dripping the mixed sample liquid into the absolute ethyl alcohol, and carrying out heat preservation stirring treatment on the mixture formed by the two steps to ensure that the nano silicon dioxide can be fully coated on the surface of the copper powder, so that a layer of compact inorganic protective film is formed on the surface of the copper powder, the contact between the copper powder and the outside air is effectively reduced, the oxidation probability of the copper powder is also effectively reduced, and the chemical stability of the copper powder is improved; moreover, because a chemical reaction occurs between the surface treatment machine and the modifier, a compact three-dimensional topological network structure is formed on the surface of the silicon oxide protective layer, and finally triphenyl phosphite is limited in the three-dimensional topological network structure and an interlayer of the silicon oxide protective layer; the antioxidant performance of the copper powder is further improved under the mutual synergism and mutual matching of triphenyl phosphite and a modifier.
Description
Technical Field
The invention relates to the technical field of metal powder processing, in particular to a preparation method of antioxidant copper powder.
Background
Copper is a chemical element, designated as Cu, and is a soft, ductile metal with high thermal and electrical conductivity. The freshly exposed pure copper surface was red-orange in color. Copper is commonly used as a component of thermal conductors, electrical conductors, building materials, and various metal alloys. Copper alloys have excellent mechanical properties and very low electrical resistivity, the most important of which are bronze and brass. In addition, copper is also a durable metal that can be recycled many times without compromising its mechanical properties.
Copper is widely used in various fields because of its many excellent properties as described above. For example, copper powder is widely used in the fields of powder metallurgy, electrical carbon products, electronic materials, metal coatings, chemical catalysts, filters, heat dissipation tubes and other electromechanical parts and electronic aviation.
Although copper powder has many of the excellent properties described above, it has the disadvantage of being easily oxidized by air, which affects its own conductivity to some extent. At present, the means for slowing down the oxidation of copper powder are relatively more, but most of the copper powder is coated with a layer of organic coating agent or antioxidant (organic coating machine is stearic acid, sodium stearate, oleic acid and the like; antioxidant is ascorbic acid, phosphoric acid and salts thereof, metaphosphoric acid and salts thereof and the like) on the surface of the copper powder, so that the oxidation probability of the copper powder is slowed down. However, this method is not very effective in suppressing oxidation of copper powder. Therefore, it is an urgent technical problem to be solved by those skilled in the art!
Disclosure of Invention
The invention aims to provide a preparation method of antioxidant copper powder, wherein a layer of compact inorganic protective film is formed on the surface of the prepared copper powder, so that the contact between the copper powder and the outside air is effectively reduced, and the probability of oxidation of the copper powder is also effectively reduced, thereby improving the chemical stability of the copper powder.
In order to achieve the purpose, the invention provides the following technical scheme:
the preparation method of the antioxidant copper powder comprises the following steps:
firstly, preparing inorganic powder coated copper powder;
weighing a proper amount of absolute ethyl alcohol, respectively adding 0.02-0.55% of distilled water and 0.4-1.8% of tetraethyl silicate by volume, then dropwise adding a proper amount of ammonia water, and carrying out heat preservation and stirring treatment at the temperature of 35-45 ℃ for 40-60 min; after the reaction is finished, the obtained mixture is marked as mixed sample liquid;
II, putting the pretreated copper powder into a proper amount of absolute ethyl alcohol according to a material ratio of 0.08-0.12 g/mL, performing ultrasonic dispersion for 10-15 min, and storing the obtained dispersion for later use;
III, according to the proportion of 1: slowly dripping a proper amount of the mixed sample liquid prepared in the step I into the dispersion liquid obtained in the step II according to the volume ratio of 2.0-3.0, and carrying out heat preservation and stirring reaction for 4-7 h at the temperature of 40-60 ℃; after the reaction is finished, sequentially carrying out centrifugation and drying treatment on the obtained reaction product to obtain an inorganic powder coated copper powder finished product;
secondly, preparing anti-oxidation copper powder;
step one, dipping the inorganic powder coated copper powder in a proper amount of organic solvent according to a solid-to-liquid ratio of 0.05-0.1 g/mL, then adding a surface treatment agent with the mass 1.0-1.5 times of that of the inorganic powder coated copper powder into the inorganic powder coated copper powder, reacting at the temperature of 60-70 ℃ for 20-25 hours, filtering the inorganic powder coated copper powder after the reaction is finished, removing the organic solvent, washing the filtered solid component with an organic cleaning agent, and drying the solid component, wherein the obtained solid powder is stored for later use;
secondly, adding the obtained solid powder into a proper amount of toluene according to a solid-liquid ratio of 0.02-0.05 g/mL, then adding triphenyl phosphite with the mass of 8-12% of the solid powder into the toluene, uniformly mixing and dispersing, adding a modifier with the mass of 20-30% of the solid powder and N, N-dimethylaniline with the volume of 2.5-3.8% of the toluene into the mixture while stirring, and carrying out heat preservation reaction on the obtained mixed phase at 25-35 ℃ for 20-30 h under the nitrogen atmosphere;
and step three, after the reaction is finished, filtering and washing the obtained mixed phase, respectively washing the solid filter material for 3-4 times by using toluene and ethanol, and finally drying to obtain the finished product of the antioxidant copper powder.
Furthermore, the concentration of the ammonia water is 20-30%, and the dosage of the ammonia water is 0.8-3 times of the volume of the distilled water.
Furthermore, the copper powder is selected from commercially available spherical-like copper powder, and the average particle size of the copper powder is 1.5-2.0 μm.
Furthermore, the pretreatment process of the copper powder comprises the following steps: firstly, carrying out magnetic stirring cleaning on copper powder for 20-30 min by using a dilute sulfuric acid solution with the concentration of 2-4%; after washing, standing and pouring out the supernatant; then soaking the substrate in acetone at a temperature of 55-65 ℃, stirring and cleaning for 30-40 min; and after washing, standing and pouring out supernatant, and finally drying at the temperature of 60-70 ℃ to finish the pretreatment of the copper powder.
Furthermore, the organic solvent is any one of N, N-dimethylformamide, benzene and toluene.
Furthermore, the surface treating agent is any one of 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane and N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane.
Further, the preparation method of the modifier comprises the following steps: and (3) adding an antioxidant into a proper amount of oxalyl chloride according to the material ratio of 0.02-0.05 g/mL, carrying out reflux reaction until no irritant gas escapes, and recovering the residual oxalyl chloride by a distillation method to obtain the finished modifier.
Furthermore, the antioxidant is any one of 3, 5-di-tert-butyl-4-hydroxy-phenylpropionic acid and 3, 5-di-tert-butyl-4-hydroxy-benzoic acid.
Furthermore, in the preparation process of the antioxidant copper powder, the organic cleaning agent is selected from one or a combination of two of N, N-dimethylformamide, toluene, ethanol and acetone.
Compared with the prior art, the invention has the beneficial effects that:
1. the method comprises the steps of firstly pretreating the surface of copper powder to remove an oxidation film on the surface of the copper powder, then soaking the pretreated copper powder in absolute ethyl alcohol, simultaneously dropwise adding a mixed sample liquid into the absolute ethyl alcohol, and then carrying out heat preservation stirring treatment on a mixture formed by the two components, so that the nano silicon dioxide can be fully coated on the surface of the copper powder, a layer of compact inorganic protective film is formed on the surface of the copper powder, the contact between the copper powder and the outside air is effectively reduced, the oxidation probability of the copper powder is also effectively reduced, and the chemical stability of the copper powder is improved.
2. The prepared inorganic powder coated copper powder is soaked in an organic solvent containing a surface treating agent, and the surface treating agent and silicon oxide in a silicon dioxide coating layer on the outer surface of the copper powder are subjected to chemical reaction at a certain temperature to be bonded. And then putting the obtained solid powder into toluene containing triphenyl phosphite, uniformly dispersing triphenyl phosphite by a mixing and dispersing method, finally uniformly adsorbing the triphenyl phosphite on the surface of the silicon oxide protective layer, and then supplementing a proper amount of modifier and N, N-dimethylaniline into the mixture to ensure that a surface processor bonded on the outer surface of the silicon oxide protective layer and the modifier generate chemical reaction under the action of the N, N-dimethylaniline to form a bond, and finally, the modifier is indirectly grafted on the surface of the silicon oxide protective layer successfully. Wherein, because of chemical reaction between the surface processor and the modifier, a compact three-dimensional topological network structure is formed on the surface of the silicon oxide protective layer, and finally triphenyl phosphite is limited in the three-dimensional topological network structure and the 'interlayer' of the silicon oxide protective layer; the antioxidant performance of the copper powder is further improved under the mutual synergism and mutual matching of triphenyl phosphite and a modifier.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The preparation method of the oxidation-resistant copper powder comprises the following steps:
firstly, preparing inorganic powder coated copper powder;
weighing a proper amount of absolute ethyl alcohol, respectively adding 0.02% of distilled water and 0.4% of tetraethyl silicate by volume, then dropwise adding a proper amount of ammonia water, and carrying out heat preservation and stirring treatment at the temperature of 35 ℃ for 40 min; after the reaction is finished, the obtained mixture is marked as mixed sample liquid; wherein the concentration of the ammonia water is 20 percent, and the dosage of the ammonia water is 0.8 time of the volume of the distilled water;
II, putting the pretreated copper powder into a proper amount of absolute ethyl alcohol according to a material ratio of 0.08g/mL, performing ultrasonic dispersion for 10min, and storing the obtained dispersion for later use; wherein, the copper powder is selected from the commercial spherical copper powder, and the average grain diameter of the copper powder is 1.5 mu m;
III, according to the proportion of 1: 2.0, slowly dripping a proper amount of the mixed sample liquid prepared in the step I into the dispersion liquid obtained in the step II, and carrying out heat preservation and stirring reaction for 4 hours at the temperature of 40 ℃; after the reaction is finished, sequentially carrying out centrifugation and drying treatment on the obtained reaction product to obtain an inorganic powder coated copper powder finished product;
secondly, preparing anti-oxidation copper powder;
step one, soaking the inorganic powder coated copper powder in a proper amount of N, N-dimethylformamide according to a solid-to-liquid ratio of 0.05g/mL, then adding 3-aminopropyltriethoxysilane which is 1.0 time of the inorganic powder coated copper powder in mass, reacting at the temperature of 60 ℃ for 20 hours, filtering the mixture after the reaction is finished, removing an organic solvent, washing a solid component obtained by filtering for 3 times by using N, N-dimethylformamide, and drying the solid component, wherein the obtained solid powder is stored for later use;
step two, putting the obtained solid powder into proper amount of toluene according to a solid-liquid ratio of 0.02g/mL, then adding triphenyl phosphite with the mass of 8% of the solid powder into the toluene, uniformly mixing and dispersing the mixture, adding a modifier with the mass of 20% of the solid powder and N, N-dimethylaniline with the volume of 2.5% of the toluene into the mixture while stirring, and keeping the temperature of the obtained mixed phase at 25 ℃ for reaction for 20 hours in a nitrogen atmosphere;
and step three, after the reaction is finished, filtering and washing the obtained mixed phase, respectively washing the solid filter material for 3 times by using toluene and ethanol, and finally drying to obtain the finished product of the antioxidant copper powder.
The pretreatment process of the copper powder comprises the following steps: firstly, carrying out magnetic stirring and cleaning on copper powder for 20min by using a dilute sulfuric acid solution with the concentration of 2%; after washing, standing and pouring out the supernatant; soaking in acetone at 55 deg.C, stirring, and cleaning for 30 min; after washing, standing and pouring out the supernatant, and finally drying at the temperature of 60 ℃ to finish the pretreatment of the copper powder.
The preparation method of the modifier comprises the following steps: adding 3, 5-di-tert-butyl-4-hydroxy-phenylpropionic acid into a proper amount of oxalyl chloride according to the material ratio of 0.02g/mL, carrying out reflux reaction until no irritant gas escapes, and recovering the residual oxalyl chloride by a distillation method to obtain the finished modifier.
Example 2
The preparation method of the antioxidant copper powder comprises the following steps:
firstly, preparing inorganic powder coated copper powder;
weighing a proper amount of absolute ethyl alcohol, respectively adding 0.3% of distilled water and 1.2% of tetraethyl silicate by volume, then dropwise adding a proper amount of ammonia water, and carrying out heat preservation and stirring treatment at the temperature of 40 ℃ for 50 min; after the reaction is finished, the obtained mixture is marked as mixed sample liquid; wherein the concentration of the ammonia water is 25 percent, and the dosage of the ammonia water is 2 times of the volume of the distilled water;
II, putting the pretreated copper powder into a proper amount of absolute ethyl alcohol according to a material ratio of 0.1g/mL, performing ultrasonic dispersion for 10min, and storing the obtained dispersion for later use; wherein, the copper powder is selected from the commercial spherical copper powder, and the average grain diameter of the copper powder is 1.8 mu m;
III, according to the proportion of 1: 2.5, slowly dripping a proper amount of the mixed sample liquid prepared in the step I into the dispersion liquid obtained in the step II according to the volume ratio, and carrying out heat preservation and stirring reaction for 5 hours at the temperature of 50 ℃; after the reaction is finished, sequentially carrying out centrifugation and drying treatment on the obtained reaction product to obtain an inorganic powder coated copper powder finished product;
secondly, preparing anti-oxidation copper powder;
step one, soaking the inorganic powder coated copper powder in a proper amount of benzene according to a solid-to-liquid ratio of 0.08g/mL, then adding 3-aminopropylmethyldimethoxysilane with the mass 1.2 times of that of the inorganic powder coated copper powder into the benzene, reacting for 23 hours at the temperature of 65 ℃, filtering the mixture after the reaction is finished, removing the organic solvent, washing the solid component obtained by filtering for 3 times by using toluene, and drying the solid component, wherein the obtained solid powder is stored for later use;
step two, putting the obtained solid powder into proper toluene according to a solid-liquid ratio of 0.04g/mL, then adding triphenyl phosphite with the mass of 10% of the solid powder into the toluene, uniformly mixing and dispersing the mixture, adding a modifier with the mass of 25% of the solid powder and N, N-dimethylaniline with the volume of 3.2% of the toluene into the mixture while stirring, and keeping the temperature of the obtained mixed phase at 30 ℃ for reaction for 25 hours in a nitrogen atmosphere;
and step three, after the reaction is finished, filtering and washing the obtained mixed phase, respectively washing the solid filter material for 4 times by using toluene and ethanol, and finally drying to obtain the finished product of the antioxidant copper powder.
The pretreatment process of the copper powder comprises the following steps: firstly, carrying out magnetic stirring and cleaning on copper powder for 25min by using a dilute sulfuric acid solution with the concentration of 3%; after washing, standing and pouring out the supernatant; soaking in acetone at 60 deg.C, stirring, and cleaning for 35 min; after washing, standing and pouring out the supernatant, and finally drying at 65 ℃ to finish the pretreatment of the copper powder.
The preparation method of the modifier comprises the following steps: 3, 5-di-tert-butyl-4-hydroxy-benzoic acid is added into a proper amount of oxalyl chloride according to the material ratio of 0.035g/mL, reflux reaction is carried out until no irritant gas escapes, and the residual oxalyl chloride is recovered by a distillation method, so that the finished product of the modifier is obtained.
Example 3
The preparation method of the antioxidant copper powder comprises the following steps:
firstly, preparing inorganic powder coated copper powder;
i, weighing a proper amount of absolute ethyl alcohol, respectively adding 0.55% of distilled water and 1.8% of tetraethyl silicate by volume, then dropwise adding a proper amount of ammonia water, and carrying out heat preservation and stirring treatment at the temperature of 45 ℃ for 60 min; after the reaction is finished, the obtained mixture is marked as mixed sample liquid; wherein the concentration of the ammonia water is 30 percent, and the dosage of the ammonia water is 3 times of the volume of the distilled water;
II, putting the pretreated copper powder into a proper amount of absolute ethyl alcohol according to a material ratio of 0.12g/mL, performing ultrasonic dispersion for 15min, and storing the obtained dispersion for later use; wherein, the copper powder is selected from the commercial spherical copper powder, and the average grain diameter of the copper powder is 2.0 μm;
III, according to the proportion of 1: slowly dripping a proper amount of the mixed sample liquid prepared in the step I into the dispersion liquid obtained in the step II according to the volume ratio of 3.0, and carrying out heat preservation and stirring reaction for 7 hours at the temperature of 60 ℃; after the reaction is finished, sequentially centrifuging and drying the obtained reaction product to obtain an inorganic powder coated copper powder finished product;
secondly, preparing anti-oxidation copper powder;
step one, soaking the inorganic powder coated copper powder in a proper amount of toluene according to a solid-to-liquid ratio of 0.1g/mL, then adding N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane with the mass 1.5 times that of the inorganic powder coated copper powder into the mixture, reacting the mixture at the temperature of 70 ℃ for 25 hours, filtering the mixture after the reaction is finished, removing an organic solvent, cleaning a solid component obtained by filtering the mixture for 3 times by using N, N-dimethylformamide, cleaning the solid component for 3 times by using toluene, and then drying the solid component, and storing the obtained solid powder for later use;
step two, putting the obtained solid powder into proper amount of toluene according to a solid-liquid ratio of 0.05g/mL, then adding triphenyl phosphite with the mass of 12% of the solid powder into the toluene, uniformly mixing and dispersing the mixture, adding a modifier with the mass of 30% of the solid powder and N, N-dimethylaniline with the volume of 3.8% of the toluene into the mixture while stirring, and keeping the temperature of the obtained mixed phase at 35 ℃ for reaction for 30 hours in a nitrogen atmosphere;
and step three, after the reaction is finished, filtering and washing the obtained mixed phase, respectively washing the solid filter material for 4 times by using toluene and ethanol, and finally drying to obtain the finished product of the antioxidant copper powder.
The pretreatment process of the copper powder comprises the following steps: firstly, carrying out magnetic stirring and cleaning on copper powder for 30min by using a dilute sulfuric acid solution with the concentration of 4%; after washing, standing and pouring out the supernatant; soaking in 65 deg.C acetone, stirring, and cleaning for 40 min; after washing, standing and pouring out the supernatant, and finally drying at the temperature of 70 ℃ to finish the pretreatment of the copper powder.
The preparation method of the modifier comprises the following steps: adding 3, 5-di-tert-butyl-4-hydroxy-phenylpropionic acid into a proper amount of oxalyl chloride according to the material ratio of 0.05g/mL, carrying out reflux reaction until no irritant gas escapes, and recovering the residual oxalyl chloride by a distillation method to obtain the finished modifier.
Comparative example 1: spherical-like copper powder having an average particle size of 2.0 μm is commercially available;
comparative example 2: the surface of the copper powder is coated with sodium stearate and the commercial spherical copper powder with the average grain diameter of 2.0 mu m; the preparation method comprises the following steps: cleaning the surface of the copper powder by using 2% dilute sulfuric acid solution, then soaking the copper powder in 2 wt% sodium stearate ethanol solution, stirring for 20min, filtering and drying to obtain the copper powder;
comparative example 3: the surface of the copper powder is coated with sodium hexametaphosphate and commercially available spherical copper powder with the average grain diameter of 2.0 mu m; the preparation method comprises the following steps: cleaning the surface of the copper powder by using 2% dilute sulfuric acid solution, then soaking the copper powder in 3 wt% sodium hexametaphosphate aqueous solution, stirring for 20min, then filtering and drying to obtain the copper powder;
performance testing
The copper powders prepared in examples 1 to 3 of the present invention were described as experimental examples 1 to 3; the copper powder provided by the comparative example is recorded as comparative example 1-3; then, the copper powders provided in the experimental examples 1 to 3 and the comparative examples 1 to 3 were subjected to heat treatment to test the oxidation resistance thereof, and the obtained data are recorded in the following table:
note: the "+" in the table indicates the weight gain of the copper powder after heat treatment.
It can be seen from the comparison and analysis of the relevant data in the table that the weight of the copper powder provided in comparative examples 1 to 3 and experimental examples 1 to 3 increases in different ranges with the increase of the heat treatment time, because the surface of the copper powder undergoes oxidation-reduction reaction with oxygen in the air, so that a copper oxide film is formed on the surface of the copper powder, and the quality of the copper powder is increased to a certain extent. In addition, as can be seen from the data in the table, the rate of weight change was greatest for the copper powder provided in comparative example 1 as the heat treatment temperature increased, while the rates of weight change decreased in the order of comparative example 2, comparative example 3, experimental example 1, experimental example 3, and experimental example 2 for the copper powder products provided. Therefore, compared with the copper powder product provided by the comparative example, the copper powder prepared by the invention has better oxidation resistance and stability. Therefore, the copper powder product produced by the method has wider market prospect and is more suitable for popularization.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best understand the invention for and utilize the invention. The invention is limited only by the claims and their full scope and equivalents.
Claims (9)
1. The preparation method of the antioxidant copper powder is characterized by comprising the following steps of:
firstly, preparing inorganic powder coated copper powder;
weighing a proper amount of absolute ethyl alcohol, respectively adding 0.02-0.55% of distilled water and 0.4-1.8% of tetraethyl silicate by volume, then dropwise adding a proper amount of ammonia water, and carrying out heat preservation and stirring treatment at the temperature of 35-45 ℃ for 40-60 min; after the reaction is finished, the obtained mixture is marked as mixed sample liquid;
II, putting the pretreated copper powder into a proper amount of absolute ethyl alcohol according to a material ratio of 0.08-0.12 g/mL, performing ultrasonic dispersion for 10-15 min, and storing the obtained dispersion for later use;
III, according to the proportion of 1: slowly dripping a proper amount of the mixed sample liquid prepared in the step I into the dispersion liquid obtained in the step II according to the volume ratio of 2.0-3.0, and carrying out heat preservation stirring reaction for 4-7 hours at the temperature of 40-60 ℃; after the reaction is finished, sequentially carrying out centrifugation and drying treatment on the obtained reaction product to obtain an inorganic powder coated copper powder finished product;
secondly, preparing anti-oxidation copper powder;
step one, impregnating the inorganic powder coated copper powder in a proper amount of organic solvent according to a solid-to-liquid ratio of 0.05-0.1 g/mL, then adding a surface treatment agent with the mass being 1.0-1.5 times of that of the inorganic powder coated copper powder into the inorganic powder coated copper powder, reacting at the temperature of 60-70 ℃ for 20-25 hours, filtering the inorganic powder coated copper powder after the reaction is finished, removing the organic solvent, washing the filtered solid component with an organic cleaning agent, and drying the solid component, wherein the obtained solid powder is stored for later use;
secondly, adding the obtained solid powder into a proper amount of toluene according to a solid-liquid ratio of 0.02-0.05 g/mL, then adding triphenyl phosphite with the mass of 8-12% of the solid powder into the toluene, uniformly mixing and dispersing, adding a modifier with the mass of 20-30% of the solid powder and N, N-dimethylaniline with the volume of 2.5-3.8% of the toluene into the mixture while stirring, and carrying out heat preservation reaction on the obtained mixed phase at 25-35 ℃ for 20-30 h under the nitrogen atmosphere;
and step three, after the reaction is finished, filtering and washing the obtained mixed phase, respectively washing the solid filter material for 3-4 times by using toluene and ethanol, and finally drying to obtain the finished product of the antioxidant copper powder.
2. The method for preparing the antioxidant copper powder as claimed in claim 1, wherein the method comprises the following steps: the concentration of the ammonia water is 20-30%, and the dosage of the ammonia water is 0.8-3 times of the volume of the distilled water.
3. The method for preparing oxidation-resistant copper powder according to claim 1, wherein the method comprises the following steps: the copper powder is selected from commercially available spherical copper powder, and the average particle size of the copper powder is 1.5-2.0 mu m.
4. The method for preparing the antioxidant copper powder as claimed in claim 1, wherein the pretreatment process of the copper powder comprises the following steps: firstly, carrying out magnetic stirring cleaning on copper powder for 20-30 min by using a dilute sulfuric acid solution with the concentration of 2-4%; after washing, standing and pouring out the supernatant; then soaking the substrate in acetone with a temperature of 55-65 ℃, stirring and cleaning for 30-40 min; and after washing, standing and pouring out supernatant, and finally drying at the temperature of 60-70 ℃ to finish the pretreatment of the copper powder.
5. The method for preparing oxidation-resistant copper powder according to claim 1, wherein the method comprises the following steps: the organic solvent is any one of N, N-dimethylformamide, benzene and toluene.
6. The method for preparing oxidation-resistant copper powder according to claim 1, wherein the method comprises the following steps: the surface treating agent is any one of 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane and N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane.
7. The method for preparing the antioxidant copper powder as claimed in claim 1, wherein the method for preparing the modifier comprises the following steps: and (3) adding an antioxidant into a proper amount of oxalyl chloride according to the material ratio of 0.02-0.05 g/mL, carrying out reflux reaction until no irritant gas escapes, and recovering the residual oxalyl chloride by a distillation method to obtain the finished modifier.
8. The method for preparing oxidation-resistant copper powder according to claim 7, wherein the method comprises the following steps: the antioxidant is any one of 3, 5-di-tert-butyl-4-hydroxy-phenylpropionic acid and 3, 5-di-tert-butyl-4-hydroxy-benzoic acid.
9. The method for preparing oxidation-resistant copper powder according to claim 1, wherein the method comprises the following steps: in the preparation process of the antioxidant copper powder, the organic cleaning agent is any one or the combination of two of N, N-dimethylformamide, toluene, ethanol and acetone.
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