CN101544396B - Method for preparing high-dispersibility zinc oxide granules and colloid thereof - Google Patents
Method for preparing high-dispersibility zinc oxide granules and colloid thereof Download PDFInfo
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- CN101544396B CN101544396B CN2008100609160A CN200810060916A CN101544396B CN 101544396 B CN101544396 B CN 101544396B CN 2008100609160 A CN2008100609160 A CN 2008100609160A CN 200810060916 A CN200810060916 A CN 200810060916A CN 101544396 B CN101544396 B CN 101544396B
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- deionized water
- alkali
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 39
- 239000008187 granular material Substances 0.000 title claims abstract description 8
- 239000000084 colloidal system Substances 0.000 title claims description 4
- 238000000034 method Methods 0.000 title abstract description 22
- 239000000243 solution Substances 0.000 claims abstract description 40
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 23
- 238000002360 preparation method Methods 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000008367 deionised water Substances 0.000 claims abstract description 22
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 22
- 150000003751 zinc Chemical class 0.000 claims abstract description 20
- 239000003513 alkali Substances 0.000 claims abstract description 17
- 239000002244 precipitate Substances 0.000 claims abstract description 17
- 238000001914 filtration Methods 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 44
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 10
- 239000011701 zinc Substances 0.000 claims description 10
- 229910052725 zinc Inorganic materials 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 239000012670 alkaline solution Substances 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 5
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 claims description 4
- 229930006000 Sucrose Natural products 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 239000005720 sucrose Substances 0.000 claims description 4
- -1 sucrose fatty ester Chemical class 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- CODAYFPFZXWNLD-UHFFFAOYSA-N 2-hydroxypropanoyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC(=O)C(C)O CODAYFPFZXWNLD-UHFFFAOYSA-N 0.000 claims description 3
- GUOCOOQWZHQBJI-UHFFFAOYSA-N 4-oct-7-enoxy-4-oxobutanoic acid Chemical compound OC(=O)CCC(=O)OCCCCCCC=C GUOCOOQWZHQBJI-UHFFFAOYSA-N 0.000 claims description 3
- 229920002472 Starch Polymers 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- NXMUXTAGFPJGTQ-UHFFFAOYSA-N decanoic acid;octanoic acid Chemical compound CCCCCCCC(O)=O.CCCCCCCCCC(O)=O NXMUXTAGFPJGTQ-UHFFFAOYSA-N 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 235000011187 glycerol Nutrition 0.000 claims description 3
- 229920000223 polyglycerol Polymers 0.000 claims description 3
- 235000019698 starch Nutrition 0.000 claims description 3
- 239000008107 starch Substances 0.000 claims description 3
- 150000005691 triesters Chemical class 0.000 claims description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- 238000001035 drying Methods 0.000 abstract description 6
- 238000005054 agglomeration Methods 0.000 abstract description 2
- 230000002776 aggregation Effects 0.000 abstract description 2
- 239000012266 salt solution Substances 0.000 abstract 2
- 239000003381 stabilizer Substances 0.000 abstract 1
- 238000002604 ultrasonography Methods 0.000 abstract 1
- 239000003643 water by type Substances 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 18
- 238000005303 weighing Methods 0.000 description 10
- 239000002245 particle Substances 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 5
- 206010013786 Dry skin Diseases 0.000 description 5
- 241000237502 Ostreidae Species 0.000 description 5
- 229960000935 dehydrated alcohol Drugs 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 235000020636 oyster Nutrition 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- 239000013543 active substance Substances 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 239000012808 vapor phase Substances 0.000 description 4
- IIZPXYDJLKNOIY-JXPKJXOSSA-N 1-palmitoyl-2-arachidonoyl-sn-glycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCC\C=C/C\C=C/C\C=C/C\C=C/CCCCC IIZPXYDJLKNOIY-JXPKJXOSSA-N 0.000 description 3
- 229920000881 Modified starch Polymers 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 229960004756 ethanol Drugs 0.000 description 3
- 239000000787 lecithin Substances 0.000 description 3
- 235000010445 lecithin Nutrition 0.000 description 3
- 229940067606 lecithin Drugs 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 235000019426 modified starch Nutrition 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 235000013904 zinc acetate Nutrition 0.000 description 3
- JGPSMWXKRPZZRG-UHFFFAOYSA-N zinc;dinitrate;hexahydrate Chemical class O.O.O.O.O.O.[Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O JGPSMWXKRPZZRG-UHFFFAOYSA-N 0.000 description 3
- 239000004368 Modified starch Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 239000012716 precipitator Substances 0.000 description 2
- UVGUPMLLGBCFEJ-SWTLDUCYSA-N sucrose acetate isobutyrate Chemical compound CC(C)C(=O)O[C@H]1[C@H](OC(=O)C(C)C)[C@@H](COC(=O)C(C)C)O[C@@]1(COC(C)=O)O[C@@H]1[C@H](OC(=O)C(C)C)[C@@H](OC(=O)C(C)C)[C@H](OC(=O)C(C)C)[C@@H](COC(C)=O)O1 UVGUPMLLGBCFEJ-SWTLDUCYSA-N 0.000 description 2
- DJWUNCQRNNEAKC-UHFFFAOYSA-L zinc acetate Chemical class [Zn+2].CC([O-])=O.CC([O-])=O DJWUNCQRNNEAKC-UHFFFAOYSA-L 0.000 description 2
- 241000024287 Areas Species 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000005291 magnetic effect Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 229920001289 polyvinyl ether Polymers 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000011540 sensing material Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000010671 solid-state reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005118 spray pyrolysis Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010897 surface acoustic wave method Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
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Abstract
The invention relates to a method for preparing high-dispersibility zinc oxide granules, which comprises the following steps: (1) dissolving soluble zinc salt into deionized water, and stirring the mixture to prepare 0.1 to 10 percent of zinc salt solution in percentage by mass; (2) dissolving alkali in the deionized water according to a molar ratio of the zinc salt to the alkali of 1:2 to prepare alkali solution; (3) dissolving hydrophilic emulsifying agent of which adding amount is 0.5 to 20.0 percent of the mass of the zinc salt into the deionized water; (4) at a temperature of between 20 and 90 DEG C, fully stirring the emulsifying agent solution, adding the zinc salt solution and the alkali solution into the emulsifying agent solution drop by drop to obtain white precipitate, and filtering and separating the white precipitate; and (5) washing the separated white precipitate, drying the washed white precipitate at a temperature of between 40 and 120 DEG C to obtain zinc oxide powder, dispersing the zinc oxide powder into water by ultrasound, and adding 0.1 to 10 percent of stabilizing agent to obtain zinc oxide sol. Compared with the prior art, the method has the advantages that the preparation cost is low, and the size and shape of the zinc oxide granules are easy to control; and the prepared zinc oxide granules have even grain diameter and high dispersibility and do not have the problem of agglomeration.
Description
Technical field
The present invention relates to a kind of preparation method of high-dispersibility zinc oxide granules, further, the invention still further relates to a kind of high-dispersibility zinc oxide colloidal preparation method.
Background technology
ZnO has many high-quality character, and is nontoxic harmless to the person as ZnO itself, also can absorb ultraviolet ray in visible transparent, has bigger electromechanical coupling factor.Utilize its marvellous performance at aspects such as light, electricity, magnetic, sensitivities, nano zine oxide not only can replace common zinc oxide in traditional Application Areass such as rubber industry, coatings industry, ceramic industries, also show wide application prospect at current compelling high-technology field, as gas alarm, ultraviolet filter, effective catalyst, environment purification, short wavelength laser, solar cell, surface acoustic wave and piezoelectric etc.
The prerequisite that zinc oxide has good function is even particle distribution, good dispersity, and form is controlled.At present, the method for preparation of industrialization zinc oxide is divided three classes substantially: solid phase method, liquid phase method and vapor phase process.
The solid state reaction method have need not solvent, transformation efficiency height, technology is simple, energy consumption is low, the characteristics of easily-controlled reaction conditions, but reaction is often carried out not exclusively or process in liquefaction phenomenon may appear.With reference to Chinese invention patent: ZL200410064521.X, " a kind of preparation method of high-purity zinc oxide powder " (Granted publication number: CN1267355C) is disclosed, this invention uses high-purity zinc powder to be raw material, utilizes the mechanical ball milling hydrolysis method to prepare high-purity zinc oxide powder.
Vapor phase process mainly contains induced with laser vapour deposition process, gas-phase reaction synthesis method, spray pyrolysis and chemical vapor phase oxidation process.Vapor phase process is in the lab scale stage at present in China, desires to reach suitability for industrialized production, also will solve a series of engineering problems and equipment material problem, is difficult to realize large-scale industrial production.Specifically can be with reference to Chinese patent literature CN1308968C, CN1982220A etc.
Liquid phase method mainly comprises the precipitator method, overweight force method, microemulsion method, hydrothermal method and sol-gel method etc.During the liquid phase method nano zine oxide was produced, the most frequently used preparation method was a sluggish precipitation.Adopt the precipitator method to prepare nano zine oxide to have that technology is simple, good product quality, be easy to characteristics such as control, production cost is low, be considered to a kind of preparation method of tool industrialization development prospect.Be easy to reunite but shortcoming is a Zinc oxide particles, the single nano zinc oxide material of size distribution synthetic has very big difficulty.Open with reference to Chinese invention patent: CN1616354A, a kind of " method of coordination Preparation by Uniform Precipitation nano zine oxide " disclosed, this application is a raw material with zinc oxide or zinc salt, is coordination agent with ammoniacal liquor and carbonate.Again with reference to Chinese invention patent: ZL02109078.5, (Granted publication number: CN1239395C), this method also comprises pyrolysis and calcining step, will certainly increase preparation cost to disclose a kind of " preparation method of nano zinc oxide material ".
Because tensio-active agent can form the electrostatic double layer protective membrane of one deck densification on solid-liquid interface, often be applied to preparing in the reaction of zinc oxide again, to hinder the OH in the solution
-And Zn
2+Assemble in the precipitation surface that has generated, thereby suppressed growing up of nucleus, and make the precipitation in the solution be in dispersion state highly, promoted the formation of new nucleus.In the preparation nano zine oxide, tensio-active agent commonly used is Sodium dodecylbenzene sulfonate, alkylphenol polyvinyl ether series and polyoxyethylene glycol, polyvinylpyrrolidone (PVP) etc.But the zinc oxide that adopts above-mentioned additive method to prepare high dispersing can make that usually cost raises significantly, is unfavorable for industrialized mass.With reference to Chinese invention patent: 200410015790.7, a kind of " manufacture method of nano zine oxide " (Granted publication number: CN1235807C), control the speed of growth of nucleus with the control particle size by the hydrophilic promoting agent polyvinyl alcohol (PVA) that shows in this patent is disclosed.Similarly also have Chinese patent literature CN1944265A, CN1887720A etc.
Summary of the invention
First technical problem to be solved by this invention be provide at the above-mentioned state of the art a kind of polymolecularity, with low cost, prepare, be easy to industrialized Zinc oxide particles preparation method at low temperatures.
Second technical problem to be solved by this invention be provide at the above-mentioned state of the art a kind of polymolecularity, with low cost, prepare, be easy to industrialized zinc oxide colloid preparation method at low temperatures.
The present invention solves the problems of the technologies described above the technical scheme that is adopted: a kind of preparation method of high-dispersibility zinc oxide granules comprises the steps:
1. get soluble zinc salt and be dissolved in the deionized water, stir, the mass percent that is configured to is 0.1%～10% zinc solution;
2. be about 1: 2 and get alkali by the molar ratio of zinc salt and alkali and be dissolved in deionized water, be configured to alkaline solution;
3. get hydrophilic emulsifier and be dissolved in the deionized water, the amount that emulsifying agent adds is 0.5%～20.0% of a zinc salt quality;
4. under 20～90 ℃ of conditions, emulsifier solution is fully stirred, stir, simultaneously zinc solution and alkaline solution are dropwise joined in the emulsifier solution, obtain white precipitate, filtering separation;
5. the white precipitate washing that above-mentioned separation is obtained, dry under 40～120 ℃ of conditions, promptly obtain Zinc oxide powder.
The zinc salt of step described in 1. can be one or more mixture of zinc chloride, zinc nitrate, zinc sulfate, zinc acetate etc.
The alkali lye of step described in 2. can be sodium hydroxide, water glass, lithium hydroxide, potassium hydroxide, one or more mixtures in ammoniacal liquor, the organic amine.
The emulsifying agent of step described in 3. can be one or more mixtures of trimerization monoglyceride, Yelkin TTS, sucrose fatty ester, polyglycerol ester, Sucrose acetoisobutyrate, molecule distillating monoglyceride, octenyl succinate, stearoyl lactate, Glycerin, mixed triester with caprylic acid capric acid or treated starch.
The microtexture of the Zinc oxide powder of step described in 5. can be stratiform, spherical or hexagonal shape.
A kind of high-dispersibility zinc oxide colloidal preparation method comprises the steps:
1. get soluble zinc salt and be dissolved in the deionized water, stir, the mass percent that is configured to is 0.1%～10% zinc solution;
2. be to get alkali at 1: 2 to be dissolved in deionized water by the molar ratio of zinc salt and alkali, be configured to alkaline solution;
3. get hydrophilic emulsifier and be dissolved in the deionized water, the amount that emulsifying agent adds is 0.5%～20.0% of a zinc salt quality;
4. under 20～90 ℃ of conditions, emulsifier solution is fully stirred, simultaneously zinc solution and alkaline solution are dropwise joined in the emulsifier solution, obtain white precipitate, filtering separation;
5. the white precipitate washing that above-mentioned separation is obtained, dry under 40～120 ℃ of conditions;
6. with above-mentioned dried Zinc oxide powder ultra-sonic dispersion in deionized water, the mass percent concentration scope of zinc oxide is less than 40%, adds stablizer, makes consistent dose reach 0.01～1% mass percent, promptly obtains high dispersive zinc oxide colloid.
The stablizer of step described in 6. can be one or more the mixture in ethanol, n-propyl alcohol, Virahol, propyl carbinol and the ethylene glycol.
In the technical scheme, preferably making the alkali lye of hydroxyl-containing ion and the solution that contains zine ion is the equivalent reaction, reaches the perfect purpose of reaction, certainly, allowing that proportioning has certain leeway between them, be controlled at the 10% excessive or amount of owing, also is to obtain similar effect substantially.
Compared with prior art, the invention has the advantages that: mainly adopt hydrophilic emulsifier as tensio-active agent, by the conditioned reaction temperature, reaction times, reactant concn controlled oxidation zinc particulate size and pattern, the tensio-active agent that adopts in the reaction is water-soluble, nontoxic pollution-free, raw materials cost is cheap, preparation technology is simple, the reaction conditions gentleness, the zinc oxide particle diameter that makes is even, pattern is controlled, there is not agglomeration traits, obviously be better than the Zinc oxide powder and the colloidal sol of ordinary method preparation, can be used as catalytic material, absorbing material, luminescent material, and sensing material is used.
Description of drawings
Fig. 1 is the electron scanning micrograph of embodiment 1 layer zinc oxide.
Fig. 2 is the electron scanning micrograph of embodiment 4 hexagonal shape zinc oxide.
Embodiment
Embodiment describes in further detail the present invention below in conjunction with accompanying drawing.
Embodiment 1:
Get 2000 gram deionized waters, join in the reactor that reflux exchanger is housed, add 20 gram zinc nitrate hexahydrates, start agitator to all dissolvings; Take by weighing 5.4 gram sodium hydroxide and join in the 2000 gram deionized waters, start agitator to all dissolvings; Take by weighing 2 gram Yelkin TTS and be dissolved in 1000 gram deionized waters, start agitator and be warming up to 80 ℃, to all dissolvings; Above-mentioned solution zinc nitrate hexahydrate solution and sodium hydroxide are joined in the lecithin soln with the speed of 400ml/h respectively, and keeping temperature of reaction is 80 ℃, adds afterreaction 2 hours; Reaction solution obtains white precipitate after filtration, uses 200ml deionized water wash 5 times earlier, washs respectively 2 times with the 50ml dehydrated alcohol then.Then in 100 ℃ of dryings 5 hours.Promptly obtain Zinc oxide powder.
The scanning electron microscope diagram sheet of gained Zinc oxide powder is seen Fig. 1.The Zinc oxide particles size is about 400 nanometers, specific surface area 225m
2/ g is laminate structure.
Get gained Zinc oxide powder 5 grams and be scattered in 25 gram deionized waters, behind ultra-sonic dispersion, add 0.3 gram Virahol, get the oyster white dispersion liquid.Promptly obtain high dispersive zinc oxide colloidal sol.
Embodiment 2:
Get 2000 gram deionized waters, join in the reactor that reflux exchanger is housed, add 60 gram zinc nitrate hexahydrates, start agitator to all dissolvings; Take by weighing 16.2 gram sodium hydroxide and join in the 2000 gram deionized waters, start agitator to all dissolvings; Take by weighing 2 gram Yelkin TTS and be dissolved in 1000 gram deionized waters, start agitator and be warming up to 80 ℃, to all dissolvings; Above-mentioned solution zinc nitrate hexahydrate solution and sodium hydroxide are joined in the lecithin soln with the speed of 400ml/h respectively, and keeping temperature of reaction is 80 ℃, adds afterreaction 2 hours; Reaction solution obtains white precipitate after filtration, uses 200ml deionized water wash 5 times earlier, washs respectively 2 times with the 50ml dehydrated alcohol then.Then in 100 ℃ of dryings 5 hours.Promptly obtain Zinc oxide powder.
Gained Zinc oxide particles size is about 720 nanometers, specific surface area 210m
2/ g is laminate structure.
Get gained Zinc oxide powder 5 grams and be scattered in 25 gram deionized waters, behind ultra-sonic dispersion, add 0.1 gram Virahol, get the oyster white dispersion liquid.Promptly obtain high dispersive zinc oxide colloidal sol.
Embodiment 3:
Get 2000 gram deionized waters, join in the reactor that reflux exchanger is housed, add 20 gram zinc nitrate hexahydrates, start agitator to all dissolvings; Take by weighing 5.4 gram sodium hydroxide and join in the 2000 gram deionized waters, start agitator to all dissolvings; Take by weighing 0.2 gram esterification modified starch and be dissolved in 1000 gram deionized waters, start agitator and be warming up to 80 ℃, to all dissolvings; Above-mentioned solution zinc nitrate hexahydrate solution and sodium hydroxide are joined in the lecithin soln with the speed of 400ml/h respectively, and keeping temperature of reaction is 80 ℃, adds afterreaction 2 hours; Reaction solution obtains white precipitate after filtration, uses 200ml deionized water wash 5 times earlier, washs respectively 2 times with the 50ml dehydrated alcohol then.Then in 100 ℃ of dryings 5 hours.Promptly obtain Zinc oxide powder.
Gained Zinc oxide particles size is about 250 nanometers, specific surface area 225m
2/ g is laminate structure.
Get gained Zinc oxide powder 5 grams and be scattered in 25 gram deionized waters, behind ultra-sonic dispersion, add 0.1 gram ethanol, get the oyster white dispersion liquid.Promptly obtain high dispersive zinc oxide colloidal sol.
Embodiment 4:
Get 2000 gram deionized waters, join in the reactor that reflux exchanger is housed, add 20 grams, two hydration zinc acetates, start agitator to all dissolvings; Take by weighing 7.2 gram sodium hydroxide and join in the 2000 gram deionized waters, start agitator to all dissolvings; Take by weighing 1.5 gram Sucrose acetoisobutyrates and be dissolved in 1000 gram deionized waters, start agitator and be warming up to 60 ℃, to all dissolvings; Above-mentioned solution zinc nitrate hexahydrate solution and sodium hydroxide are joined in the Sucrose acetoisobutyrate solution with the speed of 400ml/h respectively, and keeping temperature of reaction is 60 ℃, adds afterreaction 3 hours; Reaction solution obtains white precipitate after filtration, uses 200ml deionized water wash 5 times earlier, washs respectively 2 times with the 50ml dehydrated alcohol then.Then in 100 ℃ of dryings 5 hours.Promptly obtain the high dispersive Zinc oxide powder.
The gained Zinc oxide powder is spherical in shape.
Get gained Zinc oxide powder 5 grams and be scattered in 25 gram deionized waters, behind ultra-sonic dispersion, add 0.3 gram Virahol, get the oyster white dispersion liquid.Promptly obtain high dispersive zinc oxide colloidal sol.
Embodiment 5:
Get 2000 gram deionized waters, join in the reactor that reflux exchanger is housed, add 20 grams, two hydration zinc acetates, start agitator to all dissolvings; Take by weighing 7.2 gram sodium hydroxide and join in the 2000 gram deionized waters, start agitator to all dissolvings; Take by weighing 2.5 gram esterification modified starches and be dissolved in 1000 gram deionized waters, start agitator and be warming up to 40 ℃, to all dissolvings; Above-mentioned solution zinc nitrate hexahydrate solution and sodium hydroxide are joined in the esterification modified starch solution with the speed of 400ml/h respectively, and keeping temperature of reaction is 40 ℃, adds afterreaction 3 hours; Reaction solution obtains white precipitate after filtration, uses 200ml deionized water wash 5 times earlier, washs respectively 2 times with the 50ml dehydrated alcohol then.Then in 100 ℃ of dryings 5 hours.Promptly obtain the high dispersive Zinc oxide powder.
The scanning electron microscope diagram sheet of gained Zinc oxide powder is seen Fig. 2, specific surface area 85m
2/ g is hexagonal shape structure.
Get gained Zinc oxide powder 2 grams and be scattered in 25 gram deionized waters, behind ultra-sonic dispersion, add 0.1 gram ethanol, get the oyster white dispersion liquid.Promptly obtain high dispersive zinc oxide colloidal sol.
Claims (5)
1. the preparation method of a high-dispersibility zinc oxide granules comprises the steps:
1. get soluble zinc salt and be dissolved in the deionized water, stir, the mass percent that is configured to is 0.1%～10% zinc solution;
2. be to get alkali at 1: 2 to be dissolved in deionized water by the molar ratio of zinc salt and alkali, be configured to alkaline solution;
3. get hydrophilic emulsifier and be dissolved in the deionized water, the amount that emulsifying agent adds is 0.5%～20% of a used zinc salt quality;
4. under 20～90 ℃ of conditions, emulsifier solution is fully stirred, simultaneously zinc solution and alkaline solution are dropwise joined in the emulsifier solution, obtain white precipitate, filtering separation;
5. the white precipitate washing that above-mentioned separation is obtained, dry under 40～120 ℃ of conditions, promptly obtain Zinc oxide powder, the emulsifying agent of step described in 3. is one or more mixtures of Yelkin TTS, sucrose fatty ester, polyglycerol ester, molecule distillating monoglyceride, octenyl succinate, stearoyl lactate, Glycerin, mixed triester with caprylic acid capric acid or treated starch.
2. preparation method according to claim 1 is characterized in that the zinc salt described in step 1. is one or more a mixture of zinc chloride, zinc nitrate, zinc sulfate, zinc acetate.
3. preparation method according to claim 1 is characterized in that the alkali described in step 2. is sodium hydroxide, lithium hydroxide, potassium hydroxide, one or more mixtures in ammoniacal liquor, the organic amine.
4. preparation method according to claim 1, the microtexture that it is characterized in that the Zinc oxide powder described in step 5. are stratiform, spherical or hexagonal shape.
5. a high-dispersibility zinc oxide colloidal preparation method comprises the steps:
1. get soluble zinc salt and be dissolved in the deionized water, stir, the mass percent that is configured to is 0.1%～10% zinc solution;
2. be to get alkali at 1: 2 to be dissolved in deionized water by the molar ratio of zinc salt and alkali lye, be configured to alkali lye solution;
3. get hydrophilic emulsifier and be dissolved in the deionized water, the amount that emulsifying agent adds is 0.5%～20% of a used zinc salt quality;
4. under 20～90 ℃ of conditions, emulsifier solution is stirred, simultaneously zinc solution and alkali lye solution are dropwise joined in the emulsifier solution, obtain white precipitate, filtering separation;
5. the white precipitate washing that above-mentioned separation is obtained, dry under 40～120 ℃ of conditions,
6. with dried Zinc oxide powder ultra-sonic dispersion in deionized water, mass percent concentration is less than 40%, adds stablizer, makes consistent dose reach 0.01～1% mass percent, promptly obtains high dispersive zinc oxide colloid,
The emulsifying agent of step described in 3. is one or more mixtures of Yelkin TTS, sucrose fatty ester, polyglycerol ester, molecule distillating monoglyceride, octenyl succinate, stearoyl lactate, Glycerin, mixed triester with caprylic acid capric acid or treated starch,
The stablizer of step described in 6. is one or more the mixture in ethanol, n-propyl alcohol, Virahol, propyl carbinol and the ethylene glycol.
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