CN102554263B - Preparation method for Cu/Fe3O4 composite nanoparticles having good dispersity in organic medium - Google Patents
Preparation method for Cu/Fe3O4 composite nanoparticles having good dispersity in organic medium Download PDFInfo
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- 239000002105 nanoparticle Substances 0.000 title claims abstract description 43
- 239000002131 composite material Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 title abstract 6
- 239000010949 copper Substances 0.000 claims abstract description 38
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 16
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 16
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- 239000003495 polar organic solvent Substances 0.000 claims abstract description 7
- 150000001879 copper Chemical class 0.000 claims abstract description 6
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 5
- 239000012074 organic phase Substances 0.000 claims abstract description 3
- 238000000926 separation method Methods 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 29
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 28
- 239000007864 aqueous solution Substances 0.000 claims description 18
- 150000002505 iron Chemical class 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 150000001412 amines Chemical class 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- 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 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- 150000001924 cycloalkanes Chemical class 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 24
- 238000002156 mixing Methods 0.000 abstract description 11
- 239000002245 particle Substances 0.000 abstract description 11
- 238000009776 industrial production Methods 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract 2
- 150000003839 salts Chemical class 0.000 abstract 2
- 239000000243 solution Substances 0.000 description 72
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 16
- 229910052802 copper Inorganic materials 0.000 description 16
- 238000007865 diluting Methods 0.000 description 15
- 239000012153 distilled water Substances 0.000 description 15
- 239000010410 layer Substances 0.000 description 12
- 239000012044 organic layer Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 8
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 8
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 8
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 8
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 8
- 239000005642 Oleic acid Substances 0.000 description 8
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 8
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 8
- 229920013639 polyalphaolefin Polymers 0.000 description 8
- 230000005291 magnetic effect Effects 0.000 description 7
- 230000009467 reduction Effects 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 239000007791 liquid phase Substances 0.000 description 5
- 239000012263 liquid product Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000013517 stratification Methods 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 239000002199 base oil Substances 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 239000010687 lubricating oil Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- GOKIPOOTKLLKDI-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O.CC(O)=O GOKIPOOTKLLKDI-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000003701 mechanical milling Methods 0.000 description 1
- 238000010303 mechanochemical reaction Methods 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound 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
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 239000003870 refractory metal Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
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Abstract
The invention relates to a preparation method for Cu/Fe3O4 composite nanoparticles having good dispersity in organic medium, which comprises steps of adding a hydrazine hydrate water solution containing ammonia water into a copper salt water solution to react for 1-30min; adding a mixing water solution of ferrous salt and ferric salt to react for 10-60min; and finally adding a non-polar or weak-polar organic solvent dissolving with a dressing agent to react for 10-20min, standing for separation, taking the organic phase, and concentrating to obtain the Cu/Fe3O4 composite nanoparticles having good dispersity in organic medium, wherein the molar ratio of the copper salt, the hydrazine hydrate, the ferrous salt and the dressing agent is 1:1-10:0.1-1:0.25-2, the molar ratio of the ammonia water to the hydrazine hydrate is 4.4-11:1, and the molar ratio of the ferric salt to the ferrous salt is 2:1. The method is simple in process, and low in cost, and has easily available and cheap raw materials; and the nanoparticles prepared by the method are small in particle diameter, good in dispersity and stability, and suitable for large-scale industrial production.
Description
Technical field
The invention belongs to new function nano material preparing technical field, be specifically related to a kind of organic dispersed Cu/Fe
3o
4the preparation method of Magnetic nano composite particles.
Background technology
The soft metal nano-particle of copper is the characteristics such as specific area is large, quantum size effect, macro quanta tunnel effect because having, and be widely used in catalysis, electronics, magnetics, optics, calorifics, coating, the field such as lubricated, such as being applied to effective catalyst, electrocondution slurry and lube oil additive etc.Research about preparation, performance and the application of nano-particle of copper in recent years receives much attention.Chinese patent 200610165009.3 discloses a kind of method that adopts high-gravity technology to prepare nano copper lubricating oil additive, it utilizes the alternate transmission invigoration effect of RPB and the characteristic that microcosmic mixes, first mantoquita and reducing solution are reduced in supergravity reactor, and then distillate and dressing agent are modified it in reaction kettle for reaction, last decompression distillation obtains the brownish red oily liquids of finishing, i.e. nano copper lubricating oil additive.It is fast that this method has reaction speed, and product is reproducible, and product quality is high, the yield advantages of higher, but the instrument adopted is harsher, to production equipment, requires higher.The people such as high more honor adopt the method for complexing reduction in patent 96105280.5, by active metal powder, as reducing agent, prepare nano-particle of copper, and the method is difficult for cleaning because of reactive metal powder reducing agent after reaction completes, and may have influence on the purity of copper nanoparticle.In addition, also have using plasma method, electric radiation method, mechanochemical reaction, thermal decomposition method or solvent-thermal method etc. to prepare nano-particle of copper.Wherein, plasma method equipment is simple, easy to operate, speed of production is fast, but energy consumption is large, and the high temperature bottom electrode is easy to melt and pollution products.Although Radiation Synthesis Method preparation technology is simple, granularity is easily controlled, productive rate is high, the product obtained is in the dispersoid state, collects very difficultly, is difficult for scale.Although mechanochemistry method technique is simple, can prepare refractory metal, ceramic-metal composite etc. that other conventional methods are difficult to preparation, its shortcoming is that crystal is inhomogeneous, easily introduces impurity in mechanical milling process.Thermal decomposition method is quicker, economical with respect to other method, but realizes that institute's temperature that requires is higher, and also immature to the control technology of particle diameter and pattern, apart from industrial production, also differs greatly.Solvent-thermal method working pressure device, high to the device materials requirement, condition is relatively harsh, is difficult for expanding production.
In recent years, preparing the more active method of nano-particle of copper is liquid phase reduction.Patent CN1188700A discloses a kind of sodium dithionite that adopts and reduced the method for bivalent cupric ion in the mixed solvent of water and organic substance.Patent CN1381328A discloses a kind of under higher temperature and pressure, prepares the method for nano-particle of copper with the hydrogen reduction mantoquita.Although existing these liquid-phase reduction methods can make tens metal particles to the hundreds of nanometer, but because surface does not obtain sufficient modification, still can't solve the nanoparticle of preparing property stable in the air poor, and the problem such as dispersiveness in organic media is bad, be difficult to extensive use.
Summary of the invention
The object of the present invention is to provide a kind of organic dispersed Cu/Fe
3o
4the preparation method of composite nano particle, the nanoparticle grain diameter made is little, dispersiveness and good stability.
For achieving the above object, the present invention adopts following technical scheme:
A kind of organic dispersed Cu/Fe
3o
4the preparation method of composite nano particle, it comprises the steps: that the hydrazine hydrate aqueous solution that will contain ammoniacal liquor joins in copper salt solution and reacts 1～30min; The mixed aqueous solution reaction 10～60min that adds again divalent iron salt and trivalent iron salt, finally add the nonpolar or weakly polar organic solvent reaction 10～120min that is dissolved with dressing agent, and standing separation, get organic phase, concentrated after and get final product.Reaction temperature is controlled between 20-80 ℃ and is advisable.
The mol ratio of described mantoquita and hydrazine hydrate, divalent iron salt, dressing agent is 1: 1-10: 0.1-1: 0.25-2, and the mol ratio of ammoniacal liquor and hydrazine hydrate aqueous solution is 4.4-11: 1, the mol ratio of trivalent iron salt and divalent iron salt is 2: 1.The mass fraction of ammoniacal liquor is advisable with 25-28%, and the hydrazine hydrate aqueous solution mass fraction is advisable with 50-85%, and the molar concentration of copper salt solution is advisable with 0.2-0.7mol/l.
Concrete, described mantoquita is preferably one or more in water-soluble mantoquitas such as copper sulphate, copper chloride, copper nitrate and copper acetate.
Described divalent iron salt is preferably one or more in ferrous sulfate, frerrous chloride, ferrous nitrate, ferrous acetate; Described trivalent iron salt is preferably one or more in ferric sulfate, iron chloride, ferric nitrate, ferric acetate.
Described dressing agent can be that carbochain is at C
6-C
40between organic carboxyl acid and/or organic amine.As organic carboxylic acid can be saturated, unsaturated, straight chain, side chain or containing one or more the mixture in aromatic hydrocarbon group.The preferred carbochain of dressing agent is at C
10-C
20between organic carboxyl acid and/or organic amine.
Described nonpolar or weakly polar organic solvent is that carbon number is not less than one or more the mixture in 5 alkane, cycloalkane, aromatic hydrocarbon and chlorohydrocarbon.Organic solvent can also be the saturated alkane mixture in addition, as benzinum (mixture of pentane and hexane) etc.
The characteristic that the inventive method utilizes tri-iron tetroxide easily to be modified by coating material, the method by liquid-phase reduction prepares Cu/Fe
3o
4composite nano particle, solved metallic nano-particle and be difficult to the difficult problem by sulfur-bearing, phosphorus dressing agent are not modified.The method mainly is divided into two large steps: 1) prepare copper colloidal sol: will contain disposable the joining in copper salt solution of hydrazine hydrate aqueous solution of ammoniacal liquor, under magnetic agitation, reaction obtains faint yellow transparent copper colloidal sol.2) divalence and the trivalent iron salt aqueous solution are joined in copper colloidal sol, after reaction a period of time, add the organic solvent that is dissolved with dressing agent, be isolated to oil-soluble tri-iron tetroxide coated copper nanoparticle thick, finishing after reaction.Prepared product has good dispersiveness in organic solvent; There is good oxidation stability in air.Good dispersiveness refers to that product is dispersed in described nonpolar or weakly polar organic solvent with 1% mass concentration, occurs without sedimentation in 180 days herein.Good oxidation stability refers to that product is dispersed in described nonpolar or weakly polar organic solvent with 1% mass concentration, in 180 days without any change color.
The method that the inventive method adopts the tri-iron tetroxide coating technology to combine with liquid-phase reduction, solve nano-particle of copper surface in the liquid phase reduction and be not easy the problem of modifying, gained nanoparticle grain diameter little (between 2-15nm) and uniform particle diameter, dispersiveness and good stability.The method has that process equipment is simple, environmental protection, raw material is cheap and easy to get, cost is low, and the productive rate high of product, can obtain the controlled composite nano particle of particle diameter by controlling reaction temperature condition (20-80 ℃), is applicable to large-scale industrial production.Generally, the particle diameter in lower temperature gained nanoparticle is especially little; And the nanoparticle particle diameter made under higher temperature is larger.As obtained the composite nano particle particle diameter when the room temperature reaction, be 2nm; The composite nano particle particle diameter obtained when 60 ℃ of reactions is 15nm.The method gained nanoparticle is scattered in base oil, in air, can steady in a long-termly exist, and has prospects for commercial application widely.The gained composite nano particle has magnetic in addition, after using, than being easier to, reclaims, environmentally friendly.
The accompanying drawing explanation:
Fig. 1 is the Cu/Fe that the oleic acid that makes of embodiment 1, oleyl amine are modified
3o
4the transmission electron microscope picture of nanoparticle;
Fig. 2 is the Cu/Fe that the oleic acid that makes of embodiment 1, oleyl amine are modified
3o
4nanoparticle is scattered in the optics picture in PAO;
Fig. 3 is the Cu/Fe that the oleic acid that makes of embodiment 1, oleyl amine are modified
3o
4the magnetic result of the test of nanoparticle;
Fig. 4 is the Cu/Fe that the oleic acid that makes of embodiment 2, oleyl amine are modified
3o
4the transmission electron microscope picture of nanoparticle;
Fig. 5 is the Cu/Fe that the oleic acid that makes of embodiment 2, oleyl amine are modified
3o
4nanoparticle is scattered in the optics picture in PAO.
The specific embodiment
In order to understand better the present invention, below by preferred embodiment, the inventive method is described in further detail, but protection scope of the present invention is not limited to this.
Embodiment 1
A kind of organic dispersed Cu/Fe
3o
4the preparation method of composite nano particle, it comprises the steps:
1) get the CuSO that 4ml concentration is 0.5mol/l
4the aqueous solution obtains solution A with distilled water diluting to 50ml;
2), after getting hydrazine hydrate aqueous solution that the ammoniacal liquor that the 6ml mass fraction is 25-28% (analyze pure, purchased from the Luoyang magnificent chemical reagent of sky Co., Ltd) is 80% with the 0.8ml mass fraction and mixing, with distilled water diluting, obtain solution B to 50ml;
3) get 1ml concentration 1mol/l FeCl
3with 0.25ml concentration 2mol/l FeCl
2obtain solution C with distilled water diluting to 30ml after mixing; 2mmol oleyl amine and 2mmol oleic acid are dissolved in the 100ml benzinum obtaining to solution D;
4) solution A is proceeded in the three-neck flask of 500ml, react 2min (now solution is transparent yellow solution) under normal temperature, stirring condition, solution B being joined to solution A, dropwise add again solution C, reaction 30min solution gradually becomes the rufous suspension, last property adds solution D reaction 1h, reaction is transferred to stratification in separatory funnel by solution system after finishing, solution divides two-layer (upper strata brownish black organic layer, the colourless water layer of lower floor), getting the upper strata organic layer revolves and steams to obtain brownish red viscous liquid product.
The products obtained therefrom particle diameter is (being shown in Fig. 1) evenly, and average grain diameter is about 2nm; It is dissolved in PAO (polyalphaolefin) (mass fraction is 1wt% in PAO), and the optical photograph after standing 30 days is shown in Fig. 2, and it has good dispersiveness in base oil as seen from Figure 2.In order to verify whether tri-iron tetroxide is coated on nano-particle of copper and after coating whether have magnetic, test as follows: its mother liquor is carried out to attraction, as shown in Figure 3, under the attraction of magnet, material all attracted to one side of magnet (in Fig. 3 as can be seen from Figure 3, left side is magnet), all the other solution that are clear, illustrate that nano-particle of copper is all coated by tri-iron tetroxide, and have stronger magnetic after coating.
Embodiment 2
A kind of organic dispersed Cu/Fe
3o
4the preparation method of composite nano particle, it comprises the steps:
1) get the CuSO that 4ml concentration is 0.5mol/l
4the aqueous solution obtains solution A with distilled water diluting to 50ml;
2), after getting hydrazine hydrate aqueous solution that ammoniacal liquor that the 6ml mass fraction is 25-28% is 80% with the 0.8ml mass fraction and mixing, with distilled water diluting, obtain solution B to 50ml;
3) get 1ml concentration 1mol/l FeCl
3with 0.25ml concentration 2mol/l FeCl
2obtain solution C with distilled water diluting to 30ml after mixing; 2mmol oleyl amine and 2mmol oleic acid are dissolved in the 100ml benzinum obtaining to solution D;
4) solution A is proceeded in the three-neck flask of 500ml, react 2min (now solution is transparent yellow solution) under 60 ℃, stirring condition, solution B being joined to solution A, dropwise add again solution C, reaction 30min solution gradually becomes the rufous suspension, last property adds solution D reaction 1h, reaction is transferred to stratification in separatory funnel by solution system after finishing, solution divides two-layer (upper strata brownish black organic layer, the colourless water layer of lower floor), getting the upper strata organic layer revolves and steams to obtain brownish black viscous liquid product.
The products obtained therefrom particle diameter is (being shown in Fig. 4) evenly, and average grain diameter is about 15nm; It is dissolved in PAO (polyalphaolefin) (mass fraction is 1wt% in PAO), and the optical photograph after standing 30 days is shown in Fig. 5, and it has good dispersiveness in base oil as seen from Figure 5.
Embodiment 3
A kind of organic dispersed Cu/Fe
3o
4the preparation method of composite nano particle, it comprises the steps:
1) get the copper acetate aqueous solution that 4ml concentration is 0.25mol/l and obtain solution A with distilled water diluting to 50ml;
2), after getting hydrazine hydrate aqueous solution that ammoniacal liquor that the 3ml mass fraction is 25-28% is 50% with the 0.7ml mass fraction and mixing, with distilled water diluting, obtain solution B to 50ml;
3) get 0.5ml concentration 1mol/l Fe (NO
3)
3with 0.125ml concentration 2mol/l Fe (NO
3)
2obtain solution C with distilled water diluting to 30ml after mixing; 1mmol n-octyl amine and 1mmol oleic acid are dissolved in the 100ml chloroform obtaining to solution D;
4) solution A is proceeded in the three-neck flask of 500ml, react 2min (now solution is transparent pale yellow solution) under 45 ℃, stirring condition, solution B being joined to solution A, dropwise add again solution C, reaction 30min solution gradually becomes the reddish dark brown suspension, last property adds solution D reaction 1h, reaction is transferred to stratification in separatory funnel by solution system after finishing, solution divides two-layer (the colourless water layer in upper strata, lower floor's brown color organic layer), taking off a layer organic layer revolves and steams to obtain brown color viscous liquid product.
Embodiment 4
A kind of organic dispersed Cu/Fe
3o
4the preparation method of composite nano particle, it comprises the steps:
1) get the CuCl that 6ml concentration is 0.5mol/l
2the aqueous solution obtains solution A with distilled water diluting to 50ml;
2), after getting hydrazine hydrate aqueous solution that ammoniacal liquor that the 6ml mass fraction is 25-28% is 50% with the 1.6ml mass fraction and mixing, with distilled water diluting, obtain solution B to 50ml;
3) get 1ml concentration 1mol/l Fe (SO
4)
3with 0.25ml concentration 2mol/l Fe (SO
4)
2obtain solution C with distilled water diluting to 30ml after mixing; 0.5mmol oleyl amine and 0.5mmol stearic acid are dissolved in the 100ml chloroform obtaining to solution D;
4) solution A is proceeded in the three-neck flask of 500ml, react 2min (now solution is transparent yellow solution) under 45 ℃ of stirring conditions, solution B being joined to solution A, dropwise add again solution C, reaction 30min solution gradually becomes brown suspension, last property adds solution D reaction 1h, reaction is transferred to stratification in separatory funnel by solution system after finishing, solution divides two-layer (the colourless water layer in upper strata, the brown organic layer of lower floor), taking off a layer organic layer revolves and steams to obtain brown viscous liquid product.
Embodiment 5
A kind of organic dispersed Cu/Fe
3o
4the preparation method of composite nano particle, it comprises the steps:
1) get the Cu (NO that 4ml concentration is 0.5mol/l
3)
2the aqueous solution obtains solution A with distilled water diluting to 50ml;
2), after getting hydrazine hydrate aqueous solution that ammoniacal liquor that the 6ml mass fraction is 25-28% is 50% with the 1.2ml mass fraction and mixing, with distilled water diluting, obtain solution B to 50ml;
3) get 2ml concentration 1mol/l FeCl
3with 0.5ml concentration 2mol/l FeCl
2obtain solution C with distilled water diluting to 30ml after mixing; 1mmol n-octyl amine and 1mmol tetradecylic acid are dissolved in the 100ml benzinum obtaining to solution D;
4) solution A is proceeded in the three-neck flask of 500ml, react 2min (now solution is transparent yellow solution) under normal temperature, stirring condition, solution B being joined to solution A, dropwise add again solution C, reaction 60min solution gradually becomes the dark-brown suspension, last property adds solution D reaction 1h, reaction is transferred to stratification in separatory funnel by solution system after finishing, solution divides two-layer (upper strata dark-brown organic layer, the colourless water layer of lower floor), getting the upper strata organic layer revolves and steams to obtain brown viscous liquid product.
Claims (4)
1. an organic dispersed Cu/Fe
3o
4the preparation method of composite nano particle, is characterized in that, comprises the steps: that the hydrazine hydrate aqueous solution that will contain ammoniacal liquor joins in copper salt solution to react 1～30min; The mixed aqueous solution reaction 10～60min that adds again divalent iron salt and trivalent iron salt, finally add the nonpolar or weakly polar organic solvent reaction 10～120min that is dissolved with dressing agent, and standing separation, get organic phase, concentrated after and get final product; The mol ratio of described mantoquita and hydrazine hydrate, divalent iron salt, dressing agent is 1:1-10:0.1-1:0. 25-2, and the mol ratio of ammoniacal liquor and hydrazine hydrate is 4.4-11:1, and the mol ratio of trivalent iron salt and divalent iron salt is 2:1; Described dressing agent is that carbochain is at C
6-C
40between organic carboxyl acid and/or organic amine; Described nonpolar or weakly polar organic solvent is that carbon number is not less than one or more the mixture in 5 alkane, cycloalkane, aromatic hydrocarbon and chlorohydrocarbon.
2. organic dispersed Cu/Fe as claimed in claim 1
3o
4the preparation method of composite nano particle, is characterized in that, described mantoquita is one or more in copper sulphate, copper chloride, copper nitrate and copper acetate.
3. organic dispersed Cu/Fe as claimed in claim 1
3o
4the preparation method of composite nano particle, is characterized in that, described divalent iron salt is one or more in ferrous sulfate, frerrous chloride, ferrous nitrate, ferrous acetate; Described trivalent iron salt is one or more in ferric sulfate, iron chloride, ferric nitrate, ferric acetate.
4. organic dispersed Cu/Fe as claimed in claim 1
3o
4the preparation method of composite nano particle, is characterized in that, described dressing agent is that carbochain is at C
10-C
20between organic carboxyl acid and/or organic amine.
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