CN104817856B - Aqueous aluminum powder pigment, preparation method and purposes - Google Patents
Aqueous aluminum powder pigment, preparation method and purposes Download PDFInfo
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Abstract
The present invention relates to a kind of aqueous aluminum powder pigment, preparation method and purposes, the surface coating layer of the aqueous aluminum powder pigment is silica, and inside is aluminium powder, and tie point is connected with by chemical bond outside surface coating layer, and tie point is connected with polymer；The tie point is 4,4' azos（4 cyanopentanoic acids（3' dimethylchlorosilanes）Propyl ester）, the cyano group of 4 azo isobutyl cyano group 4（Valeric acid（3' dimethylchlorosilanes）Propyl ester）Or azo isobutyl dicyano phenyl（3 ethyl dimethylchlorosilanes）, the polymer obtained by polymerizable monomer by polymerisation；Initiator of the invention and polymer are firmly fixed on silica surface, have good protecting effect to the aluminium powder of its inside, there is good dispersiveness in water paint, ink.
Description
Technical field
The present invention relates to the technical field of surface of metallic pigments, it is specifically related to a kind of aqueous aluminum powder pigment, prepares
Method and purposes.
Background technology
Aluminium powder pigment is one of most common metallic pigments, with the flash of light of its uniqueness, is covered and decorative effects, deep to be designed
The pro-gaze of person.Its consumption is increased rapidly since last century, is even more in recent decades towards high added value, water adaptability direction
Development.Main application field has industrial coating, car paint, decoration, printing-ink, plastic processing etc..
Traditional aluminium powder pigment is solvent-borne type aluminium powder, and comparing organic volatile high is contained with its solvent based product for configuring
Environmental insults are harmful to by thing, and difficult cleaning.With continuing to develop for science and technology, people are to environment-friendly type coating, the need of ink
Ask increasing, water paint, water-based ink are in abroad eruptive growth.The Water-borne modification inevitable requirement aluminium powder of coating, ink
The Water-borne modification of pigment, the technology foreign countries of this respect are walked before China already, are counted according to 2013, the painting in the U.S. more than 65%
Material, ink are aqueous, and the aqueous aluminum powder pigment for compounding therewith is also monopolized by external each major company.
In order that aluminium powder pigment can be in aqueous medium（Weak acid or alkalescent）In use, first need solve problem
It is：Aluminium powder is easily corroded, and with medium reaction, aluminium powder pigment is lost metallic luster, and produces hydrogen, there is blast
It is dangerous；Second need solve problem be：Aluminium powder pigment is difficult to disperse in water-base resin, and the two poor compatibility causes aluminium
Powder pigment is agglomerating, glossiness reduction, is unfavorable for subsequent use.
For first problem, at present both at home and abroad it is main with organic matter absorption, it is polymer overmold, inorganic matter passivation, inorganic
The method of thing cladding keeps apart aluminium powder pigment and aqueous medium, prevents its reaction from producing hydrogen.Organic matter absorption is mainly used
Specific small-molecule substance, surfactant molecule are adsorbed in aluminium powder surface to suppress the corrosion of aluminium powder, and this kind of method is due to absorption
Effect is weaker, it is impossible to completely cut off contact of the aluminium powder pigment with corrosive medium completely, therefore protection of this method to aluminium powder is very limited.
Polymer overmold mainly uses polymerizable monomer in aluminium powder in situ Polymerization, and coated aluminum powder gets up to reach by polymer
To preventing it to be corroded, and the polymer that common in-stiu coating polymerization technique is obtained easily comes off from aluminium powder surface, to aluminium powder
Protection also than relatively limited.Inorganic matter passivation is the method for chemical protection for using earliest, and aluminium powder is processed on its surface with passivator
Passivating film is formed, most common passivator is chromate, but the harm due to hexavalent chromium to environment and human body, Ci Zhongfang
Method is progressively eliminated.Inorganic matter cladding is to be condensed to form clad and protect aluminium powder in aluminium powder surface hydrolysis with predecessor, most main
The inorganic coating thing wanted is amorphous silica, also has patent report with silane coupler hydrolytic condensation to form clad,
And then grafting organic matter carrys out modified aluminium powder pigment.
It is main using adding in compound process dispersant, levelling agent, surfactant or in aluminium for Second Problem
Cladding and the good polymer of matrix resin compatibility in powder modifying process.
Chinese Patent Application No. is that 200610123751.8 patent application discloses a kind of system of coated aluminium powder pigment
Preparation Method, adds polymerizable monomer, initiator in the aluminium powder pigment of coated with silica, and stirring reaction obtains silica
With the aluminium powder pigment of polymer overmold, finally cool down, filter, wash, be dried to obtain product.The selection of initiator is that azo two is different
Butyronitrile, potassium peroxydisulfate or ammonium persulfate, the selection of polymerizable monomer is：Styrene, divinylbenzene, methyl acrylate, first
Base methyl acrylate, butyl methacrylate, acrylic acid, methacrylic acid, maleic anhydride, carbic anhydride.The method
Belong to situ aggregation method, the research and development of the modified aseptic technic in aluminium pigment surface, Chinese corrosion and protection journal, volume 34 the
5 it is interim mention the method, initiator ammonium persulfate is not chemical bonding in the absorption driving force of aluminium surface, be electrostatic attraction,
It is easier to come off.
The content of the invention
The technical problem to be solved in the present invention is to provide a kind of aqueous aluminum powder pigment, preparation method and purposes, described aqueous
The coating of aluminium powder pigment is difficult for drop-off, and the protecting effect to aluminium powder is good.
In order to solve the above technical problems, the present invention provides a kind of aqueous aluminum powder pigment, its surface coating layer is silica,
Inside is aluminium powder, and tie point is connected with by chemical bond outside surface coating layer, and tie point is connected with polymer；The connection
Point is initiator, and initiator is 4,4'- azos（4- cyanopentanoic acids（3'- dimethylchlorosilanes）Propyl ester）, 4- azo isobutyl cyano group
4- cyano group（Valeric acid（3'- dimethylchlorosilanes）Propyl ester）Or azo isobutyl dicyano phenyl（3- ethyl dimethylchlorosilanes）, institute
Polymer is stated to be obtained by polymerisation by polymerizable monomer.
The average thickness of the aqueous aluminum powder pigment is 2700nm.
Infrared spectrum analysis is displayed in 1089cm-1There is absworption peak in place.
Element in aqueous aluminum powder pigment：The part by weight of carbon, oxygen, aluminium, silicon and chlorine is carbon：10%-38%, oxygen：10%-
20%, aluminium：35%-70%, silicon：10%-15%, chlorine：0.5%-3%.
Initiator of the invention is existing product, can be obtained using following reaction scheme：
Preferably, the polymerizable monomer is acrylic acid, methyl acrylate, methyl methacrylate, methacrylic acid
Butyl ester, dimethyl diallyl ammonium chloride, acrylyl oxy-ethyl-trimethyl salmiac, 4- vinyl benzoic acids or 2- vinylpyridines
Pyridine, it is furthermore preferred that the polymerizable monomer be dimethyl diallyl ammonium chloride, acrylyl oxy-ethyl-trimethyl salmiac,
4- vinyl benzoic acids or 2- vinylpyridines.It is acrylic acid, methyl acrylate, methacrylic acid compared to polymerizable monomer
Methyl esters, butyl methacrylate, polymerizable monomer are dimethyl diallyl ammonium chloride, acrylyl oxy-ethyl-trimethyl chlorination
When ammonium, 4- vinyl benzoic acids or 2- vinylpyridines, dispersiveness and uniformity are more excellent in an aqueous medium for the polymer of formation
Different, it is ionized in an aqueous medium, makes surface of the invention electrically charged, is conducive to the dispersion of aluminium powder, it is not easy to is formed and reunited.
Prepare the aluminium powder of the starting silica cladding of aqueous aluminum powder pigment, initiator and have the weight of polymerizable monomer
Proportioning is preferably：1-5:0.01-1:0.5-5.
Infrared spectrum analysis to aqueous aluminum powder pigment shows, in 1089cm-1There is absworption peak in place, shows aqueous aluminum powder face
There is amorphous silica in material.
The present invention also provides a kind of preparation method of aqueous aluminum powder pigment, and step is as follows：
1st, the aluminium powder of overcoating silica and solvent are mixed, adds initiator and accelerator, stirring reaction, reaction is completed
After wash above-mentioned product, be filtrated to get coating modification aluminium powder pigment, the initiator is 4,4'- azos（4- cyanopentanoic acids（3'-
Dimethylchlorosilane）Propyl ester）, 4- azo isobutyl cyano group 4- cyano group（Valeric acid（3'- dimethylchlorosilanes）Propyl ester）Or azo isobutyl
Dicyano phenyl（3- ethyl dimethylchlorosilanes）, the accelerator is alkaline matter；
2nd, above-mentioned coating modification aluminium powder pigment, solvent and polymerisable monomer are mixed, after reaction, filtering, washing, dry
To aqueous aluminum powder pigment.
Preferably, in step 1, before adding initiator, first the mixture of the aluminium powder and solvent to being cladded with silica is carried out
It is passed through nitrogen gas stirring treatment.
In step 1, the material of washed product is preferably alcohols material, most preferably methyl alcohol, ethanol or isopropanol.
In step 1, solvent is preferably nonpolar or low pole solvent, more preferably chloroform, dichloromethane, and override is
Toluene or dimethylbenzene.
Preferably, in step 1, the weight proportion for being cladded with aluminium powder, solvent, initiator and the accelerator of silica is：1-
5:30-60:0.01-1:0.1-5, preferred weight proportion is：1:30:0.1:0.1.
The accelerator is preferably alkalescent material, most preferably triethylamine, ethylenediamine or ammoniacal liquor.Due in initiator
Si-Cl keys and the Si-OH keys reaction generation HCl on cladding aluminium powder surface, so adding accelerator to neutralize the acid of generation, reach rush
Enter the purpose of reaction.
Preferably, in step 2, polymerizable monomer is：Acrylic acid, methyl acrylate, methyl methacrylate, methyl-prop
Olefin(e) acid butyl ester, dimethyl diallyl ammonium chloride, acrylyl oxy-ethyl-trimethyl salmiac, 4- vinyl benzoic acids or 2- ethene
Yl pyridines, more preferably：Dimethyl diallyl ammonium chloride, acrylyl oxy-ethyl-trimethyl salmiac, 4- vinyl benzoic acids
Or 2- vinylpyridines.It is acrylic acid, methyl acrylate, methyl methacrylate, metering system compared to polymerizable monomer
Acid butyl ester, polymerizable monomer is dimethyl diallyl ammonium chloride, acrylyl oxy-ethyl-trimethyl salmiac, 4- vinyl benzenes
When formic acid or 2- vinylpyridines, dispersiveness and uniformity are more excellent in an aqueous medium for the polymer of formation, and it is in aqueous Jie
Ionized in matter, make surface of the invention electrically charged, be conducive to the dispersion of aluminium powder, it is not easy to formed and reunited.
In step 2, deoxygenation operation is carried out first after the mixing of coating modification aluminium powder pigment, solvent and polymerisable monomer, make to gather
Close effect more preferably, the temperature of its reaction is preferably 55-75 DEG C, be more beneficial for making decomposition of initiator produce free radical.
Preferably, in step 2, the weight proportion of the coating modification aluminium powder pigment, solvent and polymerisable monomer is：1-5:
30-60:0.5-5, preferred weight proportion is：1:40:0.5.
Preferably, in step 2, the solvent be methyl alcohol, ethanol, normal propyl alcohol, isopropanol or N,N-Dimethylformamide, more
Preferably N,N-Dimethylformamide.N,N-Dimethylformamide makees the solvent of step 2 compared to alcohols, is more beneficial for system
Dispersion.
The preparation method of the aluminium powder of the overcoating silica be prior art, can use Chinese Patent Application No. for
200610123715.8 method is prepared, it would however also be possible to employ following steps are obtained：
（1）Aluminium powder and cleaning solvent are added in a reservoir, and the aluminium powder is laminar and without the aluminium powder of surface treatment,
Thickness is 5-100um, ultrasonic vibration cleaning, centrifugal filtration removal liquid, the aluminium powder after being washed；
（2）During aluminium powder after washing and solvent alcohol added into reactor, stirring, to adding organosiloxane in reactor,
Water, catalyst, stirring in water bath reaction, filtering is dried after being washed with solvent alcohol, obtains the aluminium powder of overcoating silica.
Preferably, the cleaning solvent is acetone, butanone or cyclohexanone.
Preferably, the step of above-mentioned reaction（1）In, the weight proportion of the aluminium powder and cleaning solvent is 1-5:30-80.
Preferably, the step of above-mentioned reaction（2）In, aluminium powder, solvent alcohol, organosiloxane, water after the washing and urge
The weight proportion of agent is：1-5:30-80:2-10:6-20:1-7.
Preferably, the step of above-mentioned reaction（2）In, the organosiloxane is tetramethoxy-silicane or tetraethoxy-silicane
Alkane, the catalyst is triethylamine, ethylenediamine or ammoniacal liquor, and reaction temperature is 25-40 DEG C, and the reaction time is 8-20 hours.
The present invention also provides a kind of purposes of aqueous aluminum powder pigment in coating or ink is prepared.
The beneficial effects of the invention are as follows with aluminium powder as kernel, silica is surface coating layer to the present invention, will then be triggered
Agent is carried on surface coating layer by chemical bond, and water is formed finally by triggering polymerizable monomer to be grafted to initiator surface
Property aluminium powder pigment.
Aqueous aluminum powder pigment prepared by the present invention can be used directly as aluminium pigment, with excellent storage stabilization
Property, resistance to acids and bases, good dispersiveness.
Initiator is carried on the present invention SiO for having coated aluminium powder2Surface, its process mechanism is the Si-Cl on initiator
Key replaces SiO2The hydrogen atom of surface Si-OH keys forms Si-O-Si keys.
In the original location be polymerized in, initiator be it is free, the monomer in initiation system in aluminium powder surface aggregate, this polymer bag
Coating does not have and forms firm chemical bond with aluminium powder surface, easily comes off in actual use, it is difficult to stabilization is formed to aluminium powder
Protection.In contrast to the method for in-stiu coating polymerization, containing simultaneously in initiator of the present invention can generate freedom to the present invention
The azo bond of base and the Si-Cl keys that can be reacted with Si-OH, initiator and surface coating layer form chemical bond, so polymer
It is firmly to be fixed on aluminium powder surface, difficult for drop-off, polymer and initiator can preferably protect aluminium powder and make product of the present invention
There is good compatibility with water paint or ink, there is more preferable anticorrosion ability in the presence of a harsh environment.
The modified aluminium powder that the present invention is polymerized by unsaturated bond on silane coupler again after being coated in contrast to silane coupler
Preparation method, advantage of the invention is that can regulate and control the grafting density of initiator by adjusting the amount of initiator, and then controls
The grafting density of polymer controls the surface microstructure performance of aluminium powder, and due to the introducing in advance of initiator, Ke Yigeng
Follow-up polymerisation is readily completed, yield is higher.
Aqueous aluminum powder pigment prepared by the present invention employs various polyelectrolyte monomers, therefore the aqueous aluminum powder pigment for preparing
There is good compatibility with water-base resin, there is good dispersiveness in water paint, ink.
Brief description of the drawings
Fig. 1 is microstructure schematic diagram of the invention.
Fig. 2 is the schematic diagram of reactions steps of the invention.
Fig. 3 is the electron microscope of aluminium powder.
Fig. 4 is the electron microscope of aqueous aluminum powder pigment of the invention.
Fig. 5 is the transmission electron microscope picture of aqueous aluminum powder pigment of the invention.
Fig. 6 is the infrared spectrum analysis figure of different material.
Fig. 7 is the constituent content analysis figure of the aluminium powder of overcoating silica.
Fig. 8 is the constituent content analysis figure of coating modification aluminium powder pigment of the invention.
Fig. 9 is the liberation of hydrogen spirogram that different material is changed over time in sodium hydroxide solution.
Figure 10 is the thickness distribution figure of uncoated aluminium powder.
Figure 11 is the thickness distribution figure of the aluminium powder of overcoating silica.
Figure 12 is the thickness distribution figure of aqueous aluminum powder pigment.
In figure, 1 aluminium powder, 2 silica, 3 tie points, 4 polymer.
Specific embodiment
Embodiment 1
The first step：With mass fraction（It is following same）Meter, 1 part and 30 parts toluene of aluminium powder of overcoating silica are added
Enter in reactor, room temperature leads to nitrogen gas stirring, to 0.01 part of 4,4'- azo of addition in reactor（4- cyanopentanoic acids（3'- dimethyl
Chlorosilane）Propyl ester）With 0.1 part of triethylamine, reaction 12 hours is stirred at room temperature, is then washed with ethanol, be filtrated to get coating modification
Aluminium powder pigment.
Second step：By in 1 part, 30 parts methyl alcohol of coating modification aluminium powder pigment and 0.5 part of acrylic acid addition reactor, will react
Device deoxygenation under the conditions of liquid nitrogen, then reacts 3 hours under 60 DEG C of water-baths, filtering, and washing obtains aqueous aluminum powder face after drying
Material.
The corrosion resistance of the aqueous aluminum powder pigment of the present embodiment 1：In the aqueous solution hydrogen-free air elutriation in 6 months of pH8-12 scopes
Go out.
The glossiness of the aqueous aluminum powder pigment of the present embodiment 1：After being made into water paint solidification, surface silver color, uniform in color,
Good luster, without current mark.
The dispersiveness of the aqueous aluminum powder pigment of the present embodiment 1：Aqueous aluminum powder pigment is put into aqueous medium microscope
Observation, soilless sticking is uniformly dispersed.
As shown in figure 1, as can be seen that the present invention is followed successively by aluminium powder 1, dioxy from inside to outside from microstructure of the invention
SiClx 2, tie point 3 and polymer 4, in the present embodiment 1, tie point 3 is 4,4'- azos（4- cyanopentanoic acids（3'- dimethyl
Chlorosilane）Propyl ester）.
Embodiment 2
The first step：In terms of mass fraction, during 1 part and 30 parts toluene of aluminium powder of overcoating silica are added into reactors, room
The logical nitrogen gas stirring of temperature；To 0.02 part of 4,4'- azo of addition in reactor（4- cyanopentanoic acids（3'- dimethylchlorosilanes）Propyl ester）With
0.2 part of triethylamine, is stirred at room temperature reaction 12 hours；Then washed with isopropanol, be filtrated to get coating modification aluminium powder pigment.
Second step：By in 1 part, 30 parts methyl alcohol of coating modification aluminium powder pigment and 1 part of methyl acrylate addition reactor；Will be anti-
Device deoxygenation under the conditions of liquid nitrogen is answered, is then reacted 3 hours under 70 DEG C of water-baths；Filtering, washing, obtains aqueous aluminum powder face after drying
Material.
The corrosion resistance of the aqueous aluminum powder pigment of the present embodiment 2：In the aqueous solution hydrogen-free air elutriation in 6 months of pH8-12 scopes
Go out.
The glossiness of the aqueous aluminum powder pigment of the present embodiment 2：After being made into water paint solidification, surface silver color, uniform in color,
Good luster, without current mark.
The dispersiveness of the aqueous aluminum powder pigment of the present embodiment 2：Aqueous aluminum powder pigment is put into aqueous medium microscope
Observation, soilless sticking is uniformly dispersed.
Embodiment 3
The first step：In terms of mass fraction, during 2 parts and 40 parts toluene of aluminium powder of overcoating silica are added into reactors, room
The logical nitrogen gas stirring of temperature；To 0.05 part of 4,4'- azo of addition in reactor（4- cyanopentanoic acids（3'- dimethylchlorosilanes）Propyl ester）With
0.2 part of triethylamine, is stirred at room temperature reaction 20 hours；Then washed with methyl alcohol, be filtrated to get coating modification aluminium powder pigment.
Second step：By in 2 parts, 40 parts methyl alcohol of coating modification aluminium powder pigment and 1 part of methyl methacrylate addition reactor；
The deoxygenation under the conditions of liquid nitrogen by reactor, then reacts 3 hours under 60 DEG C of water-baths；Filtering, washing, obtains aqueous aluminium after drying
Powder pigment.
The corrosion resistance of the aqueous aluminum powder pigment of the present embodiment 3：In the aqueous solution hydrogen-free air elutriation in 6 months of pH8-12 scopes
Go out.
The glossiness of the aqueous aluminum powder pigment of the present embodiment 3：After being made into water paint solidification, surface silver color, uniform in color,
Good luster, without current mark.
The dispersiveness of the aqueous aluminum powder pigment of the present embodiment 3：Aqueous aluminum powder pigment is put into aqueous medium microscope
Observation, soilless sticking is uniformly dispersed.
Embodiment 4
The first step：In terms of mass fraction, 3 parts of aluminium powder pigments and 60 parts of acetone, ultrasonic vibration cleaning 30 are added in a reservoir
Minute, centrifugal filtration removal liquid, the aluminium powder after being washed.
Second step：3 parts and 80 parts methyl alcohol of aluminium powder after washing are added in reactor, are stirred at room temperature；Added in reactor
10 parts of methyl silicates, 15 parts of water, 4 parts of ethylenediamines, stirring in water bath is reacted 10 hours, and reaction temperature is 40 DEG C；Then filtering, uses
Drying obtains the aluminium powder of overcoating silica after methyl alcohol washing.
3rd step：By in 3 parts and 50 parts toluene addition reactors of aluminium powder of overcoating silica, room temperature leads to nitrogen gas stirring；
To 0.05 part of 4,4'- azo of addition in reactor（4- cyanopentanoic acids（3'- dimethylchlorosilanes）Propyl ester）With 0.5 part of ethylenediamine,
Reaction 24 hours is stirred at room temperature；Then washed with methyl alcohol, be filtrated to get coating modification aluminium powder pigment.
4th step：By 3 parts, 50 parts N,N-Dimethylformamides of coating modification aluminium powder pigment and 2 parts of dimethyl diallyls
Ammonium chloride is added in reactor；The deoxygenation under the conditions of liquid nitrogen by reactor, then reacts 4 hours under 60 DEG C of water-baths；Filtering, washes
Wash, aqueous aluminum powder pigment is obtained after drying.
The corrosion resistance of the aqueous aluminum powder pigment of the present embodiment 4：In the aqueous solution hydrogen-free air elutriation in 6 months of pH8-12 scopes
Go out.
The glossiness of the aqueous aluminum powder pigment of the present embodiment 4：After being made into water paint solidification, surface silver color, uniform in color,
Good luster, without current mark.
The dispersiveness of the aqueous aluminum powder pigment of the present embodiment 4：Aqueous aluminum powder pigment is put into aqueous medium microscope
Observation, soilless sticking is uniformly dispersed.
Embodiment 5
The first step：In terms of mass fraction, 4 parts of aluminium powder pigments and 70 parts of cyclohexanone, ultrasonic vibration cleaning are added in a reservoir
30 minutes, centrifugal filtration removal liquid, the aluminium powder after being washed.
Second step：4 parts and 80 parts isopropanols of aluminium powder after washing are added in reactor, are stirred at room temperature；Add in reactor
Enter 10 parts of tetraethyl orthosilicates, 20 parts of water, 6 parts of triethylamines, stirring in water bath is reacted 18 hours, reaction temperature is 25 DEG C；Then filtering,
Drying obtains the aluminium powder of overcoating silica after being washed with isopropanol.
3rd step：By in 4 parts and 50 parts dimethylbenzene addition reactors of aluminium powder of overcoating silica, the logical nitrogen of room temperature is stirred
Mix；To 0.1 part of 4- azo isobutyl cyano group 4- cyano group of addition in reactor（Valeric acid（3'- dimethylchlorosilanes）Propyl ester）With 0.4 part
Triethylamine, is stirred at room temperature reaction 24 hours；Then washed with isopropanol, be filtrated to get coating modification aluminium powder pigment.
4th step：4 parts, 50 parts methyl alcohol of coating modification aluminium powder pigment and 1 part of acrylyl oxy-ethyl-trimethyl salmiac are added
In entering reactor；The deoxygenation under the conditions of liquid nitrogen by reactor, then reacts 3 hours under 65 DEG C of water-baths；Filtering, washing, drying
After obtain aqueous aluminum powder pigment.
The corrosion resistance of the aqueous aluminum powder pigment of the present embodiment 5：In the aqueous solution hydrogen-free air elutriation in 6 months of pH8-12 scopes
Go out.
The glossiness of the aqueous aluminum powder pigment of the present embodiment 5：After being made into water paint solidification, surface silver color, uniform in color,
Good luster, without current mark.
The dispersiveness of the aqueous aluminum powder pigment of the present embodiment 5：Aqueous aluminum powder pigment is put into aqueous medium microscope
Observation, soilless sticking is uniformly dispersed.
As shown in Fig. 2 polymer is the tie point surface that coating modification aluminium powder pigment is grafted in the form of brush, due to
Initiator is carried on the aluminium powder surface of overcoating silica in advance, and the microstructure for being formed has essence not with in-situ polymerization
Together.
Embodiment 6
The first step：In terms of mass fraction, 5 parts of aluminium powder pigments and 70 parts of cyclohexanone, ultrasonic vibration cleaning are added in a reservoir
30 minutes, centrifugal filtration removal liquid, the aluminium powder after being washed.
Second step：5 parts and 80 parts ethanol of aluminium powder after washing are added in reactor, are stirred at room temperature；Added in reactor
10 parts of tetraethyl orthosilicates, 18 parts of water, 6 parts of triethylamines, stirring in water bath is reacted 9 hours, and reaction temperature is 40 DEG C；Then filtering, uses
Drying obtains the aluminium powder of overcoating silica after ethanol washing.
3rd step：By in 5 parts and 60 parts dimethylbenzene addition reactors of aluminium powder of overcoating silica, the logical nitrogen of room temperature is stirred
Mix；To 0.1 part of 4- azo isobutyl cyano group 4- cyano group of addition in reactor（Valeric acid（3'- dimethylchlorosilanes）Propyl ester）With 0.5 part
Triethylamine, is stirred at room temperature reaction 20 hours；Then washed with isopropanol, be filtrated to get coating modification aluminium powder pigment.
4th step：By in 5 parts, 60 parts methyl alcohol of coating modification aluminium powder pigment and 3 parts of 4- vinyl benzoic acids addition reactors；
The deoxygenation under the conditions of liquid nitrogen by reactor, then reacts 3.5 hours under 60 DEG C of water-baths；Filtering, washing, obtains aqueous after drying
Aluminium powder pigment.
The corrosion resistance of the aqueous aluminum powder pigment of the present embodiment 6：In the aqueous solution hydrogen-free air elutriation in 6 months of pH8-12 scopes
Go out.
The glossiness of the aqueous aluminum powder pigment of the present embodiment 6：After being made into water paint solidification, surface silver color, uniform in color,
Good luster, without current mark.
The dispersiveness of the aqueous aluminum powder pigment of the present embodiment 6：Aqueous aluminum powder pigment is put into aqueous medium microscope
Observation, soilless sticking is uniformly dispersed.
Embodiment 7
The first step：In terms of mass fraction, 5 parts of aluminium powder pigments and 80 parts of cyclohexanone, ultrasonic vibration cleaning are added in a reservoir
30 minutes, centrifugal filtration removal liquid, the aluminium powder after being washed.
Second step：5 parts and 80 parts methyl alcohol of aluminium powder after washing are added in reactor, are stirred at room temperature；To adding 8 in reactor
Part tetraethyl orthosilicate, 15 parts of water, 5 parts of triethylamines, stirring in water bath is reacted 15 hours, and reaction temperature is 30 DEG C；Then filtering, uses first
Drying obtains the aluminium powder of overcoating silica after alcohol washing.
3rd step：By in 5 parts and 60 parts dimethylbenzene addition reactors of aluminium powder of overcoating silica, the logical nitrogen of room temperature is stirred
Mix；To 0.08 part of azo isobutyl dicyano phenyl of addition in reactor（3- ethyl dimethylchlorosilanes）With 0.4 part of triethylamine, room
Warm stirring reaction 24 hours；Then washed with isopropanol, be filtrated to get coating modification aluminium powder pigment.
4th step：By in 5 parts, 50 parts methyl alcohol of coating modification aluminium powder pigment and 4 parts of 2- vinylpyridines addition reactors；Will
Reactor deoxygenation under the conditions of liquid nitrogen, then reacts 4 hours under 60 DEG C of water-baths；Filtering, washing, obtains aqueous aluminum powder after drying
Pigment.
The corrosion resistance of the aqueous aluminum powder pigment of the present embodiment 7：In the aqueous solution hydrogen-free air elutriation in 6 months of pH8-12 scopes
Go out.
The glossiness of the aqueous aluminum powder pigment of the present embodiment 7：After being made into water paint solidification, surface silver color, uniform in color,
Good luster, without current mark.
The dispersiveness of the aqueous aluminum powder pigment of the present embodiment 7：Aqueous aluminum powder pigment is put into aqueous medium microscope
Observation, soilless sticking is uniformly dispersed.
As shown in Fig. 3,4 and 5, by the electron microscope of comparative analysis aluminium powder（Fig. 3）, observe aqueous aluminum powder pigment of the invention
Electron microscope and transmission electron microscope picture know, the present invention be successfully grafted polymer.
As shown in fig. 6,（a）It is aluminium powder, (b) is coated with silica aluminium powder, and (c) is aqueous aluminum powder pigment of the invention.
（b）In, it will be apparent that occur in that 1086cm-1Si-O-Si absworption peaks, it can be determined that amorphous silica is in aluminium powder surface shape
Into.（c）In, except there is 1089cm-1The absworption peak at place, have also appeared the 1724cm of carbonyl peak C=O in polymer-1The suction at place
Peak is received, i.e. the product of embodiment 2,3 and 6 occurs 1724cm-1Absworption peak.
As Figure 7-8, constituent content analysis figure of the invention knows the content of each composition, be calculated silica and
The content of polymer.
Embodiment 8
By aluminium powder（It is unmodified）, overcoating silica aluminium powder, aqueous aluminum powder pigment of the invention, acrylic acid reaction in-situ
The cladding aluminium powder after the acrylic acid reaction in-situ after cladding aluminium powder, ultrasonic vibration afterwards invades sodium hydroxide solution of the bubble in pH12
In, measure the amounts of hydrogen for separating out.
Fig. 9 is aluminium powder（It is unmodified）, the aluminium powder of overcoating silica, aqueous aluminum powder pigment of the invention, acrylic acid it is in situ
The cladding aluminium powder after acrylic acid reaction in-situ after reacted cladding aluminium powder, ultrasonic vibration is in the sodium hydroxide solution of pH12
The amounts of hydrogen for being separated out over time.After the aluminium powder of overcoating silica and aqueous aluminum powder pigment earthquake of the invention not
Occurring obvious hydrogen-separating quantity increases, and carries out test after cladding aluminium powder earthquake after acrylic acid reaction in-situ and find that cladding is protected
Shield effect reduction.
Embodiment 9
Glossiness contrast test
Using by uncoated SiO2Aluminium powder, aluminium powder, acrylic acid in-stiu coating aluminium powder, this patent system of overcoating silica
Standby aqueous aluminum powder pigment is made into coating by common scale and resin, solvent, is sprayed on ptfe plastic base plate, after drying
The glossiness of its film is determined, as a result as shown in table 1.
The glossiness contrast test result table of table 1
| Aluminium powder pigment | Glossiness |
| Uncoated aluminium powder | 69.6 |
| The aluminium powder of overcoating silica（Embodiment 4） | 45.7 |
| The aluminium powder of overcoating silica（Embodiment 5） | 44.5 |
| The aluminium powder of overcoating silica（Embodiment 6） | 52.3 |
| Acrylic acid in-stiu coating aluminium powder #1 | 56.8 |
| Acrylic acid in-stiu coating aluminium powder #2 | 62 |
| Acrylic acid in-stiu coating aluminium powder #3 | 61.5 |
| Aqueous aluminum powder pigment（Embodiment 4） | 67.5 |
| Aqueous aluminum powder pigment（Embodiment 5） | 66.8 |
Acrylic acid in-stiu coating aluminium powder in this experiment is obtained using acrylic acid in-stiu coating.Compared to uncoated aluminium
Powder, the glossiness of the aluminium powder of overcoating silica averagely declines 31.75%；The glossiness of acrylic acid in-stiu coating aluminium powder averagely under
Drop 13.65%；The glossiness of aqueous aluminum powder pigment averagely only declines 3.5%, has a significant effect.
Embodiment 10
Thickness measuring
The uncoated aluminium powder of equivalent, the aluminium powder of overcoating silica, aqueous aluminum powder pigment are scattered in absolute ethyl alcohol, are moved
State light scattering method characterizes its thickness（BT-90, Chinese Dandong Bai Te）.Result is as shown in figs. 10-12.
As shown in Figure 10, the average thickness of uncoated aluminium powder is 3800nm.
As shown in figure 11, the average thickness for being cladded with the aluminium powder of silica is 4250nm.
As shown in figure 12, in aqueous aluminum powder pigment of the invention, the polymer of grafting is polyacrylic acid（PAA）, its is average
Thickness is 2700nm.
SiO is coated2The average thickness of the aluminium powder of the overcoating silica for obtaining afterwards becomes big, illustrates dispersiveness variation, holds
Easily reunite.And further after graft polymers PAA, average thickness diminishes on the contrary, illustrates that being compatible with the environment property improves, it is difficult to pile up
Reunite.
Claims (9)
1. a kind of aqueous aluminum powder pigment, it is characterized in that, the surface coating layer of the aqueous aluminum powder pigment is silica, and inside is
Aluminium powder, tie point is connected with outside surface coating layer by chemical bond, and tie point is connected with polymer；The tie point is to draw
Hair agent, initiator is 4,4'- azos (4- cyanopentanoic acids (3'- dimethylchlorosilanes) propyl ester), 4- azo isobutyl cyano group 4- cyano group
(valeric acid (3'- dimethylchlorosilanes) propyl ester) or azo isobutyl dicyano phenyl (3- ethyls dimethylchlorosilane), the polymerization
Thing is obtained by polymerizable monomer by polymerisation；The polymerizable monomer is dimethyl diallyl ammonium chloride, propylene
Acyloxyethyl trimethyl ammonium chloride, 4- vinyl benzoic acids or 2- vinylpyridines.
2. aqueous aluminum powder pigment as claimed in claim 1, it is characterized in that, prepare the starting silica bag of aqueous aluminum powder pigment
The weight proportion of the aluminium powder, initiator and polymerizable monomer that cover is：1-5:0.01-1:0.5-5.
3. a kind of preparation method of aqueous aluminum powder pigment as claimed in claim 1 or 2, it is characterized in that, comprise the following steps：
1st, the aluminium powder of overcoating silica and solvent are mixed, adds initiator and accelerator, stirring reaction is washed after the completion of reaction
Above-mentioned product is washed, coating modification aluminium powder pigment is filtrated to get, the initiator is 4,4'- azos (4- cyanopentanoic acids (3'- diformazans
Base chlorosilane) propyl ester), 4- azo isobutyl cyano group 4- cyano group (valeric acid (3'- dimethylchlorosilanes) propyl ester) or azo isobutyl dicyan
Base phenyl (3- ethyls dimethylchlorosilane), the accelerator is alkaline matter；
2nd, above-mentioned coating modification aluminium powder pigment, solvent and polymerisable monomer are mixed, after reaction, filtering, washing is dried to obtain water
Property aluminium powder pigment；The polymerizable monomer is dimethyl diallyl ammonium chloride, acrylyl oxy-ethyl-trimethyl salmiac, 4-
Vinyl benzoic acid or 2- vinylpyridines.
4. preparation method as claimed in claim 3, it is characterized in that, in step 1, solvent is nonpolar or weak polar solvent.
5. the preparation method as described in claim 3 or 4, it is characterized in that, in step 1, be cladded with the aluminium powder of silica, solvent,
The weight proportion of initiator and accelerator is：1-5:30-60:0.01-1:0.1-5.
6. the preparation method as described in claim 3 or 4, it is characterized in that, the accelerator is triethylamine, ethylenediamine or ammoniacal liquor.
7. the preparation method as described in claim 3 or 4, it is characterized in that, in step 2, the coating modification aluminium powder pigment, solvent
Weight proportion with polymerisable monomer is：1-5:30-60:0.5-5.
8. the preparation method as described in claim 3 or 4, it is characterized in that, in step 2, the temperature of reaction is 55-75 DEG C.
9. a kind of aqueous aluminum powder pigment as claimed in claim 1 or 2 or as claim 3-8 any one preparation methods are obtained
Purposes of the aqueous aluminum powder pigment in coating or ink is prepared.
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| CN107652716B (en) * | 2017-10-20 | 2020-04-14 | 安徽大学 | Method for coloring aluminum pigment by using iron 5-sulfosalicylate ionic complex |
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| CN108929576B (en) * | 2018-08-06 | 2020-08-11 | 浙江画之都文化创意有限公司 | Preparation method of corrosion-resistant ultraviolet aging-resistant coated modified aluminum pigment |
| CN113999548B (en) * | 2021-11-15 | 2022-09-02 | 深圳市绚图新材科技有限公司 | Preparation method of water-based aluminum pigment and reaction kettle for preparation |
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