CN1049160C - Preparation method for transition metal oxide nuclear shell type nano meter particle - Google Patents
Preparation method for transition metal oxide nuclear shell type nano meter particle Download PDFInfo
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- CN1049160C CN1049160C CN96101878A CN96101878A CN1049160C CN 1049160 C CN1049160 C CN 1049160C CN 96101878 A CN96101878 A CN 96101878A CN 96101878 A CN96101878 A CN 96101878A CN 1049160 C CN1049160 C CN 1049160C
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- transition metal
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- metal oxide
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Abstract
The present invention belongs to a process for preparing kernel-shell type submicron powder with a one-step method of phase transition. The process for preparing kernel-shell type submicron powder with a one-step method of phase transition comprises the following steps: by taking transitional metal salt solution as raw material, adding an anionic or non-anionic surface active agent and a phase transfer agent of organic or inorganic polar compounds to generate ultramicron which takes metal oxide as a kernel and the surface active agent as a shell after stirring operation. Then after centrifugal dehydration, drying the wed powder to directly obtain the submicron powder. The present invention has the characteristics of simple process, organic solvent and industrial water saving, no environmental pollution, high productive efficiency, low cost, wide product purpose, etc., and thus, is suitable for industrial scale production.
Description
The invention belongs to the metal oxide micropowder preparing process, particularly a kind of phase transfer one-step method preparation surface is through the method for the ultra micro powder of modification.
The eighties mid-term, the someone adopts the method for finishing to make nano particles such as a class iron oxide, titanium oxide, and with its meticulous being compound in the macromolecular material, obtains many-sided application.Wherein prepare micro mist two kinds of methods are arranged: a kind of method is to be raw material preparing metal salting liquid with the slaine, adds surfactant and organic solvent, in the high degree of agitation, nano particle quenched get in the organic facies, organic facies steams organic solvent at last through reflux dewatering, obtains dry powder.This method has two not enough heres, and the first, quench the slaine hydrosol to be taken to needs a large amount of organic solvents in the organic facies; The second, this method productive rate is very low, is difficult to realize industrialization.
Second method is to be raw material with the slaine, adds alkali and becomes the slaine hydrosol, add surfactant again and get gel, with gel through ammonia scrubbing, a large amount of hot washes, oven dry is at last pulverized.This method has two weak points, and the first, because prior art adopts C
6-C
18Surfactant, even with the preparation of the high molecular surfactant of low polymerization degree, solution viscosity is bigger, therefore the nano particle for preparing will cause the industrial wastewater pollution environment with a large amount of ammoniacal liquor and hot wash; The second, need mechanical crushing, consumes energy after the oven dry of preparation gel.
The objective of the invention is to change the composition of surfactant, add consisting of phase-transferring agent, thereby cast out technical process such as washing, pulverizing, reach one and go on foot the waste of preparing the metal oxide nuclear shell type nano meter particle, avoiding a large amount of water for industrial uses and organic solvent, reach high productivity effect and reduce environmental pollution.
Technical process of the present invention can reduce: the solution with transition metal salt is raw material, adds the coating material aqueous solution and stirs 1-120 minute, and forming with the transition metal oxide cluster is nuclear, is the nano particle of shell with the coating material.After dewater, dry, loose nano powder.Feature of the present invention is, the stirring after raw material adds coating material also will add consisting of phase-transferring agent simultaneously, and said consisting of phase-transferring agent is polar organic matter or inorganic matter or substitutes consisting of phase-transferring agent with the ionic coating material.The nucleocapsid ratio of nano particle is (90-40): (10-60), and particle diameter 10-80nm.
Adding consisting of phase-transferring agent or substitute the purpose of consisting of phase-transferring agent with the ionic coating material, is the microenvironment of adjusting microparticle surfaces, changes the character of two-phase interface rapidly, and one step of nano particle is transferred to from liquid phase in the solid phase, promptly directly generates the nanoscale micro mist.Do not need organic solvent to quench and get, nano particle is shifted from water be the process of oil phase.Consisting of phase-transferring agent includes sodium acetate, ammoniacal liquor etc.
The reagent of finishing comprise anionic with nonionic.Wherein the surfactant of anionic has Sulfonates, such as alkylbenzenesulfonate, alkylsulfonate, petroleum sulfonate etc., also has metal carboxylate, such as C
2-C
18The soap of class, and olefin(e) acid salt are such as C
2-C
18The various olefin(e) acid salt that contain two keys contain the olefin(e) acid salt of side group or diacid salt etc.The coating material of nonionic has polyethylene glycols, as APEO and polyalcohols, as sorbitol ester class etc.In the reagent of above-mentioned finishing, the consisting of phase-transferring agent that can substitute of anionic works to the step formation of some transition metal oxide ultramicrons.Small molecular organic acid salt particularly is such as C
2-C
5Carboxylate or olefin(e) acid salt owing to be the coating material parcel inorganic particulate of short carbon chain, the solution viscosity of preparation usefulness is very low, ammoniacal liquor and hot water cyclic washing that therefore can be a large amount of.
Aforesaid transition metal salt is the transition metal of periodic table of elements period 4.Promptly the transition metal salt solution with Ti, V, Cr, Mn, Fe, Cu, Ni, Co, Zn is a raw material, and the transition metal oxide cluster that forms with the periodic table of elements period 4 is a nuclear, is the nano particle of shell with the coating material.Coating material is with C
2-C
5Carboxylate is best, during to preparation chromium oxide nano particle, uses neopelex to make surperficial dressing agent and is the best.
In force, in the time of the ratio of preparation transition metal salt solution, the coating material aqueous solution and consisting of phase-transferring agent, can be undertaken by following data area.The solution concentration of transition metal salt is 10
-4-5mol/L, preferably 0.1-1mol/L scope; The concentration of aqueous solution of coating material is 10
-3-10mol/L, 0.1-5mol/L preferably, the molar ratio scope between transition metal salt, coating material, the consisting of phase-transferring agent three is 1: (0.1-10): (0-1); In the reaction between the acidity-basicity ph value 1-9 of mixed solution.
Embodiment 1 hud typed Fe
2O
3The preparation of nano particle
Preparation trivalent iron salt aqueous solution 2000ml, concentration can be 1mol/L, adds n Propanoic acid sodium coating material 100ml, the concentration 1-4mol/L of n Propanoic acid sodium, stir about 10 minutes promptly has a large amount of nano particles to generate in the solution.At this moment, consisting of phase-transferring agent is substituted by n Propanoic acid sodium.The solution that generation is had nano particle is through centrifugal dehydration, the wet-milling oven dry, and bake out temperature can be between 20-100 ℃, dries by the fire anhydrous constant weight to the powder, promptly obtains Fe
2O
3The nano powder product.
The preparation of embodiment 2 hud typed CoO nano particles
Prepare cobaltous aqueous solution 2000ml, solution concentration is 0.8mol/L, adds coating material n Propanoic acid sodium water solution 100ml in the stirring, and the concentration of n Propanoic acid sodium is 1-4mol/L.Stirred for several minute promptly has nano particle generate.Through separating and dehydrating oven dry, bake out temperature 20-100 ℃.
Embodiment 3 hud typed Cr
2O
3The preparation of nano particle
Preparation chromic salt aqueous solution 2000ml, solution concentration is 1mol/L, normal temperature adds coating material sodium dodecyl benzene sulfonate aqueous solution 100ml down, concentration of aqueous solution is 1-2mol/L, in high degree of agitation, add consisting of phase-transferring agent ammoniacal liquor 10ml, there is nano particle to generate after several minutes.Through separating and dehydrating, wet-milling oven dry, about 100 ℃ of bake out temperatures.
This product is dissolved in the organic solvent, and solution is green transparent liquid.
Embodiment 4 hud typed TiO
2The preparation of nano particle
Getting titanium salt aqueous solution 1000ml concentration is 0.1-1mol/L, drips H
2SO
4The aqueous solution to solution is transparence, dripping alkaline aqueous solution then makes and settles out, solution ph is between 7-12, under 30-70 ℃ of temperature, add acid and make the precipitation dissolving, obtain the titanium oxide hydrosol, PH is between 1-7, can add coating material n-butyric acie sodium water solution 100ml this moment, and concentration of aqueous solution is 10
-3-2mol/L after the stirred for several minute, has nano particle to generate, and dries to constant weight under 20-100 ℃ through separating and dehydrating, promptly gets product.Also can adopt the method for embodiment 1, in titanium salt solution, directly add coating material and prepare nano material.
Metal oxide nanoparticles by the preparation method of the foregoing description obtains through finishing, has formed casing outside, and inorganic core is in interior hud typed structure.Can see that through the thermogravimetric analysis curve sample has a weightless peak in the time of 150 ℃, weightlessness about 15%, this is the dehydration peak; Begin weightlessness again at 350 ℃ of samples, stop weightlessness after 470 ℃, this part weightlessness is the thermal decomposition of finishing coat, and weightlessness accounts for about 20-40%.Also can see this nucleocapsid structure by electromicroscopic photograph, and the size and the shape of particle as can be seen, particle is a ball-type, diamond pattern or bar-shaped.
This particulate through finishing can both very well be dissolved in organic solvent and the high polymer monomer, such as nanometer Fe
2O
3Be dissolved in the dichloroethanes.Because nano powder absorbs the selectivity of ultraviolet light and visible light and sees through, and is widely used, such as, with Fe
2O
3Nano particle is dissolved in the high polymer monomer, adds initator, and polymerization at a certain temperature can be made transparent optical glass.Contain 0.15% nanometer Fe
2O
3The PMMA optical glass of weight all absorbs ultraviolet ray at the 400-250nm wave band, at the 700-400nm wave band, all through visible light.Utilize this class nuclear shell type nano meter particle and high molecular meticulous complex technique, can be used as pigment, have stable lasting characteristics of protecting look because the stable dimensions of inorganic material and hear resistance can not overflowed from composite.Because this class nano material energy shielding ultraviolet rays has important application at aspects such as space material, naval target, antiultraviolet clothing, cosmetics, food, medical packagings.
The preparation method of transition metal oxide nuclear shell type nano meter particle of the present invention has as follows Characteristics: 1, technology is the phase transfer one-step method, and namely raw material and one step of coating material generate solid-state Micro mist is about to Ultramicro-powder and directly is transferred to solid phase from liquid phase, compared with the prior art, removes from The organic solvent technical process such as getting, steam organic solvent, pulverizing of quenching, and saved a large amount of Organic solvent. 2, owing to make surperficial dressing agent with small molecular organic acid salt, saved ammoniacal liquor The technical process such as washing, hot water cyclic washing, and saved a large amount of water for industrial uses. 3, do not have Have the industrial wastewater blowdown to process, the water of deviating from behind every secondary response can also use next time, not only No unloading water, and contained reactant can all continue to be utilized in the water. 4, just because the worker Order is easy, has saved a large amount of organic solvents and water for industrial use, and does not have blowdown, the dehydration afterreaction Thing can all continue to be utilized, so improved production efficiency, has reduced cost, needn't examine Consider environmental pollution, product purpose is extensive, is suitable for suitability for industrialized production.
Claims (3)
1. the preparation method of a transition metal oxide nuclear shell type nano meter particle, it is characterized in that, transition metal salt solution with the periodic table of elements period 4 is a raw material, add coating material and consisting of phase-transferring agent, stirred 1-120 minute, formation is nuclear with the transition metal oxide cluster of periodic table of elements period 4, is the nano particle of shell with the coating material.Nano particle through dewatering, drying loosely; Said coating material is C
2-C
5Carboxylate or the aqueous solution of neopelex; Said consisting of phase-transferring agent is ammoniacal liquor or sodium acetate or substitutes consisting of phase-transferring agent with coating material; The nucleocapsid ratio of nano particle is (90-40): (10-60).
2. according to the preparation method of the described transition metal oxide nuclear shell type nano meter particle of claim 1, the transition metal salt solution concentration that it is characterized in that the said periodic table of elements period 4 is 10
-4-10mol/L, the concentration of aqueous solution of coating material are 10
-3-5mol/L; Molar ratio scope between transition metal salt, coating material and the consisting of phase-transferring agent three is 1: (0.1-10): (0-1).
3. according to the preparation method of claim 1 or 2 described transition metal oxide nuclear shell type nano meter particles, the aqueous solution that it is characterized in that said neopelex is made surperficial dressing agent, ammoniacal liquor is made consisting of phase-transferring agent, be used to prepare with the chromic salt aqueous solution is the chromated oxide of raw material, i.e. Cr
2O
3Nano particle.
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| CN96101878A CN1049160C (en) | 1996-02-07 | 1996-02-07 | Preparation method for transition metal oxide nuclear shell type nano meter particle |
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| CN96101878A CN1049160C (en) | 1996-02-07 | 1996-02-07 | Preparation method for transition metal oxide nuclear shell type nano meter particle |
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| CN1049160C true CN1049160C (en) | 2000-02-09 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010081268A1 (en) * | 2008-12-30 | 2010-07-22 | 中国科学院生态环境研究中心 | Methods for separating and redispersing nano-materials |
| CN101812216A (en) * | 2010-03-31 | 2010-08-25 | 江苏华天通科技有限公司 | Electronic packaging material containing transition metal oxide nanometer particles |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6262129B1 (en) * | 1998-07-31 | 2001-07-17 | International Business Machines Corporation | Method for producing nanoparticles of transition metals |
| CN1312045C (en) * | 2004-11-18 | 2007-04-25 | 王宗良 | Preparation for nanometer metal oxide and nanometer metal oxide therefrom |
| ATE541811T1 (en) * | 2005-12-06 | 2012-02-15 | Lg Chemical Ltd | PRODUCTION PROCESS FOR CORE SHELL NANOPARTICLES |
| CN101833175A (en) * | 2010-03-31 | 2010-09-15 | 江苏华天通科技有限公司 | Preparation method of 580 nanometer anti-glare resin lens |
| CN102416469B (en) * | 2011-11-25 | 2013-07-31 | 东南大学 | Method for extracting thin metal nanoparticles |
| CN103487848B (en) * | 2012-06-12 | 2016-09-21 | 江苏华天通纳米科技有限公司 | Colourless transparent resin eyeglass containing cobalt oxide nano material and manufacture method thereof |
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| CN107083827B (en) * | 2017-04-27 | 2019-01-01 | 霸州市瑞硕盈装饰装修工程有限公司 | Lacquer coating application technique |
| CN111257973A (en) * | 2020-03-18 | 2020-06-09 | 江苏新视客光电科技有限公司 | Anti-infrared spectacle lens and preparation method thereof |
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| JPH02175602A (en) * | 1988-12-28 | 1990-07-06 | Ricoh Co Ltd | Production of ultrafine particle metal oxide composition and ultrafine particle zirconium oxide composition obtained thereby |
| WO1994010090A1 (en) * | 1992-11-04 | 1994-05-11 | Nukem Gmbh | Process for producing stabilised hafnium oxide powder or a hafnium oxide-containing powder |
-
1996
- 1996-02-07 CN CN96101878A patent/CN1049160C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02175602A (en) * | 1988-12-28 | 1990-07-06 | Ricoh Co Ltd | Production of ultrafine particle metal oxide composition and ultrafine particle zirconium oxide composition obtained thereby |
| WO1994010090A1 (en) * | 1992-11-04 | 1994-05-11 | Nukem Gmbh | Process for producing stabilised hafnium oxide powder or a hafnium oxide-containing powder |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010081268A1 (en) * | 2008-12-30 | 2010-07-22 | 中国科学院生态环境研究中心 | Methods for separating and redispersing nano-materials |
| CN101812216A (en) * | 2010-03-31 | 2010-08-25 | 江苏华天通科技有限公司 | Electronic packaging material containing transition metal oxide nanometer particles |
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|---|---|
| CN1139590A (en) | 1997-01-08 |
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