CN1640947A - Inorganic pigment hydrosol and its preparation method and use - Google Patents
Inorganic pigment hydrosol and its preparation method and use Download PDFInfo
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- CN1640947A CN1640947A CN 200410001432 CN200410001432A CN1640947A CN 1640947 A CN1640947 A CN 1640947A CN 200410001432 CN200410001432 CN 200410001432 CN 200410001432 A CN200410001432 A CN 200410001432A CN 1640947 A CN1640947 A CN 1640947A
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- Prior art keywords
- water
- glycol
- multiethylene
- sol
- powder
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- Inks, Pencil-Leads, Or Crayons (AREA)
- Paints Or Removers (AREA)
Abstract
The present invention is red and green inorganic pigment hydrosol, the red pigment hydrosol contains alpha-Fe2O3 solid in 20-30 wt%, and the green pigment hydrosol contains ZnCo2O4 solid in 20-30 wt%. The preparation process includes adding FeO2 or FeO2, Zn(CH3COO)2 and Co(CH3COO)2 into triethylene glycol, heating and stirring until becoming clear, adding water for reaction to obtain red or green solid suspension; centrifugally separating the suspension, washing with ethanol, and drying to obtain alpha-Fe2O3 or ZnCo2O4 powder; and dispersing the powder in water or alcohol to obtain red or green inorganic nanometer dye hydrosol. The hydrosol is stable, has solid content up to 20 %, and may be used widely in ink, paint, drawing, etc.
Description
Technical field
The present invention relates to a kind of mineral dye water-sol.
The invention still further relates to the preparation method of the above-mentioned water-sol.
The invention still further relates to the application of the above-mentioned water-sol.
Background technology
ZnCo
2O
4, α-Fe
2O
3Deng be industrial most important several mineral dyes (G.Buxbaum, Industrial Inorganic Pigments, VCH, Weinheim, Germany, 1993,1st edn., p.85.2; Ullmanns Encyklopa
Die der Technischen Chemie, VCH, Weinheim, Germany, 1979,4th edn., p.607.), be usually used in fields such as paint, building coating, plastics, enamel, but usually will be in down preparation of high temperature (＞500 ℃), and particle diameter big (＞500nm).Application at aspects such as the plastics of ink, coating, pottery, paint, air brushing, UV stable, films then needs particle little and can form the stable water-sol.If can realize temperature production and it is prepared into nano-scale particle and the stable water-sol then can expands its range of application greatly fully.Because the color of above-mentioned pigment is by its crystalline structures shape, therefore in unusual difficulty with these pigment prepared nano-scales sizes and will obtain suitable crystal formation the time, particularly at low temperatures reaction can make that situation becomes more be difficult to control.Although many method (C.Otero Arean, M.Penarroya Mentruit, E.Escalona Platero that prepare metal oxide nano-material are at low temperatures arranged at present, F.X.Llabres Xamena and J.B.Parra, Mater.Lett, 1999,39,22; J.J.Kingsley, K.Suresh and K.C.Patil, J.Mater.Sci., 1990,25,1305; W.S.Cho and M.Kakihana, J.Alloys Compd., 1999,287,87; W.Ha
Rtl, C.Beck, M.Roth, F.Meyer and R.Hempelmann, Ber.Bunsenges.Phys.Chem., 1997,101,1714; H.Herrig and R.Hempelmann, Nanostruct.Mater., 1997,9,241; M.Veith, S.Kneip, S.Faber and E.Fritscher, Mater.Sci.Forum, 1998,269,303; J.Livage, M.Henry, C.Sanchez, Prog.Solid State Chem.1988,18,259; E.Matijevic, Chem.Mater.1993,5,412; C.Beck, W.H rtl, R.Hempelmann, J.Mater.Res.1998,13,3174; O.Palchik, J.Zhu, A.Gedanken, J.Mater.Res.2000,10,1251; Y.Xia, B.Gates, Y.Yin, Y.Lu, Adv.Mater.2000,12,693.), but seldom be used to prepare inorganic nano pigment (Fuller, S.B.; Wilhelm, E.J.; Jacobson, J.M.J.Microelectromech.Syst.2002,11,54; Bermel, A.D.; Bugner, D.E.J.ImagingSci.1999,43,320; H.Ohta, Y.Kurokawa, J.Mater.Sci.Lett.1992,11,868; C.R.Ronda, M.Bredol, J.Colloid Interface Sci.1995,173,328; L.Armelao, A.Armigliato, R.Bozio, P.Colombo, J.Mater.Res.1997,12,1441; W.S.Cho, M.Kakihana, J.Alloys Compd.1999,287,87; P.M.Kumar, S.Badrinarayanan, M.Sastry, Thin Solid Films 2000,358,122; L.E.McNeil, R.H.French, Acta Mater.2000,48,4571.).The polyol method is a kind of very sophisticated method (P.Toneguzzo, G.Viau, O.Acher, F.Fievet-Vincent, F.Fievet, Adv.Mater.1998,10,1032 of preparation metallic oxide nanocrystal; C.Feldmann, H.O.Jungk, Angew.Chem.Int.Ed.2001,40,359; Angew.Chem.2001,113,372.), have many advantages, low as temperature of reaction, crystalline structure easy to control, the nanocrystalline colloid of generation can be regulated and control its solvability by the change condition.
Summary of the invention
The object of the present invention is to provide a kind of mineral dye water-sol, comprise α-Fe
2O
3(redness) and ZnCo
2O
4(green), solid content can reach 20-30%, and the inorganic nano pigment water-sol of the present invention can be stablized in water more than two weeks at least.
Another object of the present invention is to provide a kind of method for preparing the inorganic nano pigment water-sol.
Preparation method provided by the invention, its key step is:
The more volatile ferrous salt of acid after the hydrolysis such as iron protochloride, ferrous acetate or Ferrox is joined in the multiethylene-glycol (as glycol ether, triglycol, Tetraglycol 99, Macrogol 200-400), and ratio is that every 100ml multiethylene-glycol adds the above-mentioned ferrous salt of 3-10 gram; Being heated to 180-300 ℃ and the ferrous salt that is stirred to adding dissolves fully, treat to add water after the solution becomes clarification, the add-on of water is that every 100ml multiethylene-glycol adds 4-10ml water, react and obtain red solid suspension after 12-20 hour, be chilled to room temperature, with this suspension centrifugation, use washing with alcohol, obtained α-Fe down in dry 1-4 hour at 50-80 ℃
2O
3Powder, productive rate 85%.
With α-Fe
2O
3Powder is redistributed and promptly obtain the red inorganic nano dyestuff colloidal sol that solid content can reach 20-30% in water, and its stability can reach more than two weeks.With α-Fe
2O
3Powder is dispersed in the water miscible alcohol (as ethanol, ethylene glycol etc.), and the gained colloid is more stable, and solid content is higher.
At preparation α-Fe
2O
3On the basis of powder, add Zn (CH again
3COO)
2And Co (CH
3COO)
2Can prepare green ZnCo
2O
4Powder, concrete steps are:
Add 1-3 gram Zn (CH by every 100ml multiethylene-glycol
3COO)
2With 2-6 gram Co (CH
3COO)
2Ratio add Zn (CH
3COO)
2With 2-6 gram Co (CH
3COO)
2, then according to preparation α-Fe
2O
3The step of powder is carried out.
With ZnCo
2O
4Powder is redistributed and is promptly obtained solid content can reach 20% green inorganic nano dyestuff colloidal sol in water, and its stability can reach more than two weeks.With ZnCo
2O
4Powder is dispersed in the water miscible alcohol (as ethanol, ethylene glycol etc.), and the gained colloid is more stable, and solid content is higher.
The mineral dye water-sol provided by the invention can be widely used in fields such as the plastics, film of ink, coating, pottery, air brushing, paint, UV stable.
Description of drawings
Fig. 1 is α-Fe
2O
3Sem photograph.
Fig. 2 is ZnCo
2O
4Sem photograph.
Embodiment
Will be in following examples to concrete synthetic being described of each pigment of the present invention.
Embodiment one, α-Fe
2O
3The preparation method of (redness):
In two mouthfuls of flasks of 500mL, add FeCl
27H
2(2.53g 10mmol) in the triglycol of 200mL, is heated to 240 ℃ and vigorous stirring rapidly to O.Work as FeCl
2Dissolving back solution becomes clarification fully drips 10mL water to reaction flask from the prolong upper end.React and obtain red solid suspension after 12 hours, be chilled to room temperature,,, obtained powder, productive rate 85% down in dry 2 hours at 80 ℃ with washing with alcohol twice with this suspension centrifugation.
Scanning electron microscope (SEM) test result such as Fig. 1 ask, gained α-Fe
2O
3Particle dia is 30-70nm, and size distribution is narrower, and mean diameter is about 50nm.The SEM specimen preparation is as follows: with 1mg α-Fe
2O
3Sample dispersion is got one after another drop ofly on slide glass in 5mL secondary water then, is bonded on the sample table with conductive resin behind the metal spraying and tests.
With α-Fe
2O
3Powder is added to the water by required part by weight (＜30%), promptly can obtain to stablize more than two weeks in ultrasonic agitation 0.5-1 hour, and solid content can reach the water-sol of 20-30% (weight ratio).
With α-Fe
2O
3Powder joins in the water miscible alcohol by required part by weight (＜30%), as ethanol, ethylene glycol or multiethylene-glycol (glycol ether, triglycol, Tetraglycol 99, Macrogol 200-400), can obtain longer colloid steady time in ultrasonic agitation 0.5-1 hour, its solid content can reach 30%.
Embodiment two, ZnCo
2O
4The preparation method of the water-sol of (green):
Zn (CH
3COO)
22H
2O (2.1g, 9.4mmol) and Co (CH
3COO)
24H
2(4.18g 16.8mmol) in two mouthfuls of flasks of 500mL, adds FeCl to O
27H
2(2.53g 10mmol) in the triglycol of 200mL, is heated to 180 ℃ and vigorous stirring to O.Solution becomes clarification (about 2 hours) after these two kinds of salt dissolve fully, drip 2mL water to reaction flask from the prolong upper end, continued heated and stirred 4 hours, obtain green solid suspension after getting final product, be chilled to room temperature,, use twice of washing with alcohol this suspension centrifugation, obtained powder, productive rate 85% down in dry 2 hours at 80 ℃.If this powder is redistributed in water, then can obtain to stablize more than two weeks, solid content can reach 20% the water-sol.If be dispersed in the embodiment 1 described water miscible alcohol, the gained colloid is more stable, and solid content is higher.Sem test result (as Fig. 2) shows, gained ZnCo
2O
4Particle dia is 15-50nm, and size distribution is narrower, average out to 35nm, and formed larger-diameter nanometer ball by self-assembly, diameter is 200-400nm.The SEM specimen preparation is as follows: with 1mg ZnCo
2O
4Sample dispersion is got one after another drop ofly on slide glass in 5mL secondary water then, is bonded on the sample table with conductive resin behind the metal spraying and tests.
Claims (10)
1. mineral dye water-sol, color are red and green; Wherein, the red pigment water-sol contains α-Fe of 20-30%
2O
3Solid substance, the green water-sol contains the ZnCo of 20-30%
2O
4Solid substance.
2. one kind prepares the method for the mineral dye water-sol according to claim 1, and its key step is:
The first step: iron protochloride, ferrous acetate or Ferrox are joined in the multiethylene-glycol, and ratio is the above-mentioned ferrous salt that every 100ml multiethylene-glycol adds the 3-10 gram;
Second step: be heated to 180-300 ℃ and the ferrous salt that is stirred to adding and dissolve fully;
The 3rd step: treat to add water after the solution becomes clarification, the add-on of water is that every 100ml multiethylene-glycol adds 4-10ml water, reacts to obtain red solid suspension after 12-20 hour, is chilled to room temperature;
The 4th step: with this suspension centrifugation, use washing with alcohol, obtained α-Fe down in dry 1-4 hour at 50-80 ℃
2O
3Powder;
The 5th step: with α-Fe
2O
3Powder is redistributed and promptly obtain red inorganic nano dyestuff colloidal sol in water.
3. preparation method as claimed in claim 2 is characterized in that, is with α-Fe in the 5th step
2O
3Powder is dispersed in the water miscible alcohol.
4. preparation method as claimed in claim 3 is characterized in that, described water-soluble alcohol is ethanol, ethylene glycol or multiethylene-glycol.
5. as claim 2 or 4 described preparation methods, it is characterized in that described multiethylene-glycol is that glycol ether, triglycol, Tetraglycol 99 are or/and Macrogol 200-400.
6. one kind prepares the method for the mineral dye water-sol according to claim 1, and its key step is:
The first step: add 1-3 gram Zn (CH by every 100ml multiethylene-glycol
3COO)
2, 2-6 gram Co (CH
3COO)
2With the ratio of 3-10 gram iron protochloride, ferrous acetate or Ferrox, with Zn (CH
3COO)
2, Co (CH
3COO)
2Join in the multiethylene-glycol with above-mentioned ferrous salt;
Second step: be heated to 180-300 ℃ and be stirred to above-mentioned salt and dissolve fully;
The 3rd step: treat to add water after the solution becomes clarification, the add-on of water is that every 100ml multiethylene-glycol adds 4-10ml water, reacts to obtain red solid suspension after 4-20 hour, is chilled to room temperature;
The 4th step: with this suspension centrifugation, use washing with alcohol, obtained ZnCo down in dry 1-4 hour at 50-80 ℃
2O
4
The 5th step: with ZnCo
2O
4Powder is redistributed and promptly obtain green inorganic nano dyestuff colloidal sol in water.
7. preparation method as claimed in claim 6 is characterized in that, is with ZnCo in the 5th step
2O
4Powder is dispersed in the water miscible alcohol.
8. preparation method as claimed in claim 6 is characterized in that, described water-soluble alcohol is ethanol, ethylene glycol or multiethylene-glycol.
9. as claim 6 or 8 described preparation methods, it is characterized in that described multiethylene-glycol is that glycol ether, triglycol, Tetraglycol 99 are or/and Macrogol 200-400.
According to claim 1 the mineral dye water-sol in the plastics of ink, coating, pottery, air brushing, paint, UV stable, the application aspect the film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410001432 CN1640947A (en) | 2004-01-08 | 2004-01-08 | Inorganic pigment hydrosol and its preparation method and use |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410001432 CN1640947A (en) | 2004-01-08 | 2004-01-08 | Inorganic pigment hydrosol and its preparation method and use |
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| Publication Number | Publication Date |
|---|---|
| CN1640947A true CN1640947A (en) | 2005-07-20 |
Family
ID=34867117
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|---|---|---|---|
| CN 200410001432 Pending CN1640947A (en) | 2004-01-08 | 2004-01-08 | Inorganic pigment hydrosol and its preparation method and use |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103788716A (en) * | 2014-02-12 | 2014-05-14 | 铜陵瑞莱科技有限公司 | Iron oxide red pigment containing madder extract |
| CN105175014A (en) * | 2015-09-18 | 2015-12-23 | 洛阳师范学院 | Preparation method of cobalt-zinc green nano ceramic pigment |
-
2004
- 2004-01-08 CN CN 200410001432 patent/CN1640947A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103788716A (en) * | 2014-02-12 | 2014-05-14 | 铜陵瑞莱科技有限公司 | Iron oxide red pigment containing madder extract |
| CN105175014A (en) * | 2015-09-18 | 2015-12-23 | 洛阳师范学院 | Preparation method of cobalt-zinc green nano ceramic pigment |
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