CN100441510C - Method of preparing nano hydroxyl zinc stannate and nano zinc stannate - Google Patents
Method of preparing nano hydroxyl zinc stannate and nano zinc stannate Download PDFInfo
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- CN100441510C CN100441510C CNB2005100178556A CN200510017855A CN100441510C CN 100441510 C CN100441510 C CN 100441510C CN B2005100178556 A CNB2005100178556 A CN B2005100178556A CN 200510017855 A CN200510017855 A CN 200510017855A CN 100441510 C CN100441510 C CN 100441510C
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Abstract
The invention provides a preparation method for nanometer zinc hydroxystannate and nanometer zinc stannate. Said method uses tin compounds as raw materials to prepare zinc hydroxystannate with particle size of 2-100 nm. Nanometer zinc stannate can be obtained by sintering the zinc hydroxystannate at high temperature. Zinc hydroxystannate (xZnO*ySnO*zH2O) has a molar ratio of x : y : z at 1 : 0.8-1.4 : 1-5. They can be used alone or mixed for polymer materials, and has a good effect on flame retardancy and smoke suppression. Nanometer zinc hydroxystannate can merely be used in the material operating less than 180DEG C, while nanometer zinc stannate can be used for various polymer materials. In addition, both can be also used for gas-sensitive materials and lubricant additives.
Description
Technical field
The invention belongs to preparation method's technical field of nanometer tinbase compound, be specifically related to the preparation method of nano zinc hydroxyl stannate and nano-zinc stannate.
Background technology
Middle 1980s, International Tin Research Institute took up to study the flame retardant properties and the smoke suppressing of tin compound, think that zinc hydroxyl stannate and zinc are ideal tinbase anti-flaming smoke-inhibiting agents, the Halogen superpolymer of they and Halogen superpolymer and halogen-containing flame retardant all has synergy.These superpolymer comprise PVC, unsaturated polyester, Synolac plastics, chloride thermoplastics etc.Compare with antimonous oxide, zinc hydroxyl stannate and zinc have following advantage: the growing amount of cigarette, carbonic acid gas and carbon monoxide when reducing material combustion, nontoxic, safety, consumption are low.The decomposition temperature of zinc hydroxyl stannate is 204 ℃, so it only limits to use in temperature is lower than the material of 180 ℃ of operations, and zinc can be used in any polymer system.
Preparation about these two kinds of tin compounds: English Patent No.2230255 (nineteen ninety) is raw material, makes modifier with polyacrylic acid with sodium stannate and zinc chloride, has made zinc hydroxyl stannate and the zinc of particle diameter less than 0.2 μ m; MIT (1992) is that raw material makes the zinc that particle diameter is 2-5 μ m with tin tetrachloride or stannic oxide and zinc salt; Japanese Patent (No.24831, No.24832, No.24833, No2.4834, No.24835) (1993) is a raw material with the acid solution of tetravalent tin ion and zine ion, add a certain amount of alkali lye, made crystal formation and the unformed zinc hydroxyl stannate of particle diameter at 0.2-1.0 μ m; United States Patent (USP) (No.5891362, No.6001164, No.6040372) (1999,2000) is the reaction of raw material and zinc salt with the sodium stannate, has made crystal formation and the unformed zinc hydroxyl stannate of particle diameter at 2-200nm to add hydrogen peroxide and not add hydrogen peroxide respectively; Chinese patent (No.00119199) (2000) is that raw material has made zinc hydroxyl stannate and the zinc of particle diameter at 0.4-6 μ m with sodium stannate and zinc chloride.With the sodium stannate is raw material, and the price comparison costliness is difficult in the application promoting.
Summary of the invention:
The nano zinc hydroxyl stannate that it is feedstock production particle diameter 2-100nm that the object of the invention is a kind of stannic compound with cheapness is provided and the method for nano-zinc stannate.
For reaching above-mentioned purpose, the present invention adopts following technical scheme: the nano zinc hydroxyl stannate preparation method, stannic compound and zinc salt are mixed to be dissolved in the dilute hydrochloric acid solution, under agitation dropping sodium solution forms precipitation again, precipitation is mixed with organic solvent, then component distillation, the dry nano zinc hydroxyl stannate that gets; Stannic compound is tin tetrachloride or tindioxide, and zinc salt is zinc chloride, zinc sulfate, zinc nitrate, zinc acetate or Zinc Gluconate, and the mol ratio of stannic compound and zinc salt is 1: 1.1-1.5; Organic solvent is methyl alcohol, propyl carbinol or benzene, and the volume ratio of water is 3-20 in organic solvent and the throw out: 1; Reaction PH=3-12, temperature of reaction is 15-100 ℃, reaction times 1-8 hour; Drying temperature 80-105 ℃, 3-10 hour time of drying.
Add the aqueous hydrogen peroxide solution mixing before the dropping sodium solution earlier.
Reaction pH=5-9, temperature are 20-90 ℃.
The preparation method of nano-zinc stannate utilizes above-mentioned preparation method to prepare nano zinc hydroxyl stannate, the gained nano zinc hydroxyl stannate under 300-600 ℃ of temperature calcination 1-30 hour nano-zinc stannate.
Among the present invention, precipitation can be mechanical stirring, emulsification or ultra-sonic dispersion with organic solvent blended mode, and component distillation can be air distillation or underpressure distillation.
Utilize the present invention, can make raw material, make zinc hydroxyl stannate and the zinc of particle diameter at 2-100nm with the stannic compound of cheapness.
Description of drawings
Fig. 1 is armorphous nano zinc hydroxyl stannate TEM figure;
Fig. 2 is crystal type nano zinc hydroxyl stannate TEM figure;
Fig. 3 is armorphous nano zinc hydroxyl stannate TG/DTA figure;
Fig. 4 is crystal type nano zinc hydroxyl stannate TG/DTA figure;
Fig. 5 is the XRD figure of crystal type nano zinc hydroxyl stannate.
The used instrument of TEM is JEM100CX-type transmission electron microscope (Japanese JEOL company), and the sample dispersion solvent is a distilled water; The used instrument of thermogravimetric analysis is EXSTAR6200 type thermal analyzer (Japanese SeiloInstruments Inc.), heats up under air atmosphere, and temperature rise rate is 10 ℃/min; The used instrument of XRD analysis is XPert ProX ray powder diffraction instrument (Dutch Philip company), adopts the CuK excitaton source.
Embodiment
Embodiment 1,0.9g stannic chloride pentahydrate and 0.4g zinc chloride are dissolved in the 0.5moL/L hydrochloric acid soln of 10mL, adding distil water is diluted to 120mL, the content that adds 20mL again is 28% aqueous hydrogen peroxide solution, under stirring state, drip the sodium hydroxide solution of 0.5moL/L, adjust pH is about 8, after dropwising, be warming up to 90 ℃, temperature control reaction 5 hours, the white precipitate filtration washing of institute is to the AgNO of usefulness 0.2moL/L
3Behind the no Cl-ion of solution check, precipitation is distributed in the propyl carbinol of 40mL component distillation.The product that component distillation is obtained under 105 ℃ condition dry 3 hours promptly obtains amorphous nano zinc hydroxyl stannate.The 500 ℃ of calcinations 5 hours in muffle furnace of this product promptly obtain amorphous nano-zinc stannate.
Claims (4)
1, nano zinc hydroxyl stannate preparation method, it is characterized in that stannic compound and zinc salt are mixed be dissolved in the dilute hydrochloric acid solution, under agitation dropping sodium solution forms precipitation again, precipitation is mixed with organic solvent, then component distillation, the dry nano zinc hydroxyl stannate that gets; Stannic compound is tin tetrachloride or tindioxide, and zinc salt is zinc chloride, zinc sulfate, zinc nitrate, zinc acetate or Zinc Gluconate, and the mol ratio of stannic compound and zinc salt is 1: 1.1-1.5; Organic solvent is methyl alcohol, propyl carbinol or benzene, and the volume ratio of water is 3-20 in organic solvent and the throw out: 1; Reaction PH=3-12, temperature of reaction is 15-100 ℃, reaction times 1-8 hour; Drying temperature 80-105 ℃, 3-10 hour time of drying.
2, preparation method as claimed in claim 1 is characterized in that, adds the aqueous hydrogen peroxide solution mixing before the dropping sodium solution earlier.
3, preparation method as claimed in claim 1 is characterized in that, reaction pH=5-9, temperature are 20-90 ℃.
4, the preparation method of nano-zinc stannate is characterized in that, utilizes the described preparation method of claim 1 to prepare nano zinc hydroxyl stannate, the gained nano zinc hydroxyl stannate under 300-600 ℃ of temperature calcination 1-30 hour nano-zinc stannate.
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| CNB2005100178556A CN100441510C (en) | 2005-08-04 | 2005-08-04 | Method of preparing nano hydroxyl zinc stannate and nano zinc stannate |
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| CNB2005100178556A CN100441510C (en) | 2005-08-04 | 2005-08-04 | Method of preparing nano hydroxyl zinc stannate and nano zinc stannate |
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| CN100441510C true CN100441510C (en) | 2008-12-10 |
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Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101844798B (en) * | 2010-05-14 | 2011-08-24 | 北京科技大学 | Preparation method of high-dispersion nano zinc hydroxyl stannate array with controllable size |
| CN101943692B (en) * | 2010-08-11 | 2014-02-26 | 上海师范大学 | Air-sensitive material with high-sensitivity and quick-response, and preparation method and application thereof |
| CN102515185B (en) * | 2011-12-08 | 2014-02-05 | 西北师范大学 | Zinc hydroxystannate-palygorskite clay compound, its preparation and application as fire retardant |
| CN102627831B (en) * | 2012-04-16 | 2014-04-02 | 河南大学 | Zinc hydroxystannate/melamine-dicyandiamide formaldehyde resin phosphate composite powder and preparation method thereof |
| CN102698732B (en) * | 2012-06-01 | 2014-05-14 | 福州大学 | Photocatalyst and preparation method and application thereof |
| CN103274450B (en) * | 2013-06-06 | 2014-11-19 | 吉林大学 | Preparation method of submicron hydroxy zinc stannate cubic material |
| CN103601234B (en) * | 2013-10-23 | 2016-08-17 | 三棵树涂料股份有限公司 | The preparation method of nano-zinc stannate |
| CN104150527B (en) * | 2014-06-24 | 2016-06-22 | 济南大学 | A kind of preparation method of hollow tetrakaidecahedron structural hydroxyl zinc gas sensitive |
| CN104310462A (en) * | 2014-10-14 | 2015-01-28 | 安徽科技学院 | Method of synthesizing hydroxyl stannate microcrystals by hydrothermal process |
| CN105236470A (en) * | 2015-10-30 | 2016-01-13 | 江苏格罗瑞化学有限公司 | Method for preparing nano-zinc stannate |
| CN106115773B (en) * | 2016-06-21 | 2017-12-12 | 广西新晶科技有限公司 | A kind of zinc stannate raw powder's production technology |
| CN106009036A (en) * | 2016-07-04 | 2016-10-12 | 沈阳化工大学 | Preparation method for nanometer composite flame retardant |
| CN109678198A (en) * | 2018-12-17 | 2019-04-26 | 天津理工大学 | A kind of synthetic method of the nano-zinc stannate material for N-shaped transparent semiconductor film |
| CN116947086B (en) * | 2023-08-01 | 2024-03-05 | 东北师范大学 | Pomegranate type Zn 2 SnO 4 Preparation method and application of nano flame retardant |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1304880A (en) * | 2000-07-19 | 2001-07-25 | 云南锡业公司 | Process for preparing powdered zinc hydroxytannate |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1304880A (en) * | 2000-07-19 | 2001-07-25 | 云南锡业公司 | Process for preparing powdered zinc hydroxytannate |
Non-Patent Citations (2)
| Title |
|---|
| ZnSnO3纳米粉体的合成及其汽敏特性研究. 徐甲强.硅酸盐学报，第30卷第3期. 2002 |
| ZnSnO3纳米粉体的合成及其汽敏特性研究. 徐甲强.硅酸盐学报，第30卷第3期. 2002 * |
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