CN104893368A - Coated modified aluminum powder pigment, and preparation method and use thereof - Google Patents
Coated modified aluminum powder pigment, and preparation method and use thereof Download PDFInfo
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Abstract
The invention relates to a coated modified aluminum powder pigment, and a preparation method and a use thereof; a surface coating layer of the coated modified aluminum powder pigment is silicon dioxide, the interior is an aluminum powder, the exterior of the surface coating layer is connected with a connection point through a chemical bond, and the connection point is 4,4'-azo(4-cyanovaleric acid(3'-dimethylchlorosilane)propyl ester), 4-azoisobutyl cyano 4-cyano(valeric acid(3'-dimethylchlorosilane)propyl ester) or azoisobutyl dicyano phenyl(3-ethyldimethylchlorosilane); the connection point is firmly fixed on the surface of silicon dioxide and has a quite good protective effect on the internal aluminum powder, and the coated modified aluminum powder pigment has quite good dispersibility in waterborne coatings and printing inks.
Description
Technical field
The present invention relates to the technical field of surface of metallic pigment, specifically relate to a kind of coating modification aluminium powder pigment, preparation method and purposes.
Background technology
Aluminium powder pigment is one of modal metallic pigment, and with the flash of light of its uniqueness, covering and decorative effects, the parent deeply by planner looks at.Its consumption increases rapidly from last century, in recent decades especially towards high added value, aqueous phase adaptability future development.Main Application Areas has industrial coating, car paint, decoration, printing-ink, plastic working etc.
Traditional aluminium powder pigment is solvent-borne type aluminium powder, contains higher organic volatile with the solvent based product of its configuration, and difficult cleaning, all harmful to Environmental insults.Along with the development of science and technology, the demand of people to environment-friendly type coating, ink is increasing, and water-borne coatings, water color ink are abroad in eruptive growth.The Water-borne modification of the Water-borne modification inevitable requirement aluminium powder pigment of coating, ink, the technology of this respect is abroad walked already before China, according to 2013 statistics, coating, the ink of the U.S. more than 65% are water-based, and aqueous aluminum powder pigment composite with it also monopolize by external each major company.
In order to make aluminium powder pigment can use in aqueous medium (weak acid or weakly alkaline), the problem of first needs solution is: aluminium powder is easily corroded, and reacts with medium, not only makes aluminium powder pigment lose metalluster, and produces hydrogen, has the danger of blast; The problem of second needs solution is: aluminium powder pigment is difficult to dispersion in water-base resin, and the two poor compatibility, causes aluminium powder pigment agglomerating, and glossiness reduces, and is unfavorable for follow-up use.
For first problem, aluminium powder pigment and aqueous medium are kept apart by the method that at present both at home and abroad main Adsorption of Organic, polymer overmold, inorganics passivation, inorganics are coated, prevent it from reacting generation hydrogen.Adsorption of Organic is mainly adsorbed in the surperficial corrosion suppressing aluminium powder of aluminium powder with specific small-molecule substance, surfactant molecule; this kind of method due to adsorption more weak; cannot completely cut off contacting of aluminium powder pigment and corrosive medium completely, therefore this method is very limited to the protection of aluminium powder.Polymer overmold mainly utilizes polymerisable monomer at aluminium powder in situ Polymerization; getting up to reach by coated aluminum powder by polymkeric substance prevents it to be corroded; and the polymkeric substance that common in-stiu coating polymerization technique obtains easily comes off from aluminium powder surface, also more limited to the protection of aluminium powder.Inorganics passivation is the method for chemical protection used the earliest, and form passive film with passivator process aluminium powder on its surface, modal passivator is chromic salt, but because hexavalent chromium is to the harm of environment and human body, this kind of method is progressively eliminated.Inorganics is coated is form coating layer with precursor in the condensation of aluminium powder surface hydrolysis to protect aluminium powder; topmost inorganic coating thing is amorphous silica; also have patent report silane coupling agent hydrolytic condensation to form coating layer, and then grafting organism carrys out modified aluminium powder pigment.
For Second Problem, mainly adopt in compound process, add dispersion agent, flow agent, tensio-active agent or the coated polymkeric substance good with matrix resin consistency in aluminium powder modifying process.
Chinese Patent Application No. is the preparation method that application discloses a kind of coated aluminium powder pigment of 200610123751.8, polymerisable monomer, initiator is added in the aluminium powder pigment of coated with silica, stirring reaction obtains the aluminium powder pigment of silicon-dioxide and polymer overmold, finally cool, filter, wash, drying obtains product.Initiator be chosen as Diisopropyl azodicarboxylate, Potassium Persulphate or ammonium persulphate, being chosen as of polymerisable monomer: vinylbenzene, Vinylstyrene, methyl acrylate, methyl methacrylate, butyl methacrylate, vinylformic acid, methacrylic acid, maleic anhydride, norbornene dicarboxylic anhydride.This method belongs to situ aggregation method, the research and development of aluminium surface of pigments modification aseptic technic, Chinese corrosion and protection journal, 34th volume the 5th is interim to be mentioned in this method, initiator ammonium persulfate is not chemical bonding in the absorption motivating force on aluminium surface, being electrostatic attraction, coming off than being easier to.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of coating modification aluminium powder pigment, preparation method and purposes, the coating difficult drop-off of described coating modification aluminium powder pigment, good to the protected effect of aluminium powder.
For solving the problems of the technologies described above, the invention provides a kind of coating modification aluminium powder pigment, its surface coating layer is silicon-dioxide, inside is aluminium powder, tie point is connected to by chemical bond-linking in surface coating layer outside, described tie point is initiator, and initiator is 4,4'-azo (4-cyanopentanoic acid (3'-dimethylchlorosilane) propyl ester), 4-azo isobutyl cyano group 4-cyano group (valeric acid (3'-dimethylchlorosilane) propyl ester) or azo isobutyl dicyano phenyl (3-ethyl dimethylchlorosilane).
Infrared spectroscopy is presented at 1089cm
-1there is absorption peak in place.
Initiator of the present invention is existing product, and following reaction scheme can be adopted to obtain:
The weight proportion of the aluminium powder that the starting silica of preparation coating modification aluminium powder pigment is coated and initiator is preferably: 1-5:0.01-1.
The Infrared spectroscopy of coating modification aluminium powder pigment is shown, at 1089cm
-1there is absorption peak in place, shows to have amorphous silica in coating modification aluminium powder pigment.
The present invention also provides a kind of preparation method of coating modification aluminium powder pigment, and step is as follows:
Aluminium powder and the solvent of silicon-dioxide will be covered outward, add initiator and promotor, stirring reaction, react the above-mentioned product of rear washing, filtration obtains coating modification aluminium powder pigment, described initiator is 4,4'-azo (4-cyanopentanoic acid (3'-dimethylchlorosilane) propyl ester), 4-azo isobutyl cyano group 4-cyano group (valeric acid (3'-dimethylchlorosilane) propyl ester) or azo isobutyl dicyano phenyl (3-ethyl dimethylchlorosilane), and described promotor is alkaline matter.
Preferably, before adding initiator, the mixture of the aluminium powder and solvent that first externally cover silicon-dioxide carries out passing into nitrogen gas stirring process.
The material of washed product is preferably alcohols material, most preferably is methyl alcohol, ethanol or Virahol.
Solvent is preferably solvent that is nonpolar or low-pole, and be more preferably chloroform, methylene dichloride, override is toluene or dimethylbenzene.
Preferably, cover outward the aluminium powder of silicon-dioxide, solvent, initiator and promotor weight proportion be: 1-5:30-60:0.01-1:0.1-5, preferred weight proportion is: 1:30:0.1:0.1.
Described promotor is preferably weakly alkaline material, most preferably is triethylamine, quadrol or ammoniacal liquor.Because the Si-OH key reaction on the Si-Cl key in initiator and coated aluminium powder surface generates HCl, so add promotor to neutralize the acid of generation, reach the object promoting reaction.
Described coating modification aluminium powder pigment graftomer of the present invention can prepare aqueous aluminum powder pigment, and the step of its preparation method is:
Coating modification aluminium powder pigment, solvent and polymerisable monomer are mixed, after reaction, filter, washing, drying obtains aqueous aluminum powder pigment.
Preferably, polymerisable monomer is: vinylformic acid, methyl acrylate, methyl methacrylate, butyl methacrylate, dimethyl diallyl ammonium chloride, acrylyl oxy-ethyl-trimethyl salmiac, 4-vinyl benzoic acid or 2-vinyl pyridine, be more preferably: dimethyl diallyl ammonium chloride, acrylyl oxy-ethyl-trimethyl salmiac, 4-vinyl benzoic acid or 2-vinyl pyridine.Be vinylformic acid, methyl acrylate, methyl methacrylate, butyl methacrylate compared to polymerisable monomer, when polymerisable monomer is dimethyl diallyl ammonium chloride, acrylyl oxy-ethyl-trimethyl salmiac, 4-vinyl benzoic acid or 2-vinyl pyridine, the polymkeric substance formed is dispersed and uniformity is more excellent in an aqueous medium, it ionizes in an aqueous medium, make surface band electric charge of the present invention, be conducive to the dispersion of aluminium powder, be not easy to be formed and reunite.
First carry out deoxygenation operation after the mixing of coating modification aluminium powder pigment, solvent and polymerisable monomer, make polymerization effect better, the temperature of its reaction is preferably 55-75 DEG C, is more conducive to making decomposition of initiator produce free radical.
Preferably, the weight proportion of described coating modification aluminium powder pigment, solvent and polymerisable monomer is: 1-5:30-60:0.5-5, and preferred weight proportion is: 1:40:0.5.
Preferably, described solvent is methyl alcohol, ethanol, n-propyl alcohol, Virahol or nitrogen dimethylformamide, is more preferably nitrogen dimethylformamide.Nitrogen dimethylformamide makees solvent compared to alcohols, is more conducive to the dispersion of system.
The described outer preparation method covering the aluminium powder of silicon-dioxide is prior art, can adopt Chinese Patent Application No. be 200610123715.8 method prepare, following steps also can be adopted to obtain:
(1) add aluminium powder and cleaning solvent in a reservoir, described aluminium powder is flake and without surface-treated aluminium powder, thickness is 5-100um, and ultrasonic vibration cleans, and liquid is removed in centrifuging, obtains the aluminium powder after washing;
(2) add in reactor by the aluminium powder after washing and solvent alcohol, stir, add organo-siloxane, water, catalyzer in reactor, stirring in water bath is reacted, and filters, washs post-drying with solvent alcohol, obtains the outer aluminium powder covering silicon-dioxide.
Preferably, described cleaning solvent is acetone, butanone or pimelinketone.
Preferably, in the step (1) of above-mentioned reaction, the weight proportion of described aluminium powder and cleaning solvent is 1-5:30-80.
Preferably, in the step (2) of above-mentioned reaction, the weight proportion of the aluminium powder after described washing, solvent alcohol, organo-siloxane, water and catalyzer is: 1-5:30-80:2-10:6-20:1-7.
Preferably, in the step (2) of above-mentioned reaction, described organo-siloxane is tetramethoxy-silicane or tetraethoxysilane, and described catalyzer is triethylamine, quadrol or ammoniacal liquor, and temperature of reaction is 25-40 DEG C, and the reaction times is 8-20 hour.
What the present invention also provided a kind of coating modification aluminium powder pigment is preparing the purposes in coating or ink.
The invention has the beneficial effects as follows, the present invention take aluminium powder as kernel, and silicon-dioxide is surface coating layer, is carried on surface coating layer by initiator subsequently obtains coating modification aluminium powder pigment by chemical bond.
Coating modification aluminium powder pigment prepared by the present invention can directly use as aluminium pigment, has excellent package stability, resistance to acids and bases, good dispersiveness.
The SiO that initiator has been carried on aluminium powder coated by the present invention
2surface, its process mechanism is that the Si-Cl key on initiator replaces SiO
2the hydrogen atom of surface Si-OH key forms Si-O-Si key.
In position in polymerization, initiator is free, and the monomer in initiator system is at aluminium powder surface aggregate, and this polymer covering layer does not have and aluminium powder surface forms firmly chemical bond, easily comes off in actual use, is difficult to form stable protection to aluminium powder.The present invention in contrast to the method for in-stiu coating polymerization; simultaneously containing the azo bond that can generate free radical and the Si-Cl key that can react with Si-OH in initiator of the present invention; initiator and surface coating layer define chemical bond; so initiator is fixed on aluminium powder surface firmly; difficult drop-off; initiator can better be protected aluminium powder and make product of the present invention and water-borne coatings or ink have good consistency, has better anticorrosion ability in the presence of a harsh environment.
The present invention in contrast to silane coupling agent coated after again by silane coupling agent unsaturated link(age) polymerization modified aluminium powder preparation method, advantage of the present invention is the grafting density by regulating the amount of initiator can regulate and control initiator, control the surface microstructure performance of aluminium powder, products collection efficiency is higher.
Coating modification aluminium powder pigment of the present invention is as intermediate, and for the preparation of obtaining aqueous aluminum powder pigment, the effect of the protection aluminium powder of described aqueous aluminum powder pigment is very good, good dispersity, is not easy to reunite.
Coating modification aluminium powder pigment surface coverage initiator prepared by the present invention, the coating modification aluminium powder pigment of preparation and water-base resin have good consistency, in water-borne coatings, ink, have good dispersiveness.
Accompanying drawing explanation
Fig. 1 is microtexture schematic diagram of the present invention.
Fig. 2 is the microtexture schematic diagram of aqueous aluminum powder pigment of the present invention.
Fig. 3 is the schematic diagram of reactions steps of the present invention.
Fig. 4 is the Electronic Speculum figure of aluminium powder.
Fig. 5 is the Electronic Speculum figure of aqueous aluminum powder pigment of the present invention.
Fig. 6 is the transmission electron microscope picture of aqueous aluminum powder pigment of the present invention.
Fig. 7 is the Infrared spectroscopy figure of different substances.
Fig. 8 is the outer constituent content analysis figure covering the aluminium powder of silicon-dioxide.
Fig. 9 is the constituent content analysis figure of coating modification aluminium powder pigment of the present invention.
Figure 10 is different substances time dependent liberation of hydrogen spirogram in sodium hydroxide solution.
Figure 11 is the thickness distribution figure of not coated aluminium powder.
Figure 12 is the outer thickness distribution figure covering the aluminium powder of silicon-dioxide.
Figure 13 is the thickness distribution figure of aqueous aluminum powder pigment.
In the drawings, 1 aluminium powder, 2 silicon-dioxide, 3 tie points, 4 polymkeric substance.
Embodiment
embodiment 1
In mass fraction (following identical with it), the aluminium powder 1 part and 30 parts of toluene that cover silicon-dioxide are outward added in reactor, room temperature leads to nitrogen gas stirring, 0.01 part 4 is added in reactor, 4'-azo (4-cyanopentanoic acid (3'-dimethylchlorosilane) propyl ester) and 0.1 part of triethylamine, stirring at room temperature reacts 12 hours, uses washing with alcohol subsequently, filters and obtains coating modification aluminium powder pigment.
The erosion resistance of the coating modification aluminium powder pigment of the present embodiment 1: separate out at the aqueous solution 6 months no hydrogens of pH8-12 scope.
The glossiness of the coating modification aluminium powder pigment of the present embodiment 1: after being made into water-borne coatings solidification, surperficial silver color, uniform in color, good luster, without current mark.
The dispersiveness of the coating modification aluminium powder pigment of the present embodiment 1: aqueous aluminum powder pigment is put into aqueous medium microscopic examination, soilless sticking, be uniformly dispersed.
As shown in Figure 1, as can be seen from microtexture of the present invention, the present invention is followed successively by aluminium powder 1, silicon-dioxide 2 and tie point 3 from inside to outside, and in the present embodiment 1, tie point 3 is 4,4'-azo (4-cyanopentanoic acid (3'-dimethylchlorosilane) propyl ester).
embodiment 2
The first step: in mass fraction, add in reactor by the aluminium powder 1 part and 30 parts of toluene that cover silicon-dioxide outward, room temperature leads to nitrogen gas stirring; In reactor, add 0.02 part of 4,4'-azo (4-cyanopentanoic acid (3'-dimethylchlorosilane) propyl ester) and 0.2 part of triethylamine, stirring at room temperature reacts 12 hours; Use washed with isopropyl alcohol subsequently, filter and obtain coating modification aluminium powder pigment.
Second step: coating modification aluminium powder pigment 1 part, 30 parts of methyl alcohol and 1 part of methyl acrylate are added in reactor; By reactor deoxygenation under liquid nitrogen condition, react 3 hours under 70 DEG C of water-baths subsequently; Filter, washing, obtains aqueous aluminum powder pigment after oven dry.
The erosion resistance of the aqueous aluminum powder pigment of the present embodiment 2: separate out at the aqueous solution 6 months no hydrogens of pH8-12 scope.
The glossiness of the aqueous aluminum powder pigment of the present embodiment 2: after being made into water-borne coatings solidification, surperficial 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 microscopic examination, soilless sticking, be uniformly dispersed.
As shown in Figure 2, as can be seen from microtexture of the present invention, aqueous aluminum powder pigment of the present invention is followed successively by aluminium powder 1, silicon-dioxide 2, tie point 3 and polymkeric substance 4 from inside to outside, in the present embodiment 2, tie point 3 is 4,4'-azo (4-cyanopentanoic acid (3'-dimethylchlorosilane) propyl ester).
embodiment 3
The first step: in mass fraction, add in reactor by the aluminium powder 2 parts and 40 parts of toluene that cover silicon-dioxide outward, room temperature leads to nitrogen gas stirring; In reactor, add 0.05 part of 4,4'-azo (4-cyanopentanoic acid (3'-dimethylchlorosilane) propyl ester) and 0.2 part of triethylamine, stirring at room temperature reacts 20 hours; Use methanol wash subsequently, filter and obtain coating modification aluminium powder pigment.
Second step: coating modification aluminium powder pigment 2 parts, 40 parts of methyl alcohol and 1 part of methyl methacrylate are added in reactor; By reactor deoxygenation under liquid nitrogen condition, react 3 hours under 60 DEG C of water-baths subsequently; Filter, washing, obtains aqueous aluminum powder pigment after oven dry.
The erosion resistance of the aqueous aluminum powder pigment of the present embodiment 3: separate out at the aqueous solution 6 months no hydrogens of pH8-12 scope.
The glossiness of the aqueous aluminum powder pigment of the present embodiment 3: after being made into water-borne coatings solidification, surperficial 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 microscopic examination, soilless sticking, be uniformly dispersed.
embodiment 4
The first step: in mass fraction, add 3 parts of aluminium powder pigments and 60 parts of acetone in a reservoir, ultrasonic vibration cleans 30 minutes, and liquid is removed in centrifuging, obtains the aluminium powder after washing.
Second step: the aluminium powder after washing 3 parts and 80 parts of methyl alcohol add in reactor, stirring at room temperature; In reactor, add 10 parts of methyl silicates, 15 parts of water, 4 parts of quadrols, stirring in water bath reacts 10 hours, and temperature of reaction is 40 DEG C; Subsequent filtration, obtains the outer aluminium powder covering silicon-dioxide by methanol wash post-drying.
3rd step: add in reactor by the aluminium powder 3 parts and 50 parts of toluene that cover silicon-dioxide outward, room temperature leads to nitrogen gas stirring; In reactor, add 0.05 part of 4,4'-azo (4-cyanopentanoic acid (3'-dimethylchlorosilane) propyl ester) and 0.5 part of quadrol, stirring at room temperature reacts 24 hours; Use methanol wash subsequently, filter and obtain coating modification aluminium powder pigment.
4th step: coating modification aluminium powder pigment 3 parts, 50 parts of nitrogen dimethylformamides and 2 parts of dimethyl diallyl ammonium chlorides are added in reactor; By reactor deoxygenation under liquid nitrogen condition, react 4 hours under 60 DEG C of water-baths subsequently; Filter, washing, obtains aqueous aluminum powder pigment after oven dry.
The erosion resistance of the aqueous aluminum powder pigment of the present embodiment 4: separate out at the aqueous solution 6 months no hydrogens of pH8-12 scope.
The glossiness of the aqueous aluminum powder pigment of the present embodiment 4: after being made into water-borne coatings solidification, surperficial 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 microscopic examination, soilless sticking, be uniformly dispersed.
embodiment 5
The first step: in mass fraction, add 4 parts of aluminium powder pigments and 70 parts of pimelinketone in a reservoir, ultrasonic vibration cleans 30 minutes, and liquid is removed in centrifuging, obtains the aluminium powder after washing.
Second step: the aluminium powder after washing 4 parts and 80 parts of Virahols add in reactor, stirring at room temperature; In reactor, add 10 parts of tetraethoxys, 20 parts of water, 6 parts of triethylamines, stirring in water bath reacts 18 hours, and temperature of reaction is 25 DEG C; Subsequent filtration, obtains the outer aluminium powder covering silicon-dioxide by washed with isopropyl alcohol post-drying.
3rd step: add in reactor by the aluminium powder 4 parts and 50 parts of dimethylbenzene that cover silicon-dioxide outward, room temperature leads to nitrogen gas stirring; In reactor, add 0.1 part of 4-azo isobutyl cyano group 4-cyano group (valeric acid (3'-dimethylchlorosilane) propyl ester) and 0.4 part of triethylamine, stirring at room temperature reacts 24 hours; Use washed with isopropyl alcohol subsequently, filter and obtain coating modification aluminium powder pigment.
4th step: coating modification aluminium powder pigment 4 parts, 50 parts of methyl alcohol and 1 part of acrylyl oxy-ethyl-trimethyl salmiac are added in reactor; By reactor deoxygenation under liquid nitrogen condition, react 3 hours under 65 DEG C of water-baths subsequently; Filter, washing, obtains aqueous aluminum powder pigment after oven dry.
The erosion resistance of the aqueous aluminum powder pigment of the present embodiment 5: separate out at the aqueous solution 6 months no hydrogens of pH8-12 scope.
The glossiness of the aqueous aluminum powder pigment of the present embodiment 5: after being made into water-borne coatings solidification, surperficial 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 microscopic examination, soilless sticking, be uniformly dispersed.
As shown in Figure 3, polymkeric substance is the tie point surface grafting on coating modification aluminium powder pigment with the form of brush, and because initiator is carried on the outer aluminium powder surface covering silicon-dioxide in advance, the microtexture formed and in-situ polymerization have the different of essence.
embodiment 6
The first step: in mass fraction, add 5 parts of aluminium powder pigments and 70 parts of pimelinketone in a reservoir, ultrasonic vibration cleans 30 minutes, and liquid is removed in centrifuging, obtains the aluminium powder after washing.
Second step: the aluminium powder after washing 5 parts and 80 parts of ethanol add in reactor, stirring at room temperature; In reactor, add 10 parts of tetraethoxys, 18 parts of water, 6 parts of triethylamines, stirring in water bath reacts 9 hours, and temperature of reaction is 40 DEG C; Subsequent filtration, obtains the outer aluminium powder covering silicon-dioxide by washing with alcohol post-drying.
3rd step: add in reactor by the aluminium powder 5 parts and 60 parts of dimethylbenzene that cover silicon-dioxide outward, room temperature leads to nitrogen gas stirring; In reactor, add 0.1 part of 4-azo isobutyl cyano group 4-cyano group (valeric acid (3'-dimethylchlorosilane) propyl ester) and 0.5 part of triethylamine, stirring at room temperature reacts 20 hours; Use washed with isopropyl alcohol subsequently, filter and obtain coating modification aluminium powder pigment.
4th step: coating modification aluminium powder pigment 5 parts, 60 parts of methyl alcohol and 3 parts of 4-vinyl benzoic acids are added in reactor; By reactor deoxygenation under liquid nitrogen condition, react 3.5 hours under 60 DEG C of water-baths subsequently; Filter, washing, obtains aqueous aluminum powder pigment after oven dry.
The erosion resistance of the aqueous aluminum powder pigment of the present embodiment 6: separate out at the aqueous solution 6 months no hydrogens of pH8-12 scope.
The glossiness of the aqueous aluminum powder pigment of the present embodiment 6: after being made into water-borne coatings solidification, surperficial 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 microscopic examination, soilless sticking, be uniformly dispersed.
embodiment 7
The first step: in mass fraction, add 5 parts of aluminium powder pigments and 80 parts of pimelinketone in a reservoir, ultrasonic vibration cleans 30 minutes, and liquid is removed in centrifuging, obtains the aluminium powder after washing.
Second step: the aluminium powder after washing 5 parts and 80 parts of methyl alcohol add in reactor, stirring at room temperature; In reactor, add 8 parts of tetraethoxys, 15 parts of water, 5 parts of triethylamines, stirring in water bath reacts 15 hours, and temperature of reaction is 30 DEG C; Subsequent filtration, obtains the outer aluminium powder covering silicon-dioxide by methanol wash post-drying.
3rd step: add in reactor by the aluminium powder 5 parts and 60 parts of dimethylbenzene that cover silicon-dioxide outward, room temperature leads to nitrogen gas stirring; In reactor, add 0.08 part of 4-azo isobutyl cyano group 4-cyano group (valeric acid (3'-dimethylchlorosilane) propyl ester) and 0.4 part of triethylamine, stirring at room temperature reacts 24 hours; Use washed with isopropyl alcohol subsequently, filter and obtain coating modification aluminium powder pigment.
4th step: coating modification aluminium powder pigment 5 parts, 50 parts of methyl alcohol and 4 parts of 2-vinyl pyridines are added in reactor; By reactor deoxygenation under liquid nitrogen condition, react 4 hours under 60 DEG C of water-baths subsequently; Filter, washing, obtains aqueous aluminum powder pigment after oven dry.
The erosion resistance of the aqueous aluminum powder pigment of the present embodiment 7: separate out at the aqueous solution 6 months no hydrogens of pH8-12 scope.
The glossiness of the aqueous aluminum powder pigment of the present embodiment 7: after being made into water-borne coatings solidification, surperficial 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 microscopic examination, soilless sticking, be uniformly dispersed.
As shown in Fig. 4,5 and 6, by the Electronic Speculum figure (Fig. 3) of comparative analysis aluminium powder, Electronic Speculum figure and the transmission electron microscope picture of observing aqueous aluminum powder pigment of the present invention are known, the present invention's success grafting polymkeric substance.
As shown in Figure 7, (a) is aluminium powder, and (b) is coated with silica aluminium powder, and (c) is aqueous aluminum powder pigment of the present invention.In (b), significantly there is 1086cm
-1si-O-Si absorption peak, can judge that amorphous silica is formed on aluminium powder surface.In (c), except there being 1089cm
-1the absorption peak at place, have also appeared 1724cm in polymer carboxyl peak C=O
-1the absorption peak at place, the product of embodiment 2,3 and 6 there will be 1724cm
-1absorption peak.
As Figure 8-9, constituent content analysis figure of the present invention knows the content of each composition, calculates the content of silicon-dioxide and polymkeric substance.
embodiment 8
Coated aluminium powder after coated aluminium powder after aluminium powder (unmodified), the aluminium powder covering silicon-dioxide outward, aqueous aluminum powder pigment of the present invention, vinylformic acid reaction in－situ, vinylformic acid reaction in－situ after ultrasonic vibration is invaded bubble in the sodium hydroxide solution of pH12, measure the amounts of hydrogen separated out.
Figure 10 is aluminium powder (unmodified), cover the aluminium powder of silicon-dioxide, aqueous aluminum powder pigment of the present invention, vinylformic acid reaction in－situ outward after coated aluminium powder, coated aluminium powder after vinylformic acid reaction in－situ after ultrasonic vibration in the sodium hydroxide solution of pH12, pass the amounts of hydrogen separated out in time.Do not occur that obvious hydrogen-separating quantity increases after covering the aluminium powder of silicon-dioxide and aqueous aluminum powder pigment of the present invention earthquake outward, and carry out test after coated aluminium powder earthquake after vinylformic acid reaction in－situ and find that coated protected effect reduces.
embodiment 9
glossiness contrast test
Adopt non-coated Si O
2the aqueous aluminum powder pigment prepared of aluminium powder, the aluminium powder covering silicon-dioxide outward, vinylformic acid in-stiu coating aluminium powder, this patent be made into coating by common scale and resin, solvent, be sprayed on ptfe plastic base plate, measure the glossiness of its film after dry, result is as shown in table 1.
Table 1 glossiness contrast test result table
| Aluminium powder pigment | Glossiness |
| Not coated aluminium powder | 69.6 |
| Cover the aluminium powder (embodiment 4) of silicon-dioxide outward | 45.7 |
| Cover the aluminium powder (embodiment 5) of silicon-dioxide outward | 44.5 |
| Cover the aluminium powder (embodiment 6) of silicon-dioxide outward | 52.3 |
| Vinylformic acid in-stiu coating aluminium powder #1 | 56.8 |
| Vinylformic acid in-stiu coating aluminium powder #2 | 62 |
| Vinylformic 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 |
Vinylformic acid in-stiu coating aluminium powder in this experiment adopts vinylformic acid in-stiu coating to obtain.Compared to not coated aluminium powder, the glossiness covering the aluminium powder of silicon-dioxide outward on average declines 31.75%; The glossiness of vinylformic acid in-stiu coating aluminium powder on average declines 13.65%; The glossiness of aqueous aluminum powder pigment on average only declines 3.5%, has a significant effect.
embodiment 10
thickness measuring
By the not coated aluminium powder of equivalent, the aluminium powder covering silicon-dioxide outward, aqueous aluminum powder colo(u)rant dispersion in dehydrated alcohol, dynamic light scattering method characterizes its thickness (BT-90, Chinese Dandong Bai Te).Result as figs 11-13.
As shown in figure 11, the mean thickness of not coated aluminium powder is 3800nm.
As shown in figure 12, the mean thickness covering the aluminium powder of silicon-dioxide is outward 4250nm.
As shown in figure 13, in aqueous aluminum powder pigment of the present invention, the polymkeric substance of grafting is polyacrylic acid (PAA), and its mean thickness is 2700nm.
Coated SiO
2after the outer mean thickness covering the aluminium powder of silicon-dioxide that obtains become large, dispersed variation is described, easily reunites.And further after graftomer PAA, mean thickness diminishes on the contrary, to illustrate and Environmental compatibility improves, not easily pile up reunion.
Claims (10)
1. a coating modification aluminium powder pigment, it is characterized in that, the surface coating layer of described coating modification aluminium powder pigment is silicon-dioxide, inside is aluminium powder, tie point is connected to by chemical bond-linking in surface coating layer outside, described tie point is initiator, and initiator is 4,4'-azo (4-cyanopentanoic acid (3'-dimethylchlorosilane) propyl ester), 4-azo isobutyl cyano group 4-cyano group (valeric acid (3'-dimethylchlorosilane) propyl ester) or azo isobutyl dicyano phenyl (3-ethyl dimethylchlorosilane).
2. coating modification aluminium powder pigment as claimed in claim 1, is characterized in that, the weight proportion of the aluminium powder that the starting silica of preparation coating modification aluminium powder pigment is coated and initiator is: 1-5:0.01-1.
3. a preparation method for coating modification aluminium powder pigment as claimed in claim 1 or 2, is characterized in that, comprise the steps:
Aluminium powder and the solvent of silicon-dioxide will be covered outward, add initiator and promotor, stirring reaction, react the above-mentioned product of rear washing, filtration obtains coating modification aluminium powder pigment, described initiator is 4,4'-azo (4-cyanopentanoic acid (3'-dimethylchlorosilane) propyl ester), 4-azo isobutyl cyano group 4-cyano group (valeric acid (3'-dimethylchlorosilane) propyl ester) or azo isobutyl dicyano phenyl (3-ethyl dimethylchlorosilane), and described promotor is alkaline matter.
4. preparation method as claimed in claim 3, is characterized in that, cover outward the aluminium powder of silicon-dioxide, solvent, initiator and promotor weight proportion be: 1-5:30-60:0.01-1:0.1-5.
5. the preparation method as described in claim 3 or 4, is characterized in that, solvent is toluene or dimethylbenzene.
6. the preparation method as described in claim 3 or 4, is characterized in that, described promotor is triethylamine, quadrol or ammoniacal liquor.
7. the preparation method as described in claim 3 or 4, is characterized in that, described alcohols material is methyl alcohol, ethanol or Virahol.
8. the preparation method as described in claim 3 or 4, is characterized in that, before adding initiator, the mixture of the aluminium powder and solvent that first externally cover silicon-dioxide carries out passing into nitrogen gas stirring process.
9. the preparation method as described in claim 3 or 4, is characterized in that, the material of washed product is methyl alcohol, ethanol or Virahol.
10. the coating modification aluminium powder pigment as claim 1 or 2 or the coating modification aluminium powder pigment that obtains as any one of claim 3-9 preparation method are preparing the purposes in coating or ink.
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| CN108929576A (en) * | 2018-08-06 | 2018-12-04 | 浙江画之都文化创意有限公司 | A kind of preparation method of the coating modification aluminium pigment of corrosion-resistant anti-ultraviolet aging |
| CN111013964A (en) * | 2019-11-19 | 2020-04-17 | 一汽解放汽车有限公司 | Method for coating wall-flow particle filter carrier assisted by polymer |
| CN112143349A (en) * | 2020-09-23 | 2020-12-29 | 深圳Tcl数字技术有限公司 | Anodic oxidation-like coating and application thereof |
| CN112552716A (en) * | 2021-01-05 | 2021-03-26 | 浙江易桂塑胶有限公司 | Method for preparing metal effect pigment without flow marks |
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| CN114517054A (en) * | 2022-03-21 | 2022-05-20 | 沈阳先进涂层材料产业技术研究院有限公司 | Preparation method of environment-friendly coating applied to surface of neodymium iron boron magnet material |
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