CN106006687B - A kind of bouquet layered double hydroxide and application thereof - Google Patents
A kind of bouquet layered double hydroxide and application thereof Download PDFInfo
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- CN106006687B CN106006687B CN201610330423.9A CN201610330423A CN106006687B CN 106006687 B CN106006687 B CN 106006687B CN 201610330423 A CN201610330423 A CN 201610330423A CN 106006687 B CN106006687 B CN 106006687B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/78—Compounds containing aluminium and two or more other elements, with the exception of oxygen and hydrogen
- C01F7/784—Layered double hydroxide, e.g. comprising nitrate, sulfate or carbonate ions as intercalating anions
- C01F7/785—Hydrotalcite
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/02—Oxides; Hydroxides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/04—Oxides; Hydroxides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/04—Oxides; Hydroxides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
- C01G9/02—Oxides; Hydroxides
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/20—Two-dimensional structures
- C01P2002/22—Two-dimensional structures layered hydroxide-type, e.g. of the hydrotalcite-type
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
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- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
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Abstract
The invention belongs to technical field of preparation for inorganic material, it is related to a kind of bouquet layered double hydroxide, Preparation method and use, layered double hydroxide piece is prepared using T-shaped or Y type micro passage reactions first, then layered double hydroxide piece and surfactant are reacted, surface modification finally is carried out to reacted layered double hydroxide piece using spray drying, layered double hydroxide is modified into the LDH bouquets that the LDH lamellas with hydrophobic performance are built into, the preparation technology is simple, it is reproducible, cost is low, production environment is friendly, with wide market prospects, in addition unique flower ball-shaped structure makes it have excellent hydrophobic performance, the water resistance of coating can be improved by being especially added in coating.
Description
Technical field
The invention belongs to technical field of preparation for inorganic material, it is related to a kind of bouquet layered double hydroxide, preparation side
Method and purposes, make duplex metal hydroxide nanometer piece be self-assembled into surfactant with hydrophobic performance by spray drying
Bouquet layered double hydroxide, flower ball-shaped layered double hydroxide can improve coating as the filler in coating
Energy.
Background technology
Layered double hydroxide（Also known as houghite, abbreviation LDHs）It is an anionoid type layer structure function material
Expect, its chemical composition formula is：[M2+ 1-x M3+ x(OH)2]x+(An-)x/n·yH2O, wherein M2+、M3+It is to be located on laminate respectively
Divalence, trivalent metal ion, An-Represent interlayer anion, this kind of material makes it due to its unique crystal structure and physicochemical characteristic
Extremely wide application prospect is shown in many fields such as ion exchange, absorption, catalysis, optical material, electricity material.Especially
It is that layered double hydroxide has good hydrophobic surface, existing water-repellent paint can be modified as filler,
Prepare environmentally friendly coating.In Patent No. CN10104194A patents, applicant uses situ synthesis techniques, on surface
The laminated double-metal hydroxide film synthesized on aluminium flake after anodic oxidation has Nano/micron composite construction, in long-chain
Carried out in soap surfactant solution after surface hydrophobicity processing, with superior hydrophobic performance, but for larger size panel
Material is not suitable for.In Patent No. ZL201210556607.9 patents, applicant utilizes layered bi-metal hydrogen prepared by microreactor
Oxide precipitation thing obtains the film with hydrophobic performance with being coated in after hard soap self assembly on matrix, but the method institute
The film of preparation wears no resistance, and is easily come off from matrix；Because LDH patterns are sheet, coating is improved as filler after drying
Hydrophobicity effect is not obvious.Therefore, seek to design that a kind of preparation method is simple, the hydrophobicity of coating can be significantly improved as filler
Layered double hydroxide it is very promising, and prepare with flower ball-shaped LDHs be solve existing issue one kind have
Efficacious prescriptions method.Wang etc. is prepared for spherical MgAl-CO using spray drying process3LDHs,（Ind. Eng. Chem. Res. 2008,
47, 5746-5750）, the distribution of the LDH pieces of gained ball surface is than comparatively dense, and lamellar spacing is about 50-100nm, but it is dredged
Water effect is poor.
The content of the invention
It is an object of the invention to overcome the shortcoming that prior art is present, seek a kind of bouquet and the layer with hydrophobic performance
Shape double-metal hydroxide hybrid and preparation method thereof, solves existing sheet layered double hydroxide wear-resisting as coating
Property is poor, is easily come off from matrix, and existing spherical MgAl-CO3LDHs surfaces lamella is too thick, the problem of hydrophobic effect is poor.
To achieve these goals, bouquet layered double hydroxide of the present invention, using surfactant and
It is spray-dried and surface modification preparation, stratiform is carried out to layered double hydroxide piece prepared by T-shaped or Y shape micro passage reaction
Double-metal hydroxide chemical formula is [M2+ 1-x M3+ x(OH)2]x+(An-)x/n·yH2O, 0.17≤x≤0.35,0≤y≤2, wherein
M2+For bivalent metal ion Mg2+、Co2+、Ni2+、Fe2+、Mn2+Or Zn2+Any one of；M3+For Al3+Or Fe3+；An-For
NO3 -、F-、Br-、Cl-、CO3 2-Or SO4 2-Any one of, the layered double hydroxide piece at interval is stood in surface shape
Into layered double hydroxide bouquet, bouquet diameter dimension be 5-10 μm, layered double hydroxide piece thickness be 10
± 2nm, there is obvious bending, and in petal-shaped, contact angle is in 90-145o, bouquet layered double hydroxide is used as filler system
Standby coating.
The step of preparation process of bouquet layered double hydroxide of the present invention is：
（1）By soluble divalent metal salt M2+ n An- 2With soluble trivalent metal salt M3+ n An- 3Mix and match somebody with somebody with deionized water
Metal ion salt solution in pairs, wherein M2+For bivalent metal ion Mg2+、Co2+、Ni2+、Fe2+、Mn2+Or Zn2+In any one
Kind；M3+For Al3+Or Fe3+；An-For NO3 -、F-、Br-、Cl-、CO3 2-Or SO4 2-Any one of, configuration quality fraction is 3%-
7% weak aqua ammonia or 0.1-0.5mol/l sodium hydroxide solution；
（2）Bimetallic ion salt solution and weak aqua ammonia or sodium hydroxide solution are added to micro passage reaction, it is fully mixed
Close generation coprecipitation reaction and obtain layered double hydroxide sediment [M2+ 1-x M3+ x(OH)2]x+(An-)x/n·yH2O,
0.17≤x≤0.35,0≤y≤2；
（3）By step（2）The layered double hydroxide sediment of preparation is fully washed with deionized water, is then disperseed
In 0.001-0.2mol/l surfactant solution, in 25-80oReacted 0.1-48 hours at a temperature of C, obtain dispersion liquid；
Wherein, the chemical formula of surfactant is Cn-1H2n-1XOO-M+, n=11-22, X represents chemical element C, S, P, M+Represent monovalence gold
Belong to ion K+、Na+；
（4）Pass through the regulation and control step that adds water（2）The solid content of the dispersion liquid of gained is spray drying at 10-30g/L, 190 DEG C
After obtain product bouquet layered double hydroxide.
The present invention compared with prior art, has obtained the bouquet layered bi-metal that surface roughness is higher, hydrophobic performance is good
Hydroxide, with very superior hydrophobic performance, its preparation technology is simple, and reproducible, cost is low, and production environment is friendly,
With wide market prospects；In addition, the LDH bouquets that the LDH lamellas with hydrophobic performance are built into, LDH pieces are stood in ball table
Face, the LDH lamellas on surface are made up of individual layer or few layer class shepardite, are had a certain distance between the lamella of surface, are formed coarse
Surface, unique flower ball-shaped structure be more beneficial for when it is prepared coating as filler play its hydrophobic performance, the painting of preparation
Material has good hydrophobicity and adhesiveness, environment-friendly.
Brief description of the drawings：
Fig. 1 is the SEM photograph that the bouquet layered double hydroxide that the embodiment of the present invention 1 is related to amplifies 3K times.
Fig. 2 is the SEM photograph that the bouquet layered double hydroxide that the embodiment of the present invention 1 is related to amplifies 30K times.
Fig. 3 is the SEM photograph that the bouquet layered double hydroxide that the embodiment of the present invention 1 is related to amplifies 50K times.
Embodiment：
Below by embodiment and the invention will be further described with reference to accompanying drawing.
Embodiment 1：
The bouquet layered double hydroxide preparation method that the present embodiment is related to, concrete technology step is：
（1）, by Zn (NO3)2With Al (NO3)3It is dissolved in 50ml deionized waters and is configured to metal ion total concentration and is
0.1mol/l mixing salt solution, prepares the sodium hydroxide solution that 50ml concentration is 0.1mol/l；
（2）, make mixing salt solution and sodium hydroxide solution be sufficiently mixed and react using micro passage reaction to obtain stratiform
Double-metal hydroxide（LDHs）Sediment, micro passage reaction is T-shaped, and reaction temperature is 30oC；
（3）, by the layered double hydroxide prepared（LDHs）Sediment is fully washed with deionized water, Ran Houfen
It is dispersed in the potassium laurate solution that 20ml concentration is 0.1mol/l, 30oReacted 2 hours under C；
（4）、190oProduct is obtained after being spray-dried under C.
Using Japanese JEOL JSM-6700F field emission scanning electron microscopes（SEM）Its surface pattern is observed, Fig. 1-3 is to implement
The SEM figures of the gained bouquet layered double hydroxide of example 1, as seen from the figure, product is 5-10 μm of spherical, the LDH pieces station on surface
The surface of ball is stood in, in petal-shaped（Fig. 2）, its Fig. 2 is chosen into local further amplification and is clear that LDH pieces have substantially
Curling, the size estimation of piece is 500nm or so, and lamellar spacing is 10nm ± 2nm（Fig. 3）, there is obvious distance between lamella,
Constitute coarse surface.Contact angle using JC2000CD contact angle instruments LDHs face coats hydrophobic to gained and water enters
Row measurement, as the measured value of last contact angle after being averaged after same sample surface measurement five times, prepared by embodiment 1
It is 142 ± 3 that contact angle is surveyed after product tablettingo。
It is that the 11% bouquet layered double hydroxide for preparing embodiment 1 is added to as filler according to mass fraction
In conventional coating, the hydrophobicity of coating improves 36%（Detailed process is shown in embodiment 5）.
Embodiment 2：
The bouquet layered double hydroxide preparation method that the present embodiment is related to, concrete technology step is：
（1）, by MgCO3With Al (NO3)3It is dissolved in 50ml deionized waters and is configured to metal ion total concentration for 0.3mol/
L mixing salt solution；Prepare the sodium hydroxide solution that 50ml concentration is 0.3mol/l；
（2）, make mixing salt solution and sodium hydroxide solution be sufficiently mixed and react using micro passage reaction to obtain stratiform
Double-metal hydroxide（LDHs）Sediment, micro passage reaction is T-shaped, and reaction temperature is room temperature；
（3）, by the layered double hydroxide prepared（LDHs）Sediment is fully washed with deionized water, Ran Houfen
It is dispersed in the sodium laurate that 20ml concentration is 0.1mol/l（C11H21COONa）In solution, 30oReacted 0.5 hour under C；
（4）、190oProduct is obtained after being spray-dried under C.
It is 96 ± 3 that contact angle is surveyed after product tabletting manufactured in the present embodiment o。
It is that the 10% bouquet layered double hydroxide for preparing embodiment 2 is added to as filler according to mass fraction
In conventional coating, the hydrophobicity of coating improves 15%.
Embodiment 3：
Flower ball-shaped that the present embodiment is related to layer double-metal hydroxide preparation method, concrete technology step is：
（1）, by Ni (NO3)2And FeCl3It is dissolved in 50ml deionized waters and is configured to metal ion total concentration for 0.1mol/
L mixing salt solution；Prepare the sodium hydroxide solution that 50ml concentration is 0.1mol/l；
（2）, make mixing salt solution and sodium hydroxide solution be sufficiently mixed and react using micro passage reaction to obtain stratiform
Double-metal hydroxide（LDHs）Sediment, micro passage reaction is T-shaped, and reaction temperature is 40oC；
（3）, by the layered double hydroxide prepared（LDHs）Sediment is fully washed with deionized water, then
It is dispersed in the potassium laurate solution that 20ml concentration is 0.001mol/l；80oReacted 0.1 hour under C；
（4）、190oProduct is obtained after being spray-dried under C.
It is 102 ± 2 that contact angle is surveyed after product tabletting manufactured in the present embodiment o。
It is that the 20% bouquet layered double hydroxide for preparing embodiment 3 is added to as filler according to mass fraction
In conventional coating, the hydrophobicity of coating improves 40%.
Embodiment 4：
The bouquet layered double hydroxide preparation method that the present embodiment is related to, concrete technology step is：
（1）, by Ni (NO3)2And FeCl3It is dissolved in 50ml deionized waters and is configured to metal ion total concentration for 0.1mol/
L mixing salt solution；Prepare 50ml 7% weak aqua ammonia；
（2）, make mixing salt solution and sodium hydroxide solution be sufficiently mixed and react using micro passage reaction to obtain stratiform
Double-metal hydroxide（LDHs）Sediment, micro passage reaction is Y shape, and reaction temperature is 40oC；
（3）, by the layered double hydroxide prepared（LDHs）Sediment is fully washed with deionized water, Ran Houfen
It is dispersed in the C that 20ml concentration is 0.2mol/l12H23In SOOK solution, 25oReacted 48 hours under C；
（4）、190oProduct is obtained after being spray-dried under C.
It is 92 ± 2 that contact angle is surveyed after product tabletting manufactured in the present embodiment o。
It is that the 15% bouquet layered double hydroxide for preparing embodiment 4 is added to as filler according to mass fraction
In conventional coating, the hydrophobicity of coating improves 20%.
Embodiment 5：
The preparation method for the bouquet layered double hydroxide coating that the present embodiment is related to, concrete technology step is：
40 grams of epoxy resin is weighed, 10 grams of organic siliconresin, 20 grams of titanium dioxide is added in agitator tank, using high speed point
Dissipate machine and disperse 1h under the conditions of 1000rpm, then add gained mixing paint vehicle in tapered mill, be ground to granularity less than 10 μm；
Defoamer 0.2g is weighed, levelling agent 0.2g, 10 grams of bouquet layered double hydroxide prepared by embodiment 1 is added after grinding
Paint vehicle in, using high speed dispersor scattered 20min at a high speed at 1500 rpm, obtain coating composition A；Weigh 50 grams of polyamide
With 50 grams of acetone, scattered 1h at a high speed, obtains coating composition B at 1500 rpm.By A：B=8：1 ratio weighs certain mass
Component A and component B, stirs, and sprays on surface treated iron plate, drying at room temperature 12h, and 60oC dries 12h, is applied
Membrane sample, measurement contact angle is 126 ± 2 o, the hydrophobicity raising 36% of coating.
Claims (2)
1. a kind of preparation method of bouquet layered double hydroxide, it is characterised in that step of preparation process is：
（1）By soluble divalent metal salt M2+ n An- 2With soluble trivalent metal salt M3+ n An- 3Mixed with deionized water with pairs
Metal ion salt solution, wherein M2+For bivalent metal ion Mg2+、Co2+、Ni2+、Fe2+、Mn2+Or Zn2+Any one of；M3+
For Al3+Or Fe3+；An-For NO3 -、F-、Br-、Cl-、CO3 2-Or SO4 2-Any one of, configuration quality fraction is dilute for 3%-7%'s
The sodium hydroxide solution of ammoniacal liquor or 0.1-0.5mol/l；
（2）Bimetallic ion salt solution and weak aqua ammonia or sodium hydroxide solution are added to micro passage reaction, hair is sufficiently mixed
Raw coprecipitation reaction obtains layered double hydroxide sediment [M2+ 1-x M3+ x(OH)2]x+(An-)x/n·yH2O, 0.17≤x
≤ 0.35,0≤y≤2；
（3）By step（2）The layered double hydroxide sediment of preparation is fully washed with deionized water, is then dispersed in
In 0.001-0.2mol/l potassium laurate solution, in 25-80oReacted 0.1-48 hours at a temperature of C, obtain dispersion liquid；
（4）Pass through the regulation and control step that adds water（2）The solid content of the dispersion liquid of gained is 10-30g/L, after being spray-dried at 190 DEG C
To product bouquet layered double hydroxide.
2. the preparation method of bouquet layered double hydroxide according to claim 1, it is characterised in that layered
Double-metal hydroxide chemical formula is [M2+ 1-x M3+ x(OH)2]x+(An-)x/n·yH2O, 0.17≤x≤0.35,0≤y≤2, wherein
M2+For bivalent metal ion Mg2+、Co2+、Ni2+、Fe2+、Mn2+Or Zn2+Any one of；M3+For Al3+Or Fe3+；An-For
NO3 -、F-、Br-、Cl-、CO3 2-Or SO4 2-Any one of, the layered double hydroxide piece at interval is stood in surface shape
Into layered double hydroxide bouquet, bouquet diameter dimension be 5-10 μm, layered double hydroxide piece thickness be 10
± 2nm, there is obvious bending, and in petal-shaped, contact angle is in 90-145o, bouquet layered double hydroxide is used as filler system
Standby coating.
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| CN110182833B (en) * | 2019-06-03 | 2021-06-15 | 肇庆学院 | Preparation method of cross-linked hydrotalcite-like compound, water-based paint and preparation method thereof |
| CN110564188B (en) * | 2019-09-11 | 2021-07-30 | 亚士漆(上海)有限公司 | Sand-in-water coating and preparation method and application thereof |
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