CN103539074B - A kind of nano transition metal oxides raw powder's production technology - Google Patents
A kind of nano transition metal oxides raw powder's production technology Download PDFInfo
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- CN103539074B CN103539074B CN201310411339.6A CN201310411339A CN103539074B CN 103539074 B CN103539074 B CN 103539074B CN 201310411339 A CN201310411339 A CN 201310411339A CN 103539074 B CN103539074 B CN 103539074B
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- 229910000314 transition metal oxide Inorganic materials 0.000 title claims abstract description 74
- 239000000843 powder Substances 0.000 title claims abstract description 26
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 7
- 238000005516 engineering process Methods 0.000 title claims abstract description 6
- 239000012702 metal oxide precursor Substances 0.000 claims abstract description 59
- 239000007787 solid Substances 0.000 claims abstract description 57
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 20
- -1 transition metal salt Chemical class 0.000 claims abstract description 20
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 14
- 238000005286 illumination Methods 0.000 claims abstract description 10
- 239000011347 resin Substances 0.000 claims abstract description 9
- 229920005989 resin Polymers 0.000 claims abstract description 9
- 150000002148 esters Chemical class 0.000 claims abstract description 8
- 239000000178 monomer Substances 0.000 claims abstract description 7
- 229920000058 polyacrylate Polymers 0.000 claims description 28
- 239000011343 solid material Substances 0.000 claims description 28
- 239000002131 composite material Substances 0.000 claims description 27
- 239000002245 particle Substances 0.000 claims description 27
- 239000011259 mixed solution Substances 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 19
- 239000012298 atmosphere Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 11
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 10
- 229910052737 gold Inorganic materials 0.000 claims description 10
- 239000010931 gold Substances 0.000 claims description 10
- 230000007704 transition Effects 0.000 claims description 10
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 6
- YYPNJNDODFVZLE-UHFFFAOYSA-N 3-methylbut-2-enoic acid Chemical compound CC(C)=CC(O)=O YYPNJNDODFVZLE-UHFFFAOYSA-N 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- AZOOXWWPWARTFV-UHFFFAOYSA-N zirconium hydrochloride Chemical group Cl.[Zr] AZOOXWWPWARTFV-UHFFFAOYSA-N 0.000 claims description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical group C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 8
- 239000002105 nanoparticle Substances 0.000 abstract description 5
- 239000011858 nanopowder Substances 0.000 abstract description 4
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 abstract description 3
- 239000003960 organic solvent Substances 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000010298 pulverizing process Methods 0.000 abstract description 2
- 239000004925 Acrylic resin Substances 0.000 abstract 1
- 238000001354 calcination Methods 0.000 abstract 1
- 238000007711 solidification Methods 0.000 description 12
- 230000008023 solidification Effects 0.000 description 12
- 239000000243 solution Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 6
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 4
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 4
- 239000008187 granular material Substances 0.000 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 description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- VNQXSTWCDUXYEZ-UHFFFAOYSA-N 1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-dione Chemical compound C1CC2(C)C(=O)C(=O)C1C2(C)C VNQXSTWCDUXYEZ-UHFFFAOYSA-N 0.000 description 3
- AMFGWXWBFGVCKG-UHFFFAOYSA-N Panavia opaque Chemical group C1=CC(OCC(O)COC(=O)C(=C)C)=CC=C1C(C)(C)C1=CC=C(OCC(O)COC(=O)C(C)=C)C=C1 AMFGWXWBFGVCKG-UHFFFAOYSA-N 0.000 description 3
- 229930006711 bornane-2,3-dione Natural products 0.000 description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- SAPGBCWOQLHKKZ-UHFFFAOYSA-N 6-(2-methylprop-2-enoyloxy)hexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCCCOC(=O)C(C)=C SAPGBCWOQLHKKZ-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000006193 liquid solution Substances 0.000 description 2
- 239000000693 micelle Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 2
- 150000003673 urethanes Chemical class 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229920006397 acrylic thermoplastic Polymers 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- XNZJTLSFOOXUAS-UHFFFAOYSA-N cobalt hydrochloride Chemical compound Cl.[Co] XNZJTLSFOOXUAS-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000005291 magnetic effect Effects 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical class [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- ZJVTYKZWDWVIFD-UHFFFAOYSA-N zinc;hydrochloride Chemical compound Cl.[Zn] ZJVTYKZWDWVIFD-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Abstract
The present invention relates to a kind of nano transition metal oxides raw powder's production technology.Present invention esters of acrylic acid unsaturated-resin monomer replaces conventional organic solvents as dicyandiamide solution, transition metal salt is dissolved in acrylate resin monomer solution, resin solution containing transition metal oxide precursor body is carried out illumination curing, carry out obtained solid pulverizing, calcining, obtain nano transition metal oxides powder body.The present invention solves organic solvent in traditional transition metal oxide nano powder body preparation process and consumes the problems such as big, nanoparticle reunion.It is an advantage of the invention that preparation method is simple, environmental friendliness.
Description
Technical field
The present invention relates to a kind of nano transition metal oxides raw powder's production technology, especially a kind of employing is non-traditional molten
Agent system prepares the method for nano transition metal oxides powder body.
Background technology
Transition metal oxide has the performance of the aspects such as optics, electricity and the magnetics of excellence, is widely used in multiple
In functional material.Nano transition metal oxides is compared tradition micron order oxide and is had more bigger serface, and more only
Special, excellent physical property.
The method preparing transition metal oxide nano powder body seeing report at present is mainly by by transition metal salt
Surfactant melts and prepares.The Chinese patent of Patent No. CN1865150A discloses a kind of nano transition metal oxygen
The preparation method of compound powder body material.Melted transition metal salt is solubilized into the mixing of hydrocarbon component and surfactant by this patent
In thing, form the titania nanoparticle of oil bag fuse salt, make the fuse salt in micelle carry out what reaction in-situ was generated with precipitant
Transition metal hydroxide is limited in micelle, obtains nano transition metal oxides through washing, drying, roast.The party
Method relates to the precipitation of complexity, separates, washs and the process such as solvent process, and manufacturing cycle is long, and nano-powder is at dry solvent
During easily produce reunion, production process uses a large amount of solvents that environment can cause bigger pressure.
Summary of the invention
The purpose of the present invention is aiming at the deficiencies in the prior art, it is provided that the system of a kind of nano transition metal oxides powder body
Preparation Method.
The present invention to the effect that uses esters of acrylic acid unsaturated-resin monomer to replace conventional solvent as dicyandiamide solution,
Transition metal salt is dissolved in this solvent, by curing unsaturated resins, obtains containing transition metal oxide precursor body
Blocks of solid, high-temperature calcination after pulverizing, obtain transition metal oxide nano powder body.
Comprising the concrete steps that of the inventive method:
Step (1). esters of acrylic acid unsaturated-resin monomer and light trigger are uniformly mixed at 60～80 DEG C,
Obtain mixed liquor；In mixed liquor, the mass content of light trigger is 0.2～2.0；
Described esters of acrylic acid unsaturated-resin monomer is bisphenol-A-glycidyl Methacrylate, two contracting three second
Ol dimethacrylate, dimethacrylate diethylene glycol ester, Ethylene glycol dimethacrylate, TEG dimethyl propylene
In olefin(e) acid ester, 1,6-hexanediol dimethacrylate, ethoxylated bisphenol dimethylacrylate or urethanes one
Plant or several；
Described light trigger be gorgeous good solid 1173, gorgeous good solid 184, gorgeous good solid 2959, gorgeous good solid 907, gorgeous good solid 369,
Gorgeous good solid 819, gorgeous good solid 754 or camphorquinone in one or several；
Step (2). transition metal salt and acrylic compounds are joined in above-mentioned mixed liquor, stir 10～30 points
Clock, obtains the mixed solution containing transition metal oxide precursor body；Every 10 grams of mixing containing transition metal oxide precursor body
Close in solution containing 1～5 gram of transition metal salt, 0～3 gram of acrylic compounds；
Described transition metal salt is one or several in nitrate, hydrochlorate, sulfate, acetate；Wherein cross
Crossing metal is chromium, manganese, ferrum, cobalt, nickel, copper, zinc or zirconium；
Described acrylic compounds is the one or two kinds of of acrylic acid, methacrylic acid.
Step (3). the above-mentioned mixed solution containing transition metal oxide precursor body is injected in mould, uses blue light
Or ultraviolet light polymerization, illumination 60～240 seconds under 5～50W power, obtain transition metal oxide precursor body/polyacrylate
Composite solid material.
Step (4). transition metal oxide precursor body/polyacrylate composite solid material is pulverized, pulverizes 1～5 point
Clock, obtains solid particle.Step (5). by above-mentioned solid particle 500～800 DEG C, calcine 2～6 hours under air atmosphere,
To nano transition metal oxides powder body.
The inventive method uses acrylics unsaturated-resin to prepare transition gold as a kind of non-traditional dicyandiamide solution
Belonging to nm-class oxide powder, the nanoparticle size of preparation is evenly distributed, and nano-particle is slightly reunited, void size between granule
Uniformly.This inventive method does not use conventional organic solvents, it is to avoid solvent process, and preparation method environmental friendliness, technique is simple.
Accompanying drawing explanation
Fig. 1 is the nano-manganese dioxide oxide powder scanning electron microscope (SEM) photograph of preparation in embodiment 1；Wherein a is high magnification
Shooting, b is low range shooting.
Detailed description of the invention
With specific embodiment, the present invention is further analyzed below in conjunction with the accompanying drawings.
Embodiment 1
Step (1). by 4 grams of bisphenol-A-glycidyl Methacrylates, 6 grams of triethylene-glycol methacrylates
Ester, it is uniformly mixed at 60 DEG C for 0.05 gram gorgeous good solid 819, obtains the mixed liquor of 10.05 grams；
Step (2). 2.5 grams of manganese acetates and 1 gram of acrylic acid are joined in above-mentioned solution, stirs 10 minutes, obtain 13.5g
Mixed solution containing transition metal oxide precursor body；
Step (3). the mixed solution containing transition metal oxide precursor body is injected in mould, uses 50W blue light
Irradiate solidification in 60 seconds, obtain transition metal oxide precursor body/polyacrylate composite solid material；
Step (4). transition metal oxide precursor body/polyacrylate composite solid material is pulverized 1 minute, consolidate
Body granule.
Step (5). above-mentioned solid particle is calcined 4 hours under 800 DEG C of air atmospheres, obtains nano-manganese dioxide oxidation
Powder.
As shown in Figure 1, the nano transition metal oxides powder body material particle diameter of embodiment 1 preparation is about 50 nanometers, nanometer
Aperture between particle is about 50 nanometers, and nanoparticle aggregation becomes the block that micron level is fluffy.
Embodiment 2
Step (1). 9.98g bisphenol-A-glycidyl Methacrylate, 0.02g gorgeous good solid 1173 are stirred at 80 DEG C
Mix mix homogeneously, obtain 10g mixed liquor；
Step (2). 3g manganese nitrate, 5.6g acrylic acid are joined in above-mentioned solution, stirs 10 minutes, obtain 18.6g mistake
Cross metal oxide precursor solution；
Step (3). above-mentioned transition metal oxide precursor liquid solution is injected in mould, uses 5W UV Light
Solidification in 240 seconds, obtains transition metal oxide precursor body/polyacrylate composite solid material；
Step (4). transition metal oxide precursor body/polyacrylate composite solid material is pulverized 5 minutes, consolidate
Body granule；Step (5). by above-mentioned solid particle at 500 DEG C, calcine 6 hours under air atmosphere, obtain nano-manganese dioxide oxidation
Powder.
Embodiment 3
Step (1). 9.8g triethylene glycolbismethyl-acrylate, 0.2g gorgeous good solid 184 stirring at 80 DEG C are mixed
Close uniformly, obtain 10g mixed liquor；
Step (2). 16.5g manganese sulfate, 6.5g acrylic acid are joined in above-mentioned solution, stirs 30 minutes, obtain 33g mistake
Cross metal oxide precursor solution；
Step (3). above-mentioned transition metal oxide precursor liquid solution is injected in mould, uses 10W blue light illumination 100
Second solidification, obtains transition metal oxide precursor body/polyacrylate composite solid material；
Step (4). transition metal oxide precursor body/polyacrylate composite solid material is pulverized 2 minutes, consolidate
Body granule；Step (5). by above-mentioned solid particle at 600 DEG C, calcine 5 hours under air atmosphere, obtain nano-manganese dioxide oxidation
Powder.
Embodiment 4
Step (1). 9.95g dimethacrylate diethylene glycol ester, 0.05g gorgeous good solid 2959 stirring at 62 DEG C are mixed all
Even, obtain 10g mixed liquor；
Step (2). 4g hydrochloric acid zinc, 6g acrylic acid are joined in above-mentioned mixed liquor, stirs 10 minutes, obtain 20g and contain
The mixed solution of transition metal oxide precursor body；
Step (3). the above-mentioned mixed solution containing transition metal oxide precursor body is injected in mould, uses 10W
Blue light illumination solidification in 220 seconds, obtains transition metal oxide precursor body/polyacrylate composite solid material；
Step (4). transition metal oxide precursor body/polyacrylate composite solid material is pulverized, pulverizes 2 minutes,
Obtain solid particle.Step (5). by above-mentioned solid particle 500 DEG C, calcine 6 hours under air atmosphere, obtain nano transition gold
Belong to oxide powder.
Embodiment 5
Step (1). 9.92g Ethylene glycol dimethacrylate, 0.08g gorgeous good solid 907 stirring at 65 DEG C are mixed all
Even, obtain 10g mixed liquor；
Step (2). 4g chromic nitrate, 4g ferric nitrate and 2g methacrylic acid are joined in above-mentioned mixed liquor, stirs 15 points
Clock, obtains 20g and contains the mixed solution of transition metal oxide precursor body；
Step (3). the above-mentioned mixed solution containing transition metal oxide precursor body is injected in mould, uses 20W
UV Light solidification in 200 seconds, obtains transition metal oxide precursor body/polyacrylate composite solid material；
Step (4). transition metal oxide precursor body/polyacrylate composite solid material is pulverized, pulverizes 4 minutes,
Obtain solid particle.Step (5). by above-mentioned solid particle 550 DEG C, calcine 5.5 hours under air atmosphere, obtain nano transition
Metal-oxide powder.
Embodiment 6
Step (1). 9.9g TEG dimethylacrylate, 0.1g gorgeous good solid 369 stirring at 68 DEG C are mixed all
Even, obtain 10g mixed liquor；
Step (2). 2g hydrochloric acid cobalt, 4g copper sulfate, 4g acrylic acid are joined in above-mentioned mixed liquor, stirs 20 minutes,
The mixed solution of transition metal oxide precursor body is contained to 20g；
Step (3). the above-mentioned mixed solution containing transition metal oxide precursor body is injected in mould, uses 25W
Blue light illumination solidification in 180 seconds, obtains transition metal oxide precursor body/polyacrylate composite solid material；
Step (4). transition metal oxide precursor body/polyacrylate composite solid material is pulverized, pulverizes 5 minutes,
Obtain solid particle.Step (5). by above-mentioned solid particle 600 DEG C, calcine 5 hours under air atmosphere, obtain nano transition gold
Belong to oxide powder.
Embodiment 7
Step (1). 9.88g 1,6-hexanediol dimethacrylate, 0.12g gorgeous good solid 754 are stirred at 70 DEG C
Mix homogeneously, obtains 10g mixed liquor；
Step (2). 9g nickel acetate, 1g methacrylic acid are joined in above-mentioned mixed liquor, stirs 25 minutes, obtain 20g
Mixed solution containing transition metal oxide precursor body；
Step (3). the above-mentioned mixed solution containing transition metal oxide precursor body is injected in mould, uses 30W
UV Light solidification in 150 seconds, obtains transition metal oxide precursor body/polyacrylate composite solid material；
Step (4). transition metal oxide precursor body/polyacrylate composite solid material is pulverized, pulverizes 5 minutes,
Obtain solid particle.Step (5). by above-mentioned solid particle 700 DEG C, calcine 4 hours under air atmosphere, obtain nano transition gold
Belong to oxide powder.
Embodiment 8
Step (1). 9.85g ethoxylated bisphenol dimethylacrylate and 0.15g camphorquinone are stirred mixing at 72 DEG C
Uniformly, mixed liquor is obtained；
Step (2). 5g hydrochloric acid zirconium is joined in above-mentioned mixed liquor, stirs 30 minutes, obtain 15g and contain oxo transition metal
The mixed solution of compound presoma；
Step (3). the above-mentioned mixed solution containing transition metal oxide precursor body is injected in mould, uses 40W
Blue light illumination solidification in 100 seconds, obtains transition metal oxide precursor body/polyacrylate composite solid material；
Step (4). transition metal oxide precursor body/polyacrylate composite solid material is pulverized, pulverizes 5 minutes,
Obtain solid particle.Step (5). by above-mentioned solid particle 800 DEG C, calcine 2 hours under air atmosphere, obtain nano transition gold
Belong to oxide powder.
Embodiment 9
Step (1). gorgeous to 9.82g urethanes, 0.09g good solid 1173,0.09g gorgeous good solid 184 is stirred at 75 DEG C
Mix mix homogeneously, obtain 10g mixed liquor；
Step (2). 3g ferric nitrate, 3g copper nitrate, 4g zinc nitrate are joined in above-mentioned mixed liquor, stirs 30 minutes,
The mixed solution of transition metal oxide precursor body is contained to 20g；
Step (3). the above-mentioned mixed solution containing transition metal oxide precursor body is injected in mould, uses 40W
Blue light illumination solidification in 80 seconds, obtains transition metal oxide precursor body/polyacrylate composite solid material；
Step (4). transition metal oxide precursor body/polyacrylate composite solid material is pulverized, pulverizes 5 minutes,
Obtain solid particle.Step (5). by above-mentioned solid particle 800 DEG C, calcine 2 hours under air atmosphere, obtain nano transition gold
Belong to oxide powder.
Embodiment 10
Step (1). by 4.8g bisphenol-A-glycidyl Methacrylate, 5g triethylene-glycol methacrylate
Ester, 0.1g are gorgeous, and good solid 1173,0.1g gorgeous good solid 184 is uniformly mixed at 78 DEG C, obtains 10g mixed liquor；
Step (2). 1.2g manganese nitrate transition metal salt is joined in above-mentioned mixed liquor, stirs 30 minutes, obtain 12g and contain
There is the mixed solution of transition metal oxide precursor body；
Step (3). the above-mentioned mixed solution containing transition metal oxide precursor body is injected in mould, uses 50W
UV Light solidification in 240 seconds, obtains transition metal oxide precursor body/polyacrylate composite solid material；
Step (4). transition metal oxide precursor body/polyacrylate composite solid material is pulverized, pulverizes 5 minutes,
Obtain solid particle.Step (5). by above-mentioned solid particle 800 DEG C, calcine 2 hours under air atmosphere, obtain nano transition gold
Belong to oxide powder.
Embodiment 11
Step (1). by gorgeous good solid to 4.8g dimethacrylate diethylene glycol ester, 5g Ethylene glycol dimethacrylate, 0.05g
184, gorgeous good solid 2959, the 0.1g gorgeous good solid 907 of 0.05g is uniformly mixed at 80 DEG C, obtains 10g mixed liquor；
Step (2). 4g manganese nitrate, 3g acrylic acid, 3g methacrylic acid are joined in above-mentioned mixed liquor, stirs 30 points
Clock, obtains 20g and contains the mixed solution of transition metal oxide precursor body；
Step (3). the above-mentioned mixed solution containing transition metal oxide precursor body is injected in mould, uses 50W
Blue light illumination solidification in 200 seconds, obtains transition metal oxide precursor body/polyacrylate composite solid material；
Step (4). transition metal oxide precursor body/polyacrylate composite solid material is pulverized, pulverizes 5 minutes,
Obtain solid particle.Step (5). by above-mentioned solid particle 500 DEG C, calcine 6 hours under air atmosphere, obtain nano transition gold
Belong to oxide powder.
Embodiment 12
Step (1). by 4.82g dimethacrylate diethylene glycol ester, 2.5g Ethylene glycol dimethacrylate, 2.5g tetrem
Gorgeous good solid 819, the 0.06g of diol dimethacrylate, 0.06g is gorgeous, and good solid 754,0.06g camphorquinone stirs mixing at 80 DEG C
Uniformly, 10g mixed liquor is obtained；
Step (2). 8g manganese nitrate, 2g methacrylic acid are joined in above-mentioned mixed liquor, stirs 30 minutes, obtain 20g
Mixed solution containing transition metal oxide precursor body；
Step (3). the above-mentioned mixed solution containing transition metal oxide precursor body is injected in mould, uses 40W
Blue light illumination solidification in 240 seconds, obtains transition metal oxide precursor body/polyacrylate composite solid material；
Step (4). transition metal oxide precursor body/polyacrylate composite solid material is pulverized, pulverizes 5 minutes,
Obtain solid particle.Step (5). by above-mentioned solid particle 800 DEG C, calcine 3 hours under air atmosphere, obtain nano transition gold
Belong to oxide powder.
Above-described embodiment is not the restriction for the present invention, and the present invention is not limited only to above-described embodiment, as long as meeting
Application claims, belongs to protection scope of the present invention.
Claims (1)
1. a nano transition metal oxides raw powder's production technology, it is characterised in that the method comprises the following steps:
Step (1), esters of acrylic acid unsaturated-resin monomer and light trigger are uniformly mixed at 60～80 DEG C, obtain
Mixed liquor；In mixed liquor, the mass content of light trigger is 0.2～2.0%；
Step (2), transition metal salt and acrylic compounds are joined in above-mentioned mixed liquor, stir 10～30 minutes,
To the mixed solution containing transition metal oxide precursor body；Every 10 grams of mixed solutions containing transition metal oxide precursor body
In containing transition metal salt 1～5 grams, acrylic compounds more than 0 and less than or equal to 3 grams；
Step (3), the above-mentioned mixed solution containing transition metal oxide precursor body is injected in mould, use blue light or
Ultraviolet light polymerization, illumination 60～240 seconds under 5～50W power, obtain transition metal oxide precursor body/polyacrylate and be combined
Solid material；
Step (4), transition metal oxide precursor body/polyacrylate composite solid material is pulverized, pulverizes 1～5 minute, must
To solid particle；
Step (5), by above-mentioned solid particle 500～800 DEG C, calcine 2～6 hours under air atmosphere, obtain nano transition gold
Belong to oxide powder；
Described esters of acrylic acid unsaturated-resin monomer is ethoxylated bisphenol dimethylacrylate；
Light trigger described in step (1) is gorgeous good solid 1173, gorgeous good solid 184, gorgeous good solid 2959, gorgeous good solid 907, gorgeous good solid
369, one or several in gorgeous good solid 819, gorgeous good solid 754；
Described transition metal salt is hydrochloric acid zirconium；
Described acrylic compounds is the one or two kinds of of acrylic acid, methacrylic acid.
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