CN1880387A - Organic inorganic laminated-column type pigment synthesis method - Google Patents
Organic inorganic laminated-column type pigment synthesis method Download PDFInfo
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- CN1880387A CN1880387A CN 200510130686 CN200510130686A CN1880387A CN 1880387 A CN1880387 A CN 1880387A CN 200510130686 CN200510130686 CN 200510130686 CN 200510130686 A CN200510130686 A CN 200510130686A CN 1880387 A CN1880387 A CN 1880387A
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- montmorillonite
- saponite
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Abstract
This invention relates to a method for synthesizing a organic and inorganic layer column red dye, comprising: the inorganic raw material selects bowlingite or montmorillonite, pillaring solution selects aluminium sol to gel or tridepolyhydroxy aluminium solution, the organic raw material selects lacmus; first fully swell the bowlingite or montmorillonite with water, then add in aluminium sol to gel or tridepolyhydroxy aluminium solution to pillar bowlingite or montmorillonite, the mixing solution is stirred at 50-80Deg C for 0.5-1.5h, and then processed by washing, filtrating and drying. The dried solid is burned at 350-500Deg C for 2-5h to produce pillared white solid of bowlingite or montmorillonite; add in lacmus solution to soak the white solid powder ,for 1-10h, and then it is processed by washing, filtrating and drying to produce the red solid compound. This red dye is characterized of non-toxicity, stable properties, solarization and rinsing resistance, and large specific surface area, and can be used in fields like ornament, printing ink and paper filler.
Description
Technical field
The invention belongs to a kind of synthetic method of organic-inorganic layer column type red pigment.
Background technology
Red pigment is the important member in the pigment family, is widely used in fields such as printing ink, plastics additive, weaving, makeup.Common red pigment has two big classes at present, and a class is organic red pigment, and another kind of is inorganic red pigment.Organic red pigment mainly contains toluidine red, red etc., and the pigment dyestuff advantage is bright in colour, but poor stability, easily aging, light fugitive is shone, not anti-scrubbing; Inorganic red pigment is common red iron oxide, red lead, cadmium red etc., and the mineral dye advantage is a good stability, but color is bright-coloured not as pigment dyestuff.
United States Patent (USP) United State patent 6,648,959 discloses a kind of method of utilizing clay and organic dye to come synthesis of solid pigment.The organic dye molecule that this method is selected comprises acridine, anthraquinone, azo dyes, indigoide colors, naphthoamide, benzoquinones, nitro-dye, phthalocyanine pigment, and the inorganic raw material of selection is cationic clay mineral and anionic water talcum mineral.Clay or hydrotalcite are reacted in solution with different organic dye molecule respectively, because the laminate of clay or hydrotalcite mineral has negative charge or positive charge, therefore organic dye molecule positively charged or negative charge can embed the interlayer structure of clay or hydrotalcite by ion exchange reaction, cause the interlamellar spacing of clay or hydrotalcite to become big, the embedding of organic dye molecule simultaneously also causes clay or hydrotalcite to produce corresponding color.
In existing document and patent, the method that with the layered clay mineral is the raw material synthetic dyestuff all is based on the interlayer that ion exchange reaction is imbedded coloured organism clay, the organism of interlayer plays a supportive role to the inorganic laminate of layered silicate, exist electrostatic interaction between laminate and the organism simultaneously, any variation that component took place of interlayer all can have influence on the interlamellar spacing and the adsorption space of compound in this case, cause the layered inorganic clay mineral that the adsorptive capacity of organic dye is easily changed, finally have influence on the colourity and the stability of pigment.
Summary of the invention
The synthetic method that the purpose of this invention is to provide a kind of organic-inorganic layer column type red pigment.
Saponite and montmorillonite all are inorganic laminated clay minerals, mainly siliceous, aluminium, magnesium and four kinds of elements of oxygen.In the saponite tetrahedrallayer, part tetravalence Siliciumatom is replaced by the trivalent aluminium atom, causes laminate electronegative; And in the montmorillonite octahedral layer, the trivalent aluminium of hexa-coordinate has caused laminate electronegative.On saponite and the montmorillonite laminate with negative charge by interlayer cation such as Na
+, K
+, Ca
2+Or its hydrated ion isoequilibrium, these positively charged ions can be by other cationic exchange, so saponite and montmorillonite all have good ion-exchange capacity.The present invention is incorporated into aluminium colloidal sol or ten trimerization oxyaluminum in saponite or the montmorillonite layer earlier by ion exchange and serves as pillar, again through calcining, obtain the pillared saponite or the pillared montmorillonite body material of stable in properties, with reindeer moss and body material reaction, obtain a layer column type red pigment then.
Inorganic raw material of the present invention is selected saponite or montmorillonite, and the molecular formula of saponite is M
x(Si
8-xAl
x) Mg
6O
20(OH)
4, wherein M is a metallic cation, x=0.2～2, and the molecular formula of montmorillonite is M
xSi
8(A1
4-xMg
x) O
20(OH)
4, wherein M is a metallic cation, x=0.2～1.8; Select aluminium colloidal sol or ten trimerization oxyaluminum solution to come pillared above-mentioned saponite and montmorillonite, the molecular formula of aluminium colloidal sol is Al
x(OH)
y, x=2～8, y=1～15, ten trimerization oxyaluminum molecular formula are AlO
4Al
12(OH)
24(H
2O)
7+ 12The organic raw material of selecting is a reindeer moss;
The synthesis step of red pigment is as follows:
Getting saponite or smectite clay mineral is soaked in water and made the abundant swelling of clay in 1～10 hour, the proportioning of clay and water is that per 10 gram clays add 100～500 ml waters, adding ten trimerization oxyaluminum or aluminium colloidal sol are made pillared solution in the good clay suspension liquid of swelling, the proportioning of clay and pillared solution is that per 10 gram clays add and contain the aluminum ions pillared solution of 30～70 mmoles, mixed solution stirred 0.5～1.5 hour down at 50～80 ℃, wash then, filter, drying, calcined 2～5 hours down at 350～500 ℃ again, obtain pillared saponite or pillared montmorillonite white solid; Get above-mentioned white solid and grind into 80～350 purpose powder, add reindeer moss solution again, the proportioning of white solid and reindeer moss is that to add 100～600 milliliters weight percent be 1～5% reindeer moss solution to per 10 gram clays, soaked 1～10 hour, wash then, filter, drying, obtain the red solid compound.
The red solid compound that the present invention obtains is an a kind of layer of column type compound, and this pigment supports laminate by metal oxide as pillar, and stronger structural stability is arranged, and it is also more stable to organic adsorptive capacity.The interlamellar spacing of this compound and adsorption space are by the height decision of metal oxide pillar, and its big I reaches 0.6～1.0 nanometer, and therefore layer column type compound has the duct similar with molecular sieve.Saponite that metal oxide is pillared or montmorillonite are compared with saponite or montmorillonite raw material, and adsorption space and specific surface area increase greatly, therefore, in as pigment, also are a kind of good solid adsorbent by the prepared material of the present invention.In addition, the component of saponite and montmorillonite is silicon, oxygen, aluminium and magnesium, and these elements do not constitute harm to human body, so saponite and montmorillonite are safe to human body, the present invention selects harmless reindeer moss as organic raw material, so environmentally safe in the production process.
Synthetic pigment of the present invention is bright red, and illumination 20 hours or wash with water after 20 times, color remains unchanged, placed 6 months under the room temperature, the color no change is after skin contact, do not speckle with any color on the skin, illustrate that reindeer moss and layer clay bonded are very firm.Its reason is, be subjected to the influence of pillared saponite and montmorillonite tart, reindeer moss becomes cationic, the concurrent colour response that changes, because reindeer moss is positively charged, can closely combine by electrostatic interaction with electronegative inorganic laminate, make it be strapped in pillared saponite or pillared montmorillonite interlayer securely, be difficult for discharging.In addition, the reindeer moss of interlayer is subjected to the protection of inorganic laminate, and character is very stable, and is not easy to change under the illumination.For confirming the acidity of organic-inorganic layer column type pigment, designed the contrast experiment, when only adsorbing reindeer moss with saponite or montmorillonite raw material, the compound that obtains only is lurid, and layer column type pigment is wine-colored, layer column type pigment adsorption space and specific surface area that this explanation the present invention obtains are big, adsorbed more dye molecule, moreover, come out in the pillared more acid of the laminate material position that makes, improved sour amount and strength of acid, thereby caused that the reindeer moss that is adsorbed in pillared saponite and the pillared montmorillonite presents redness.
Description of drawings
Accompanying drawing 1 is the X-ray powder diffraction spectrogram of embodiment 4 synthetic pigment, and a represents the saponite raw material among the figure, and b represents organic-inorganic layer column type pigment.
From accompanying drawing 1 as seen, first diffraction peak of saponite raw material is 7.3 °, and corresponding compound layer spacing is 12.1 , and first diffraction peak of layer column type pigment is 4.9 °, and corresponding interlamellar spacing is 18.7 .Obviously, compare with raw material, the interlamellar spacing of layer column type pigment has increased 7 , and the adsorption space and the specific surface area of this explanation pigment are bigger than saponite raw material.N
2The specific surface area of adsorption experiment data presentation saponite raw material is 35m
2/ g, and the specific surface area of layer column type pigment is 170m
2/ g, this explanation layer column type pigment specific surface area is big, and stronger adsorptive power is arranged.
Accompanying drawing 2 is thermogravimetric-differential thermal curve spectrograms of embodiment 4 synthetic pigment, and a represents the thermogravimetric curve of red pigment among the figure, and b represents differential scanning calorimetric analysis curve.
As can be seen from Fig. 2, when temperature is heated to more than 200 ℃, just have bigger weightlessness, this illustrate under the provide protection of inorganic laminate, the organism energy stable existence to 200 in the pigment ℃.When temperature was heated to 600 ℃, organism just full scale clearance fell, and organic content can reach 30% of gross weight in this explanation pigment.
Embodiment
Embodiment 1:
Getting 10 gram saponites soaked 1 hour with 100 ml waters, make its abundant swelling, in the good clay suspension liquid of swelling, add and contain the aluminum ions ten trimerization hydroxyl-aluminum pillared solution of 30 mmoles, stirred 0.5 hour down at 50 ℃, wash then, filter, drying, calcined 2 hours down at 350 ℃ again, obtain white solid.Get 5 gram white solids, it is ground into 80～350 purpose powder, add 50 milliliters of weight percents again and be 1% reindeer moss solution, soaks 5 hours after scouring, filtration, drying, the acquisition red compound.
Embodiment 2:
Getting 10 gram saponites soaked 6 hours with 200 ml waters, make its abundant swelling, in the good clay suspension liquid of swelling, add and contain the aluminum ions ten trimerization hydroxyl-aluminum pillared solution of 40 mmoles, stirred 1 hour down at 60 ℃, wash then, filter, drying, calcined 2 hours down at 400 ℃ again, obtain white solid.Get 5 gram white solids, it is ground into 80～350 purpose powder, add 100 milliliters of weight percents again and be 3% reindeer moss solution, soaks 5 hours after scouring, filtration, drying, the acquisition red compound.
Embodiment 3:
Getting 10 gram saponites soaked 8 hours with 350 ml waters, make its abundant swelling, in the good clay suspension liquid of swelling, add and contain the aluminum ions ten trimerization hydroxyl-aluminum pillared solution of 60 mmoles, stirred 1 hour down at 70 ℃, wash then, filter, drying, calcined 2 hours down at 450 ℃ again, obtain white solid.Get 5 gram white solids and grind into 80～350 purpose powder, add 300 milliliters of weight percents again and be 5% reindeer moss solution, soaks 5 hours after scouring, filtration, drying, the acquisition red compound.
Embodiment 4:
Getting 10 gram saponites soaked 10 hours with 500 ml waters, make its abundant swelling, in the good clay suspension liquid of swelling, add and contain the aluminum ions ten trimerization hydroxyl-aluminum pillared solution of 70 mmoles, stirred 1.5 hours down at 80 ℃, wash then, filter, drying, 500 ℃ of calcinings 2 hours down, obtain white solid again.Get 5 gram white solids, it is ground into 80～350 purpose powder, add 300 milliliters of weight percents again and be 5% reindeer moss solution, soaks 10 hours after scouring, filtration, drying, the acquisition red compound.
Embodiment 5:
Getting 10 gram smectite clay minerals soaked 8 hours with 350 ml waters, make its abundant swelling, in the good clay suspension liquid of swelling, add and contain the formulated solution of the aluminum ions aluminium colloidal sol of 65 mmoles, stirred 1 hour down at 65 ℃, wash then, filter, drying, 450 ℃ of calcinings 5 hours down, obtain white solid again.Get 5 gram white solids, it is ground into 80～350 purpose powder, add 300 milliliters of weight percents again and be 5% reindeer moss solution, soaks 1 hour after scouring, filtration, drying, the acquisition red compound.
Claims (1)
1. the synthetic method of an organic-inorganic layer column type red pigment, inorganic raw material is selected saponite or montmorillonite, and the molecular formula of saponite is M
x(Si
8-xAl
x) Mg
6O
20(OH)
4, wherein M is a metallic cation, x=0.2～2, and the molecular formula of montmorillonite is M
xSi
8(Al
4-xMg
x) O
20(OH)
4, M is a metallic cation, x=0.2～1.8; Select aluminium colloidal sol or ten trimerization oxyaluminum solution to come pillared saponite or montmorillonite, aluminium colloidal sol molecular formula is Al
x(OH)
y, x=2～8, y=1～15, ten trimerization oxyaluminum molecular formula are AlO
4Al
12(OH)
24(H
2O)
7+ 12, the organic raw material of selection is a reindeer moss;
Synthesis step is as follows:
Getting saponite or smectite clay mineral was soaked in water 1～10 hour, make the abundant swelling of clay, the proportioning of clay and water is that per 10 gram clays add 100～500 ml waters, adding ten trimerization oxyaluminum or aluminium colloidal sol are made pillared solution in the good clay suspension liquid of swelling, clay and the proportioning of pillared solution are per 10 gram clays and contain the aluminum ions pillared solution of 30～70 mmoles and mix, mixed solution stirred 0.5～1.5 hour down at 50～80 ℃, washing then, filter, dry, calcined 2～5 hours down at 350～500 ℃ again, obtain the pillared good saponite or the white solid of montmorillonite; The extracting waste solid grinds into 80～350 purpose powder, add reindeer moss solution again, the proportioning of white solid and reindeer moss be every 10g clay to add 100～600 milliliters weight percent be 1～5% reindeer moss solution, soaked 1～10 hour, wash then, filter, drying, obtain the red solid compound.
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|---|---|---|---|
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| CN1880387A true CN1880387A (en) | 2006-12-20 |
| CN100436550C CN100436550C (en) | 2008-11-26 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104861741A (en) * | 2015-03-27 | 2015-08-26 | 浙江树人大学 | Brown porous inorganic solid pigment synthesis method |
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| JPS62258329A (en) * | 1986-04-30 | 1987-11-10 | Ishihara Sangyo Kaisha Ltd | Isomerization of halogenated benzene compound |
| US5616635A (en) * | 1995-11-27 | 1997-04-01 | The Goodyear Tire & Rubber Company | Aqueous multicolor paint |
| US7052541B2 (en) * | 2002-06-19 | 2006-05-30 | Board Of Regents, The University Of Texas System | Color compositions |
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| CN104861741A (en) * | 2015-03-27 | 2015-08-26 | 浙江树人大学 | Brown porous inorganic solid pigment synthesis method |
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